Textured, anti-glare glass article and method of making the same

Abstract

A glass article is provided that includes a glass substrate comprising a thickness and a major surface, and a textured region defined by the major surface. The textured region includes a low spatial frequency region and a high spatial frequency region, the high spatial frequency region being substantially superimposed within the low spatial frequency region. Additionally, the low spatial frequency region includes an average lateral feature size that exceeds an average lateral feature size of the high spatial frequency region. Furthermore, the textured region includes a surface roughness (R a ) from about 10 nm to about 1000 nm.

Description

[0001] Divisional Application Instructions

[0002] This application is a divisional application of the invention patent application filed on September 9, 2020, with national application number 202080068981.7, entitled "Textured, Anti-glare Glass Article and Method of Manufacturing Thereof".

[0003] Cross-reference of related applications

[0004] This application claims priority to U.S. Provisional Patent Application No. 62 / 897,620, filed September 9, 2019, pursuant to 35 U.S.SC §119, the contents of which are incorporated herein by reference in their entirety.

[0005] field

[0006] This disclosure generally relates to textured, anti-glare glass products and methods of manufacturing them, specifically textured glass products with low flicker and distinctness of image (DOI) characteristics. background

[0007] Anti-glare surfaces are commonly used in display devices (such as LCD screens, tablets, smartphones, OLEDs, and touchscreens) to avoid or reduce specular reflections of ambient light. In many display devices, these anti-glare surfaces are formed by providing a certain level of roughness to one or more surfaces of the glass to propagate and scatter incident light. Anti-glare surfaces in the form of roughened glass surfaces are often used on the front surfaces of these display devices to reduce the obvious visibility of external reflections from the display and improve readability under various lighting conditions.

[0008] Display "sparkle" or "dazzle" is a phenomenon that occurs when anti-glare or light-scattering surfaces are incorporated into a display system. Sparkle is a manifestation of uneven pixel light intensity distribution. Additionally, sparkle is associated with a very fine, granular appearance; the grain pattern appears to shift as the viewing angle of the display changes. This type of sparkle is observed when viewing pixelated displays (such as LCDs) through an anti-glare surface. As the resolution of display devices continues to increase (especially for handheld electronic devices), the pixel pitch of the pixel arrays used in these devices continues to decrease, exacerbating the unwanted sparkle effect.

[0009] Conventional methods for creating textured, anti-glare glass surfaces have successfully produced surfaces with good anti-glare properties. However, these textured, anti-glare surfaces exhibit high levels of flicker. Common surface treatments and other processes designed to reduce flicker often succeed in reducing flicker, but at the cost of anti-glare properties such as DOI.

[0010] In view of these considerations, there is a need for textured glass surfaces and articles with a combination of low flicker and low DOI characteristics. There is also a need for manufacturing methods suitable for producing such surfaces and articles at low cost and high production volume. Summary of the Invention

[0011] According to one aspect of this disclosure, a glass article is provided, comprising: a glass substrate including a thickness and a main surface; and a textured region defined by the main surface. The textured region includes a low spatial frequency region and a high spatial frequency region, the high spatial frequency region substantially superimposed on the low spatial frequency region. Furthermore, the low spatial frequency region includes an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. Additionally, the textured region includes a surface roughness (Rw) ranging from about 10 nm to about 1000 nm. a ).

[0012] According to one aspect of this disclosure, a glass article is provided, comprising: a glass substrate including a thickness and a main surface; and a textured region defined by the main surface. The textured region includes a low spatial frequency region and a high spatial frequency region. The low spatial frequency region includes an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. Additionally, the textured region includes a surface roughness (R0) ranging from about 10 nm to about 1000 nm. a In addition, glass products contain less than 3% flicker and less than 70% image sharpness (DOI) as measured by pixel power distribution (PPD).

[0013] According to another aspect of this disclosure, a method for manufacturing a glass article is provided, the method comprising the steps of: first etching a main surface of a glass substrate with a first etchant to form a textured region of low spatial frequency defined by the main surface; and second etching the main surface of the glass substrate with a second etchant to form a textured region of high spatial frequency defined by the main surface and substantially superimposed on the textured region of low spatial frequency. The textured region of low spatial frequency includes an average lateral feature size that exceeds the average lateral feature size of the region of high spatial frequency. Additionally, the textured region includes a surface roughness (R0) from about 10 nm to about 1000 nm. a ).

[0014] According to a first aspect of this disclosure, a glass article is provided, comprising: a glass substrate including a thickness and a main surface; and a textured region defined by the main surface. The textured region includes a low spatial frequency region and a high spatial frequency region, the high spatial frequency region substantially superimposed on the low spatial frequency region. Furthermore, the low spatial frequency region includes an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. Additionally, the textured region includes a surface roughness (Rw) ranging from about 10 nm to about 1000 nm. a ).

[0015] According to the second aspect, a glass article of the first aspect is provided, wherein the average lateral feature size of the low spatial frequency region is about 5 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

[0016] According to the third aspect, a glass article of the first aspect is provided, wherein the average lateral feature size of the low spatial frequency region is about 10 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

[0017] According to the fourth aspect, a glass article of the first aspect is provided, wherein the average lateral feature size of the low spatial frequency region is about 20 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

[0018] According to the fifth aspect, a glass article according to any one of the first to fourth aspects is provided, wherein the surface roughness (R) of the textured area is... a Low spatial frequency components (R) included in the low spatial frequency region a1 ) and the high spatial frequency component (R) in the high spatial frequency region. a2 ), and further of which R a1 For the range from 10nm to 1000nm, and R a2 The range is from 10nm to 200nm.

[0019] According to the sixth aspect, a glass article of any one of the first to fifth aspects is provided, wherein the glass substrate comprises a composition selected from the group consisting of aluminosilicate glass, borosilicate glass, phosphosilicate glass, soda-lime glass, alkali metal aluminosilicate glass and alkali metal borosilicate glass.

[0020] According to the seventh aspect, a glass article of any one of the first to sixth aspects is provided, wherein the glass substrate further includes a compressive stress region extending from the main surface to a selected depth.

[0021] According to an eighth aspect of this disclosure, a glass article is provided, comprising: a glass substrate including a thickness and a main surface, and a textured region defined by the main surface. The textured region includes a low spatial frequency region and a high spatial frequency region. The low spatial frequency region includes an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. The textured region includes a surface roughness (R0) ranging from about 10 nm to about 1000 nm. a Additionally, glass products include less than 3% flicker and less than 70% image sharpness (DOI) as measured by pixel power distribution (PPD).

[0022] According to the ninth aspect, a glass article of the eighth aspect is provided, wherein the glass article includes flicker of less than 2% and image sharpness (DOI) of less than 60% as measured by pixel power distribution (PPD).

[0023] According to the tenth aspect, a glass article of the eighth aspect is provided, wherein the glass article includes flicker of less than 1% and image sharpness (DOI) of less than 50% as measured by pixel power distribution (PPD).

[0024] According to the eleventh aspect, a glass article of any one of the eighth to tenth aspects is provided, wherein the glass article contains a transmission haze of about 3% to about 90%.

[0025] According to the twelfth aspect, a glass article of the eighth aspect is provided, wherein the glass article contains less than 1% flicker as measured by pixel power distribution (PPD).

[0026] According to aspect thirteen, a glass article of any one of aspects eight to twelfth is provided, wherein a high spatial frequency region is substantially superimposed on a low spatial frequency region.

[0027] According to the fourteenth aspect, a glass article of any one of the eighth to thirteenth aspects is provided, wherein the average lateral feature size of the low spatial frequency region is about 20 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

[0028] According to the fifteenth aspect of this disclosure, a method for manufacturing a glass article is provided, the method comprising the steps of: first etching a main surface of a glass substrate with a first etchant to form a textured region of low spatial frequency defined by the main surface; and second etching a main surface of the glass substrate with a second etchant to form a textured region of high spatial frequency defined by the main surface and substantially superimposed on the textured region of low spatial frequency. The textured region of low spatial frequency includes an average lateral feature size that exceeds the average lateral feature size of the textured region of high spatial frequency. Additionally, the textured region includes a surface roughness (Rw) from about 10 nm to about 1000 nm. a ).

[0029] According to the sixteenth aspect, a method of the fifteenth aspect is provided, wherein the first etchant comprises a sandblasting etchant and a low pH solution etchant.

[0030] According to the seventeenth aspect, a method of the fifteenth aspect is provided, wherein the first etchant comprises hydrochloric acid and a fluoride salt, wherein the fluoride salt comprises one or more salts selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium difluoride, sodium difluoride and potassium difluoride.

[0031] According to the eighteenth aspect, a method of any one of the fifteenth to seventeenth aspects is provided, wherein the second etching is performed at an etching temperature higher than the ambient temperature, and the second etchant is a solution with a pH less than 4.

[0032] According to the nineteenth aspect, a method of any one of the fifteenth to eighteenth aspects is provided, wherein the second etchant comprises an acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, citric acid, ascorbic acid, oxalic acid and acetic acid.

[0033] According to the twentieth aspect, a method of any one of the fifteenth to nineteenth aspects is provided, wherein the second etchant comprises one or more salts comprising polyvalent metal cations.

[0034] According to aspect 21, a method of any one of aspects 18 to 20 is provided, wherein the etching temperature of the second etching is from about 60°C to about 100°C.

[0035] According to the twenty-second aspect, a method according to any one of the fifteenth to twenty-first aspects is provided, further comprising the step of treating the main surface of a glass substrate with an aqueous solution of pH greater than 9 at a temperature above ambient temperature, the treatment step being performed after the first etching step and the second etching step.

[0036] Additional features and advantages will be set forth in the following detailed description, and these features and advantages will be apparent to those skilled in the art, or may be appreciated by practicing the embodiments described herein, including the following detailed description, claims and drawings.

[0037] It should be understood that the foregoing 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 disclosed content for which protection is sought.

[0038] The accompanying drawings are attached to provide a further understanding of the principles of this disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description, serve to explain the principles and operation of this disclosure by way of example. It is to be understood that the various features of this disclosure disclosed in this specification and in the drawings can be used in any and all combinations. By way of non-limiting example, the various features of this disclosure can be combined with each other in the following ways.

[0039] Brief description of the attached diagram

[0040] These features, aspects, and advantages of this disclosure can be better understood when reading the following detailed description of the disclosure with reference to the accompanying drawings, wherein:

[0041] According to aspects of this disclosure, Figure 1 This is a cross-sectional schematic diagram of a textured, anti-glare glass product.

[0042] According to aspects of this disclosure, Figure 2 This is a graph showing the relationship between pixel power distribution (PPD) and image sharpness (DOI) for conventional anti-glare glass products and textured anti-glare glass products.

[0043] According to aspects of this disclosure, Figure 3A This is a schematic diagram of a textured, anti-glare glass product, illustrating the functional relationship between reflection flux and reflection angle.

[0044] According to aspects of this disclosure, Figure 3B A schematic diagram of a textured, anti-glare glass product and a component of the textured area of ​​the product, illustrating the sparkle level.

[0045] Figure 4A A plan view of an exemplary electronic device incorporating any of the articles of manufacture incorporating the present disclosure.

[0046] Figure 4B for Figure 4A A perspective view of an exemplary electronic device.

[0047] According to aspects of this disclosure, Figure 5 This is a schematic diagram of a process for manufacturing textured, anti-glare glass products.

[0048] According to aspects of this disclosure, Figure 6A and Figure 6B These are scanning electron microscope (SEM) images of the textured regions at low and high spatial frequencies of textured, anti-glare glass products, respectively.

[0049] According to aspects of this disclosure, Figure 6C and Figure 6D These are the angular reflectance distributions of the low-spatial-frequency textured regions and the high-spatial-frequency textured regions of textured, anti-glare glass products, respectively.

[0050] According to aspects of this disclosure, Figure 7A The angular reflectance distribution of textured, anti-glare glass products from -5° to +5° is defined as the low spatial frequency textured region and the mixed low and high spatial frequency textured regions.

[0051] According to aspects of this disclosure, Figure 7B For the general Figure 7A Angular reflectance distribution when magnified to a smaller angular range from -0.5° to +0.5°. Implementation

[0052] In the following detailed description, exemplary embodiments that disclose specific details are set forth for illustrative and not limiting purposes to provide a full understanding of the various principles of this disclosure. However, it will be apparent to those skilled in the art to which this disclosure pertains that other embodiments may be practiced that depart from the specific details disclosed herein. Furthermore, descriptions of well-known apparatuses, methods, and materials may be omitted so as not to obscure the description of the various principles of this disclosure. Finally, wherever applicable, similar reference numerals refer to similar components.

[0053] A range may be expressed herein as from “about” a specific numerical value and / or to “about” another specific numerical value. When expressing such a range, another implementation includes from a specific numerical value and / or to another specific numerical value. Similarly, when a numerical value is expressed as an approximation by using the antecedent “about”, it will be understood that the specific numerical value forms another implementation. It will be further understood that the endpoints of each range are clearly relative to and independent of the other endpoint.

[0054] The directional terms used in this article—such as up, down, right, left, front, back, top, and bottom—are for reference only with the accompanying drawings and are not intended to imply absolute directions.

[0055] Unless otherwise expressly stated, it is not intended to interpret any method described herein as requiring the steps to be performed in a specific order. Therefore, the method claims do not actually state that the steps follow a particular order, nor is there any other specific statement in the claims or embodiments that restricts the steps to a particular order, and thus no particular order is intended to be inferred in any way. This applies to interpreting any potentially unstated basis, including: logical matters concerning the arrangement of steps or operational procedures; general meanings derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0056] Unless the context explicitly specifies otherwise, the singular forms “a,” “an,” and “the” used herein include the plural referents. Therefore, unless the context explicitly specifies otherwise, for example, the reference to a “component” includes aspects having two or more such components.

[0057] This disclosure generally relates to textured, anti-glare glass articles, and more specifically, to textured, anti-glare glass articles with low flicker and low DOI. These anti-glare glass articles have textured regions, including low spatial frequency regions and high spatial frequency textured regions. This disclosure includes methods for manufacturing these articles. More generally, the method for manufacturing the textured, anti-glare glass articles of this disclosure produces a finely textured surface on a multi-component glass substrate having mixed low spatial frequency regions and high spatial frequency regions (each having an average lateral feature size greater than about 5 micrometers and less than about 5 micrometers, respectively).

[0058] See Figure 1 The textured, anti-glare glass article 100 includes a glass substrate 10 having a plurality of main surfaces 12 and 14 and a thickness 13. The glass article 100 also includes a textured region 30a defined by the main surfaces 12. In some embodiments, such as... Figure 1 As shown, the textured region 30a is formed from a portion or another portion of the substrate 10. In some embodiments (not shown), the textured region 30a is defined by the main surface 14. In other embodiments, the textured region 30a is defined by both the main surface 12 and the main surface 14.

[0059] Also Figure 1As illustrated, the textured region 30a includes a low spatial frequency region 21 and a high spatial frequency region 22. In some embodiments, the high spatial frequency region 22 is superimposed on the low spatial frequency region 21. In other embodiments, the high spatial frequency region 22 overlaps with or is separate from the low spatial frequency region 21. See again Figure 1 Each of the low spatial frequency region 21 and the high spatial frequency region 22, which have textured region 30a, includes multiple exposed features. The exposed features of the low spatial frequency region 21 have an average lateral feature size 31 and an average surface roughness R. a1 The exposure characteristics of the high spatial frequency region 22 have an average lateral feature size 32 and an average surface roughness R. a2 Additionally, the average surface roughness R of the textured region 30a is... a These are the average surface roughness values ​​of the low spatial frequency region 21 and the high spatial frequency region 22 (i.e., R, respectively). a1 and R a2 The average lateral feature size 31 of the low spatial frequency region 21 exceeds the average lateral feature size 32 of the high spatial frequency region 22. In other embodiments, the average lateral feature size 31 of the low spatial frequency region 21 is approximately equal to or greater than the average lateral feature size 32 of the high spatial frequency region 22. Therefore, the average lateral feature size 31 can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 times larger than the average lateral feature size 32, and all multiples between these values.

[0060] According to some embodiments of the textured, anti-glare glass article 100, the exposure characteristics of the textured region 30a include the average lateral feature sizes 31 and 32 of the low and high spatial frequency regions 21 and 22, and the average surface roughness value (R). a1 and R a2The design is configured to reduce the level of flicker and image sharpness (DOI) associated with the article when it is used in a display device. The average lateral feature size 31 and average lateral feature size 32 are obtained by averaging the maximum scales of each associated feature sampled from the respective low spatial frequency region 21 and high spatial frequency region 22 of the textured region 30a, according to analytical and statistical sampling techniques understood by those skilled in the art to which this disclosure pertains. Regarding analytical techniques, those skilled in the art to which this disclosure pertains may employ one or more analytical instruments to measure the average lateral feature size 31 and average lateral feature size 32, for example, an atomic force microscope (AFM) for particularly small features (e.g., <10 μm) and an interferometer for large features (e.g., >10 μm). Regarding statistical techniques, those skilled in the art may obtain the average lateral feature size by capturing an image of the main surface 12 and measuring the maximum scales of at least 10 (10) sampled features. In other cases, larger sample sizes may be used to obtain statistically significant results, as appropriate by those skilled in the art to which this disclosure pertains. Therefore, in this disclosure, the terms "average lateral feature size" and "average maximum scale" are used interchangeably for each of the low spatial frequency region 21 and the high spatial frequency region 22. In some embodiments, at least some of the features of the plurality of low and high spatial frequency regions 21 and 22 have peaks and valleys. The "maximum scale" of the exposed feature is the maximum distance from one part of the feature peak to another part of the feature peak.

[0061] In embodiments of the textured, anti-glare article 100, the average lateral feature size 31 of the low spatial frequency region 21 associated with the textured region 30a of the article 100 is about 5 micrometers or greater. According to some embodiments, the average lateral feature size 31 of the low spatial frequency region 21 is about 2.5 micrometers or greater, 5 micrometers or greater, 10 micrometers or greater, 15 micrometers or greater, 20 micrometers or greater, and all average lateral feature sizes between or above these values. Alternatively, the average lateral feature size 31 of the low spatial frequency region 21 can be about 100 micrometers, 90 micrometers, 80 micrometers, 70 micrometers, 60 micrometers, 50 micrometers, 40 micrometers, 30 micrometers, 20 micrometers, 10 micrometers, 5 micrometers, 1 micrometer, 0.5 micrometers, and all values ​​between these values.

[0062] In embodiments of the textured, anti-glare article 100, the average lateral feature size 32 of the high spatial frequency region 22 associated with the textured region 30a of the article 100 is about 5 micrometers or less. According to some embodiments, the average lateral feature size 32 of the high spatial frequency region 22 is about 5 micrometers or less, 4 micrometers or less, 3 micrometers or less, 2 micrometers or less, 1 micrometer or less, and all average lateral feature sizes between or less than these values. Alternatively, the average lateral feature size 32 of the high spatial frequency region 22 can be about 0.05 micrometers, 0.1 micrometers, 0.2 micrometers, 0.3 micrometers, 0.4 micrometers, 0.5 micrometers, 0.6 micrometers, 0.7 micrometers, 0.8 micrometers, 0.9 micrometers, 1 micrometer, 1.5 micrometers, 2 micrometers, 2.5 micrometers, 3 micrometers, 3.5 micrometers, 4 micrometers, 4.5 micrometers, 5 micrometers, and all values ​​between these values.

[0063] See again Figure 1 The textured region 30a associated with the textured, anti-glare glass product 100 shown in the figure can be used to measure the average surface roughness as surface roughness R using an interferometer or AFM. a As previously stated, the average surface roughness R of the textured region 30a is... a These are the average surface roughness values ​​of the low spatial frequency region 21 and the high spatial frequency region 22 (i.e., R, respectively). a1 and R a2 The function is ). An interferometer that can be used for this purpose is made of Manufactured by the company NEWVIEW TM 7300 Optical Surface Profilometer. When small surface roughness values ​​are readily apparent, specifically in the high spatial frequency region 22, AFM can be used to more accurately characterize the surface roughness. Unless otherwise mentioned, surface roughness is described as average surface roughness. In embodiments, the glass article 100 may employ an average surface roughness (R0) having a range from about 10 nanometers to about 1000 nanometers (nm). a The textured region 30a. According to some embodiments, the average surface roughness (R) associated with the textured region 30a is... a The values ​​range from about 10 nanometers to about 1000 nanometers, from about 10 nanometers to about 500 nanometers, from about 20 nanometers to about 1000 nanometers, from about 20 nanometers to about 500 nanometers, from about 50 nanometers to about 500 nanometers, and all values ​​between these surface roughness levels. For example, the average surface roughness (R) associated with the textured region 30a. aThe values ​​can be approximately 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 25, 10, 5, 1, 0.5, 0.1 nanometers and all surface roughness values ​​between these levels.

[0064] In an embodiment of the textured, anti-glare article 100, the average surface roughness (R0) of the low spatial frequency region 21 associated with the textured region 30a of the article 100 is... a1 The range is from about 10 nanometers to about 1000 nanometers. According to some embodiments, the average surface roughness (R0) of the low spatial frequency region 21 is... a1 The mean surface roughness (R) is approximately 10 nm or greater, 50 nm or greater, 100 nm or greater, 200 nm or greater, 300 nm or greater, 400 nm or greater, 500 nm or greater, and all average surface roughness values ​​between or above these values. a1 Additionally, the average surface roughness (R0) in the low spatial frequency region 21... a1 () can be approximately 1000 nanometers, 900 nanometers, 800 nanometers, 700 nanometers, 600 nanometers, 500 nanometers, 400 nanometers, 300 nanometers, 200 nanometers, 100 nanometers, 50 nanometers and all values ​​between these values.

[0065] In an embodiment of the textured, anti-glare article 100, the average surface roughness (R0) of the high spatial frequency region 22 associated with the textured region 30a of the article 100 is... a2 The surface roughness (R) ranges from approximately 10 nanometers to approximately 200 nanometers. According to some embodiments, the average surface roughness (R0) of the high spatial frequency region 22 is... a2 The mean surface roughness (R) is approximately 10 nm or greater, 20 nm or greater, 30 nm or greater, 40 nm or greater, 50 nm or greater, 60 nm or greater, 70 nm or greater, 80 nm or greater, 90 nm or greater, 100 nm or greater, 150 nm or greater, and all average surface roughness values ​​between or above these values. a2 Additionally, the average surface roughness (R) of the high spatial frequency region 22... a2 The values ​​can be approximately 200 nanometers, 150 nanometers, 100 nanometers, 90 nanometers, 80 nanometers, 70 nanometers, 60 nanometers, 50 nanometers, 40 nanometers, 30 nanometers, 20 nanometers, 10 nanometers, and all values ​​between these values.

[0066] according to Figure 1The embodiment of the textured, anti-glare glass article 100 illustrated herein is characterized by a low level of flicker. Typically, the roughness associated with the exposure characteristics of these articles can begin to act like multiple lenses, producing an image artifact known as "flicker." When anti-glare or light-scattering surfaces are introduced into pixelated display systems (such as, for example, LCDs, OLEDs, touchscreens, or the like), undesirable display "flicker" or "glare" side effects often occur, and these display "flicker" or "glare" differ in type and origin from the types of "flicker" or "speckle" observed and characterized in projection or laser systems. Flicker is associated with a very fine granular appearance of the display, and the granular pattern appears to shift as the viewing angle of the display changes. Display flicker can manifest as bright spots and dark spots or patches of color on an approximate pixel-scale.

[0067] As used herein, "pixel power deviation" and "PPD" refer to a quantitative measurement of display flicker. Furthermore, as used herein, "flicker," "pixel power deviation," and "PPD" are used interchangeably. PPD is calculated by image analysis of display pixels according to the following procedure. A grid box is drawn around each LCD pixel. Then, the total power within each grid box is calculated from CCD camera data and defined as the total power of each pixel. The total power of each LCD pixel is thus converted into a digital array, from which the average and standard deviation can be calculated. The PPD value is defined as the standard deviation of the total power of each pixel divided by the average power of each pixel (multiplied by 100). The total power collected from each LCD pixel by an eye-simulator camera is measured, and the standard deviation of the total pixel power (PPD) over the entire measurement area, typically containing approximately 30 × 30 LCD pixels, is calculated.

[0068] Detailed description of the measurement system and image processing calculations used to obtain PPD values ​​is found in U.S. Patent No. 9,411,180, entitled "Apparatus and Method for Determining Sparkle," the portions of which are significantly relevant to PPD measurement are incorporated herein by reference. Additionally, unless otherwise mentioned, the SMS-1000 system (Display-Messtechnik & Systeme GmbH & Co. KG) is used to generate and evaluate the PPD measurement results of this disclosure. The PPD measurement system includes: a pixelated source comprising a plurality of pixels (e.g., a 140ppi laptop computer from a Lenovo Z50), each of the plurality of pixels having reference indices i and j; and an imaging system optically positioned along an optical path originating from the pixelated source. The imaging system includes: an imaging device disposed along an optical path and having a pixelated sensitive region, the pixelated sensitive region comprising a second plurality of pixels, each of which has reference indices m and n; and an aperture disposed on the optical path between the pixelation source and the imaging device, wherein the aperture has an adjustable collection angle for the image originating from the pixelation source. Image processing calculations include: acquiring a pixelated image of a transparent sample, the pixelated image comprising a plurality of pixels; determining the boundaries between adjacent pixels in the pixelated image; calculating the integral within the boundaries to obtain the integrated energy of each source pixel in the pixelated image; and calculating the standard deviation of the integrated energy of each source pixel, wherein the standard deviation is the power per pixel dispersion. All “PPD” and “flicker” values, attributes, and limitations used herein are based on a pixel density of 140 pixels per inch (PPI) (also referred to herein as “PPD”). 140 The test setup for the display device was calculated and evaluated.

[0069] like Figure 1As illustrated in the general diagram, the textured region 30a of the textured, anti-glare glass article 100 can be configured to minimize flicker. In some embodiments, the textured region 30a is configured to minimize flicker while maintaining glare reduction functionality suitable for display device applications (e.g., regarding DOI, as outlined in more detail later in this disclosure). According to some embodiments, the textured region 30a of the textured, anti-glare glass article 100 is configured such that the article is characterized by flicker of 3% or less (measured by a PPD distribution). In other aspects, the textured, anti-glare glass article 100 of this disclosure can be configured to have flicker of 3% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1% or less, 0.5% or less, and all flicker levels between these upper limits, as measured by a PPD distribution.

[0070] See again Figure 1 The textured, anti-glare glass product 100 shown herein can also be configured for optimal anti-glare performance, such as by displaying a low image resolution (DOI) value. As used herein, "DOI" equals 100*(R). s -R 0.3° ) / R s , where R s R is the specular reflectance flux measured from incident light (at 30° to the normal) on a textured area of ​​a textured, anti-glare glass article that guides the content of this disclosure. 0.3° From the same incident light at the same specular reflection flux R s Reflected flux measured at 0.3° (see also) Figure 3A (and its corresponding description below). Unless otherwise mentioned, the DOI values ​​and measurements described in this disclosure are obtained according to the standard test method of ASTM D5767-18, which uses a Rhopoint IQ gloss, haze and DOI meter (Rhopoint Instruments, Inc.) to instrumentally measure the image sharpness (DOI) gloss of the coated surface. It is noteworthy that the textured, anti-glare glass article 100 of this disclosure can exhibit low flicker (e.g., less than 3%) without significantly reducing anti-glare performance (as indicated by a low DOI value). In embodiments, the textured, anti-glare glass article 100 of this disclosure may be configured to have a DOI of 70% or less. In other embodiments, the textured, anti-glare glass article 100 of this disclosure may be configured to have DOIs of less than 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, and all DOI levels between these upper limits.

[0071] As used herein, "transmitted haze" and "haze" refer to the percentage of transmitted light scattered beyond an angular cone of approximately ±2.5° according to ASTM D1003, entitled "Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics," the entire contents of which are incorporated herein by reference. For optically smooth surfaces, transmitted haze is typically close to zero. Figure 1 In one embodiment of the textured, anti-glare glass article 100 illustrated, the article may be characterized by a haze of 30% or less. In other embodiments, for specific applications, the textured, anti-glare glass article 100, consistent with the principles of this disclosure, may be manufactured to have a haze level up to 90%, a haze level ranging from 3% to 90%, a haze level from 3% to 30%, and all haze levels between these values.

[0072] See again Figure 1 The glass substrate 10 of the textured, anti-glare glass article 100 can be configured to have a multi-component glass composition having 40 mol% to 80 mol% silica and the remainder being one or more other components (e.g., alumina, calcium oxide, sodium oxide, boron oxide, etc.). In some embodiments, the bulk composition of the glass substrate 10 is selected from the group consisting of aluminosilicate glass, borosilicate glass, and phosphosilicate glass. In other embodiments, the bulk composition of the glass substrate 10 is selected from the group consisting of aluminosilicate glass, borosilicate glass, phosphosilicate glass, soda-lime glass, alkali metal aluminosilicate glass, and alkali metal borosilicate glass. In a further embodiment, the glass substrate 10 is a glass-based substrate, including but not limited to glass-ceramic materials comprising about 90% or more by weight of a glass component and a ceramic component.

[0073] exist Figure 1In one embodiment of the textured, anti-glare glass article 100 illustrated, the overall composition of the glass substrate 10 comprises an alkali metal aluminosilicate glass containing alumina, at least one alkali metal, and in some embodiments greater than 50 mol% of SiO2, in other embodiments at least 58 mol% and in still other embodiments at least 60 mol% of SiO2, wherein the ratio (Al2O3 (mol%) + B2O3 (mol%)) / ∑alkali metal modifier (mol%) > 1, wherein the modifier is an alkali metal oxide. In a specific embodiment, the glass comprises, is substantially composed of, or is composed of: about 58 mol% to about 72 mol% SiO2; about 9 mol% to about 17 mol% Al2O3; about 2 mol% to about 12 mol% B2O3; about 8 mol% to about 16 mol% Na2O; and 0 mol% to about 4 mol% K2O, wherein the ratio (Al2O3 (mol%) + B2O3 (mol%)) / ∑ alkali metal modifier (mol%) > 1, wherein the modifier is an alkali metal oxide.

[0074] In such Figure 1 In another embodiment of the textured, anti-glare glass article 100 shown, the alkali metal aluminosilicate glass comprising the overall composition of the glass substrate 10 comprises, substantially comprises, or comprises: about 61 mol% to about 75 mol% SiO2; about 7 mol% to about 15 mol% Al2O3; 0 mol% to about 12 mol% B2O3; about 9 mol% to about 21 mol% Na2O; 0 mol% to about 4 mol% K2O; 0 mol% to about 7 mol% MgO; and 0 mol% to about 3 mol% CaO.

[0075] In yet another embodiment, the alkali metal aluminosilicate glass comprising the overall composition of the glass substrate 10 comprises, substantially comprises, or comprises: about 60 mol% to about 70 mol% SiO2; about 6 mol% to about 14 mol% Al2O3; 0 mol% to about 15 mol% B2O3; 0 mol% to about 15 mol% Li2O; 0 mol% to about 20 mol% Na2O; 0 mol% to about 10 mol% K2O; 0 mol% to about 8 mol% MgO; 0 mol% to about 10 mol% CaO; 0 mol% to about 5 mol% ZrO2; 0 mol% to about 1 mol% SnO2; 0 mol% to about 1 mol% CeO2; and less than about 50 ppm As2. O3; and less than about 50 ppm of Sb2O3; wherein 12 mol% ≤ Li2O + Na2O + K2O ≤ 20 mol% and 0 mol% ≤ MgO + Ca ≤ 10 mol%.

[0076] In another embodiment, the alkali metal aluminosilicate glass comprising the overall composition of the glass substrate 10 comprises, substantially comprises, or comprises: about 64 mol% to about 68 mol% SiO2; about 12 mol% to about 16 mol% Na2O; about 8 mol% to about 12 mol% Al2O3; 0 mol% to about 3 mol% B2O3; about 2 mol% to about 5 mol% K2O; about 4 mol% to about 6 mol% MgO; and 0 mol% to about 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 O3≦2mol%; 2mol%≦Na2O—Al2O3≦6mol%; and 4mol%≦(Na2O+K2O)—Al2O3≦10mol%.

[0077] In other embodiments, the overall composition of the glass substrate 10 comprises SiO2, Al2O3, P2O5, and at least one alkali metal oxide (R2O), wherein 0.75 > [(P2O5(mol%) + R2O(mol%)) / M2O3(mol%)] ≤ 1.2, and wherein M2O3 ═ Al2O3 + B2O3. In some embodiments, [(P2O5(mol%) + R2O(mol%)) / M2O3(mol%)] = 1, and in some embodiments, the glass does not include B2O3 and M2O3 ═ Al2O3. In some embodiments, the glass substrate comprises: about 40 to about 70 mol% SiO2; 0 to about 28 mol% B2O3; about 0 to about 28 mol% Al2O3; about 1 to about 14 mol% P2O5; and about 12 to about 16 mol% R2O. In some embodiments, the glass substrate comprises: about 40 to about 64 mol% SiO2; 0 to about 8 mol% B2O3; about 16 to about 28 mol% Al2O3; about 2 to about 12 mol% P2O5; and about 12 to about 16 mol% R2O. The glass substrate 10 may further comprise at least one alkaline earth metal oxide, such as, but not limited to, MgO or CaO.

[0078] In some embodiments, the overall composition of the glass substrate 10 is substantially lithium-free, i.e., the glass contains less than 1 mol% Li₂O, less than 0.1 mol% Li₂O in other embodiments, 0.01 mol% Li₂O in other embodiments, and 0 mol% Li₂O in other embodiments. In some embodiments, such glass is free from at least one of arsenic, antimony, and barium; i.e., the glass contains less than 1 mol% (and less than 0.1 mol% and 0 mol% in other embodiments) of As₂O₃, Sb₂O₃, and / or BaO.

[0079] exist Figure 1 In other embodiments of the textured, anti-glare glass article 100 illustrated herein, the overall composition of the glass substrate 10 comprises, is substantially composed of, or is composed of: Eagle Glass, Glass, Glass 2 Glass 3 Glass 4 or Glass composition of glass 5.

[0080] According to other implementation methods Figure 1The glass substrate 10 of the textured, anti-glare glass article 100 illustrated may have an ion-exchangeable glass composition, which can be strengthened by chemical or thermal means known in the art. In one embodiment, the glass substrate is chemically strengthened by ion exchange. In this process, metal ions at or near the main surface 12 and / or main surface 14 of the glass substrate 10 are exchanged by larger metal ions having the same valence as the metal ions in the glass substrate. The exchange is typically performed by contacting the glass substrate 10 with an ion exchange medium (such as a molten salt bath containing larger metal ions). The metal ions are typically monovalent metal ions, such as, for example, alkali metal ions. In a non-limiting example, the chemical strengthening of a sodium-containing glass substrate 10 by ion exchange is accomplished by immersing the glass substrate 10 in an ion exchange bath containing a molten potassium salt (such as potassium nitrate (KNO3) or the like). In one specific embodiment, the ions, and larger ions, in the surface layer of the glass substrate 10 are monovalent alkali metal cations, such as Li. + (when present in glass), Na + K + 、Rb + and Cs + Alternatively, the monovalent cations in the surface layer of the glass substrate 10 can be replaced with monovalent cations other than alkali metal cations (such as Ag). + (or similar items).

[0081] exist Figure 1 In these embodiments of the textured, anti-glare glass article 100 illustrated, smaller metal ions are replaced with larger metal ions in the ion exchange process, creating a compressive stress region 50 under compressive stress in the glass substrate 10, extending from the main surface 12 to a depth 52 (referred to as the "layer depth"). It should also be understood that a depth extending from the main surface 14 to substantially equivalent to the compressive stress region 50 can be formed in the glass substrate (in... Figure 1 The compressive stress region (not shown in the diagram). More specifically, this compressive stress at the main surface of the glass substrate is balanced by tensile stress (also known as "central tension") within the glass substrate. In some embodiments, when strengthened by ion exchange, the compressive stress on the main surface 12 of the glass substrate 10 described herein is at least 350 MPa, and the region under compressive stress extends to a depth 52 (i.e., layer depth) of at least 15 μm below the main surface 12.

[0082] Ion exchange processes are typically carried out by immersing a glass substrate 10 in a molten salt bath containing larger ions to be exchanged with smaller ions in the glass. Those skilled in the art will understand that parameters used in ion exchange processes include, but are not limited to, the composition and temperature of the bath, immersion time, the number of immersions of the glass in the salt bath (or multiple salt baths), the use of multiple salt baths, and additional steps (such as annealing, cleaning, or similar steps). These parameters are typically determined by the composition of the glass and the desired layer depth and compressive stress of the glass obtained through strengthening operations. For example, ion exchange of alkali metal-containing glasses can be achieved by immersion in at least one molten bath containing salts, such as, but not limited to, nitrates, sulfates, and chlorides of larger alkali metal ions. The temperature of the molten salt bath is typically in the range of about 380°C to at most about 450°C, and the immersion time ranges from about 15 minutes to at most about 16 hours. However, different temperatures and immersion times may also be used. When this type of ion exchange treatment is used with a glass substrate 10 having an alkali metal aluminosilicate glass composition, a compressive stress region 50 is generated, which has a depth 52 (layer depth) ranging from about 10 μm to at most 50 μm, a compressive stress ranging from about 200 MPa to at most about 800 MPa, and a center tension of less than about 100 MPa.

[0083] According to some embodiments, since the etching and leaching processes used to produce the textured region 30a of the textured, anti-glare glass article 100 can remove alkali metal ions from the glass substrate 10 (otherwise, these alkali metal ions would be replaced by larger alkali metal ions during the ion exchange process), preferably, after forming and developing the textured region 30a, a compressive stress region 50 is developed in the textured glass article 100. In other embodiments, before developing the textured region 30a, the compressive stress region 50 can be developed in the glass substrate 10 to a depth 52, which is sufficient to cause some loss of layer depth in the region 50 associated with the various processes related to the formation of the textured region 30a, as summarized below.

[0084] according to Figure 1Another embodiment of the textured, anti-glare glass article 100 illustrated further includes an easy-clean (ETC) coating (not shown) disposed over the textured region 30a. In most embodiments, the ETC coating is deposited over the textured region 30a such that its surface morphology generally reflects the morphology of the underlying textured region 30a. In one embodiment, the textured glass article 100a further includes a smudge-resistant fluorine-based ETC coating disposed on at least a portion of the textured region 30a. In this embodiment, the ETC coating comprises at least one amphiphobic material with fluorine end groups, providing the textured region 30a with amphiphobic properties (i.e., hydrophobic and oleophobic, or lacking affinity for both oil and water), thereby minimizing the wetting of the surface by water and / or oil. The polarity of the fluorine end groups of the ETC coating is less than that of surfaces with -OH end groups, and therefore minimizes hydrogen (i.e., van der Waals) bonds between particles and liquids. For fingerprint oil and fingerprint-related debris, the bonding force and adhesion are minimized. Therefore, the mass transfer of fingerprint oil and debris from the human finger to the ETC coating is minimized. In one embodiment, the ETC coating is formed by exchanging hydrogen present in the OH end groups on the textured region 30a of the textured glass article 100a with a fluorine-based moiety (such as, for example, a fluorinated monomer (e.g., fluorosilane)) to form a glass with fluorinated end groups.

[0085] In another implementation, Figure 1 The ETC coating of the textured glass article 100a illustrated comprises a self-assembled monolayer of molecular chains terminally fluorinated. In yet another embodiment, the ETC coating comprises a thin fluoropolymer coating, and in yet another embodiment, the ETC coating comprises silica soot particles that have been treated to have side-chained fluorocarbon groups attached to the soot particles. Such an ETC coating can be applied to the textured region 30a of the textured glass article 100a by immersion, steam coating, spraying, application by rollers, or other suitable methods known in the art. After the ETC coating has been applied, “curing” can be performed at a temperature ranging from about 25°C to up to about 150°C, and in another embodiment, “curing” can be performed at a temperature ranging from about 40°C to up to about 100°C. The curing time can range from about 1 hour to up to about 4 hours and can be carried out in air containing 40-95% humidity. After curing, the textured glass article 100a with ETC coating can be rinsed with solvent to remove any unbonded coating and air-dried before use.

[0086] Now refer to Figure 2 For conventional anti-glare glass products, providing pixel power distribution (PPD) 140 The graph shows the functional relationship between image sharpness (DOI). The surfaces of these conventional anti-glare glass products are fabricated using any of the following processes: (1) sandblasting and wet etching (e.g., with HF); (2) wet etching (e.g., with HF, NH4F, etc.); and (3) deposition of a film using a silane precursor via sol-gel film deposition. As previously outlined, PPD is a measure of scintillation, and Figure 2 The data shown is relevant to conventional anti-glare glass products. For example, from... Figure 2 It is evident that conventional anti-glare glass products do not exhibit low flicker (PPD). 140 The combination of flicker value and low DOI value. Specifically, conventional anti-glare products did not exhibit flicker values ​​below 3.7% or DOI values ​​below 77%. In contrast, the textured, anti-glare glass articles 100 disclosed herein (see...) Figure 1 The implementation of the method (and corresponding description) is characterized by less than 3% flicker (PPD). 140 and less than 70% of DOIs, and fall into Figure 2 The boxes shown indicate "DOI < 70%, PPD < 3%". Additionally, the embodiment of the textured, anti-glare glass article 100 disclosed herein is characterized by a flicker rate of less than 2% (PPD). 140 and less than 60% of DOIs, and fall into Figure 2 The box shown indicates "DOI < 60%, PPD < 2%".

[0087] Now refer to Figure 3A According to embodiments of this disclosure, a schematic diagram of a textured, anti-glare glass article is provided, illustrating the functional relationship between reflected flux and reflection angle. As used herein, "DOI" equals 100*(R). s -R 0.3° ) / R s , where R s R is the specular flux measured from the incident light (at 30° to the normal) on the textured area of ​​the textured, anti-glare glass article that guides this disclosure. 0.3° From the same incident light at the same specular reflection flux R s The reflected flux is measured at a 0.3° angle. That is, the DOI is measured by determining the relative intensity difference between the specular angle of incidence (0°) and the relative reflection angle between 0.2° and 0.4°. (The text repeats itself here, so the translation will only include the first instance.) Figure 3AIt is evident that the reflected flux and DOI observed in curves 2, 3, and 4 are relatively low compared to those associated with profile 1. Curves 2, 3, and 4 represent textured surfaces with large to medium-sized exposure features, exhibiting an average lateral dimension ranging from approximately 10 micrometers to 200 micrometers in a relatively low spatial frequency region. In contrast, curve 1 represents a textured surface with a very large exposure feature (an average lateral dimension ranging from approximately 200 micrometers to 500 micrometers). It should also be noted that curve 1 also represents a textured surface with a higher spatial frequency (a small average lateral feature size). Therefore, from Figure 3A It is evident that textured surfaces with a low spatial frequency region and medium to large size features but not ultra-large size features tend to exhibit low DOI levels. Unbound by theory, it is believed that the textured, anti-glare glass articles 100 of this disclosure (see [reference]) Figure 1 The low spatial frequency region 21 with texture region 30a provides a significant influence in the low DOI level (<70%) exhibited.

[0088] Now refer to Figure 3B Schematic diagrams are provided for a textured, anti-glare glass article and a component of the textured area of ​​the article, as illustrated, showing the effect of the glass surface texture on the flicker level of a display. In each of the schematic diagrams A, B, and C, the display pixels shown represent red, green, and blue sub-pixels (i.e., as seen from left to right in each schematic diagram). Furthermore, each of these schematic diagrams assumes that only the green sub-pixels are illuminated. Figure 3B Schematic diagrams A, B, and C compare the differences in light uniformity of the green sub-pixels when large, small, and mixed exposure features of a textured region (e.g., textured region 30a) are applied to a glass substrate (e.g., glass substrate 10) located above the sub-pixels, as shown. In schematic diagram A, a textured glass surface (e.g., a textured region with only a low spatial frequency component, as shown) with a larger average lateral feature size compared to the average lateral feature size of the sub-pixels is placed above the green sub-pixels. The light from the left pixel is diffused and appears darker, while the light from the right pixel is focused and appears brighter to the human eye. Therefore, schematic diagram A represents a display that appears non-uniform and grainy, with a high flicker level. In schematic diagram B, a textured glass surface (e.g., a textured region with only a high spatial frequency component, as shown) with a smaller average lateral feature size compared to the average lateral feature size of the sub-pixels is placed above the green sub-pixels. The light from the left and right pixels appears similar in intensity. Therefore, Figure 3BSchematic B in the diagram represents a display that appears uniform and has low flicker. However, from... Figure 3A It is also evident that textured surfaces with high spatial frequency regions (and no additional low spatial frequency region counterparts) (such as those depicted by curve 1 in this figure) have relatively high DOI. Finally, turning to schematic diagram C, a textured glass surface (e.g., a textured, anti-glare glass article 100 mixed with both low spatial frequency textured region 21 and high spatial frequency textured region 22, as shown) that is both small and large compared to the average lateral feature size of the sub-pixel is placed on top of the green sub-pixel. The spatial frequency of the exposed features determines the direction of light scattering from the surface. Furthermore, from Figure 3B As can be seen from the schematic diagram C, the pixels on the left and right sides have similar uniformity and intensity, i.e., low flicker.

[0089] Now refer to Figure 4A and Figure 4B The textured, anti-glare glass products 100 disclosed in this article (see Figure 1 This property can be incorporated into another article, such as articles having a display (or articles with a display) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like); building articles; transport articles (e.g., automobiles, trains, airplanes, seacraft, etc.); electrical articles; or any article requiring partial transparency, scratch resistance, abrasion resistance, or a combination of the above properties. Figure 4A and Figure 4B The illustration shows exemplary articles incorporated herein by reference to any of the glass articles (including glass article 100). Specifically, Figure 4A and Figure 4B A consumer electronic device 400 is shown, comprising: a housing 402 having a front surface 404, a rear surface 406, and a side surface 408; electronic components (not shown) at least partially or entirely located within the housing, and including at least a controller, memory, and a display 410 located at or adjacent to the front surface of the housing; and a cover plate 412 located at or above the front surface of the housing, such that the cover plate is above the display. In some embodiments, at least one of the cover plate 412 or a portion of the housing 402 may include any of the glass articles disclosed herein.

[0090] Now refer to Figure 5 A schematic flowchart is provided, illustrating a method 200 for manufacturing a textured glass article, such as a textured, anti-glare glass article 100 (e.g., Figure 1 (As illustrated in the illustration). Unless otherwise stated, Figure 1 and Figure 5The similar numbered components of the textured, anti-glare glass article 100 shown in the illustration have the same or substantially similar functions and structures. For example... Figure 5 As shown, a glass substrate 10 is provided, the glass substrate having a main surface 12 and an opposite main surface 14, and a further feature of the glass substrate being a thickness 13. Figure 5 As further shown, method 200 includes step 202, which involves etching the main surface 12 of the glass substrate 10 with a first etchant to form a textured region 21 with a low spatial frequency. The textured region 21 with a low spatial frequency may be characterized by an average surface roughness R. a1 and the average lateral feature size 31. Step 202 can be performed using one or more of the following etching processes: using a low pH solution as an etchant, using sand particles as an etchant, and using grit as an etchant. For example, step 202 may include (e.g., in a separate subsequent step) etching with a sandblasting medium and a low pH solution as an etchant to produce a textured region 21 with a low spatial frequency.

[0091] See again Figure 5 The method 200 for manufacturing textured glass articles further includes step 204, which involves etching the main surface 12 of the glass substrate 10 with a second etchant to form a textured region 22 with a high spatial frequency. The textured region 22 with a high spatial frequency may be characterized by an average surface roughness R. a2and an average lateral feature size of 32. Step 204 can be performed using an etchant with a pH of about 4 or less. Suitable etchants include hydrofluoric acid-free etchants (e.g., citric acid, hydrochloric acid) and hydrofluoric acid-containing etchants. Suitable hydrofluoric acid-free etchants include hydrochloric acid, nitric acid, sulfuric acid, citric acid, ascorbic acid, oxalic acid, and acetic acid. According to one embodiment, etching step 204 is performed at an elevated temperature ranging from above ambient temperature to about 110°C. In some embodiments, etching step 204 is performed at temperatures of about 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, and all temperatures between these values. Additionally, etching step 204 can be performed from about 15 minutes to about 100 hours. In some embodiments, etching step 204 is performed from about 5 hours to about 30 hours. According to some embodiments, suitable concentration levels of the hydrochloric acid etchant range from about 0.5% to about 15% by weight, for example, about 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% and all concentrations of hydrochloric acid between these levels. According to other embodiments, suitable concentration levels of the citric acid etchant range from about 1% to 30% by weight, for example, about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% and all concentrations of citric acid between these levels. Once etching step 204 is completed, a textured region 30a is formed in the textured glass article (e.g., textured, anti-glare glass article 100). The textured region 30a includes a low spatial frequency textured region 21 and a high spatial frequency textured region 22 (see also...). Figure 1 According to some embodiments of method 200, the textured, anti-glare glass article 100 formed according to this method includes a low-textured region 21 having an average lateral feature size 31, which exceeds the average lateral feature size 32 of the high spatial frequency region 22. Additionally, each of the textured region 21 and the textured region 22 may contain a surface roughness (i.e., R0) from about 10 nanometers to about 1000 nanometers. a1 and R a2 ), or may collectively include an average surface roughness (R) ranging from about 10 nanometers to about 1000 nanometers. a ).

[0092] according to Figure 5The image shows the making of textured articles (e.g., such as...). Figure 1 In another embodiment of the method 200 (illustrated as a textured, anti-glare glass article 100), the etching step 204 may include etching the main surface 12 of a glass substrate 10 having a thickness 13 with a second etchant having a pH of about 4 or less and an additive salt. As used herein, the term "additive salt" includes salts containing one or more of the following: polyvalent metal cations (e.g., Al). 3+ ), ammonium cations (e.g., NH4) + Metal cations that are absent or present in trace amounts in the glass substrate 10 (e.g., for some compositions of the glass substrate 10, Li) + In some embodiments, the additive salt may contain polyvalent metal ions and / or ammonium ions (e.g., selected from NH4). + Al 3+ Fe 3+ Ca 2+ and Mg 2+ The additive salt can be any group consisting of monovalent anions (e.g., chloride ions, fluoride ions, hydrogen fluoride). For example, the additive salt can be NH4F, NaF, KF, NH4HF2, NaHF2, KHF2, NH4Cl, AlCl3, FeCl3, CaCl2, and MgCl2. In some embodiments, the additive salt may also include salts containing cations that are absent or present in trace amounts within the target glass substrate 10, such as NH4Cl, LiCl, CsCl, etc. According to some embodiments, etching step 204 is performed such that the concentration of the additive salt (other than the etchant without hydrochloric acid) used is from greater than about 0.1M to about 5M. According to some embodiments, the concentration of the polyvalent metal salt used in etching step 204 is from greater than about 0.1M to about 3M, from about 0.5M to about 2M, from about 0.5M to about 1.5M, and all concentration values ​​between the endpoints of these ranges. In some embodiments of etching step 204 employing additive salts, etching is performed at temperatures ranging from about 75°C to about 110°C, from about 80°C to about 110°C, from about 85°C to about 110°C, from about 90°C to about 110°C, and all temperatures between the endpoints of these ranges. Advantageously, incorporating additive salts into etching step 204 can reduce the etching time required to develop the desired level of texture within the high spatial frequency region 22 of the textured region 30a (see also...). Figure 1 According to some embodiments of etching step 204 using additive salt, etching can be performed from about 15 minutes to about 10 hours. In a preferred embodiment, etching step 204 can be performed using additive salt for about 15 minutes to about 5 hours, from about 30 minutes to about 5 hours, or even from about 30 minutes to 2 hours.

[0093] See again Figure 5 The method 200 illustrated, according to some embodiments, further includes a removal step (not shown) configured to remove excess etchant and leached substrate components from etching steps 202 and / or 204. That is, after steps 202 and 204 of method 200, excess etchant and any loose and residual components from the substrate 10 are removed by rinsing the main surface 12 with deionized water. As will be understood by those skilled in the art to which this disclosure pertains, various mechanical and / or aqueous cleaning methods can be employed in the removal step to remove excess etchant and leached substrate components without substantially affecting the surface of the substrate 10.

[0094] Still refer to Figure 5 The method 200 illustrated, according to some embodiments, further includes a step 206, which is to treat the main surface 12 of the substrate 10 with an aqueous solution with a pH greater than 9. In these embodiments, these treatment steps 206 facilitate the formation of a textured glass article formed according to method 200 (see also...). Figure 1 For example, the high spatial frequency region 22 of the textured region 30a of a textured, anti-glare glass article 100. More specifically, after etching steps 202 and 204, processing step 206 can be performed at a temperature higher than ambient temperature using a high-pH aqueous solution (pH > 9). In an embodiment, the high-pH aqueous solution used during step 206 is an aqueous alkaline solution (e.g., NaOH) having a pH range from about 10 to about 13. According to one embodiment, processing step 206 is performed at an elevated temperature from above ambient temperature to about 110°C. In some embodiments, processing step 206 is performed at temperatures of about 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, and all temperatures between these values. Furthermore, processing step 206 can be performed for from about 15 minutes to about 100 hours. In some implementations, processing step 206 takes from about 5 hours to about 30 hours. Example

[0095] The following examples describe the various features and advantages provided by this disclosure and are in no way intended to limit the invention and the appended claims.

[0096] Example 1

[0097] If consistent with the principles disclosed herein, a material with a thickness of approximately 0.6 mm can be prepared according to the following method. Textured, anti-glare glass samples of glass 3. Specifically, these samples underwent a sandblasting and etching process (step 1) to form low spatial frequency textured regions on the main surface of the glass substrate. Some of these samples (Example 1A) underwent an etching process consistent with the principles of this disclosure to obtain approximately 6% to 7% transmitted haze. The remaining samples (Example 1B) were etched according to an etching process consistent with the principles of this disclosure to obtain approximately 19% to 20% transmitted haze. Figure 6A The SEM micrographs clearly show that the low spatial frequency textured regions in all these samples (Example 1A and Example 1B) have an average lateral feature size of approximately 15 to 20 micrometers. The DOI of all these samples (Example 1A and Example 1B) is <50%. Furthermore, the PPD of the first group of samples (Example 1A) is approximately 7.6%, and the PPD of the second group of samples (Example 1B) is approximately 5.6%. In addition, after the sandblasting and etching steps, all samples were measured to have a thickness of approximately 0.55 mm.

[0098] After completing the sandblasting and etching processes (step 1 above), the samples underwent etching with a low-pH etchant and additive salt (step 2), followed by a high-pH treatment (step 3) to form high spatial frequency textured regions on the main surface of the glass substrate. Therefore, the resulting substrate has textured regions, which include both low-space-frequency and high-space-frequency textured regions. Specifically, the low-space-frequency textured regions from the samples in step 1 were further treated with a solution of 10 wt.% HCl and 16.2 wt.% FeCl3 at 95°C for 2.17 hours (Examples 1A1 and 1B1), 2.75 hours (Examples 1A2 and 1B2), or 3.42 hours (Examples 1A3 and 1B3). After the low-pH treatment, all samples were further treated with a high-pH solution of NaOH at 60°C for 10 minutes (step 3). After completing steps 2 and 3, all samples (Examples 1A1-A3 and Examples 1B1-B3) exhibited textured regions with high spatial frequencies. The exposed features of these textured regions had an average lateral feature size ranging from 0.5 micrometers to 2 micrometers. Figure 6B The SEM micrographs further confirm this. Note that... Figure 6B The SEM micrographs of the samples in the middle are control samples that only underwent steps 2 and 3 and not step 1 (Example 1D1-D3).

[0099] The DOI and PPD of the samples produced in this embodiment were evaluated. Table 1 summarizes the results of this evaluation, including the process conditions of the samples in this embodiment. In addition, Table 1 includes the DOI and PPD results of a set of control samples (Example 1C1) that were not etched or treated in steps 1-3; and the DOI and PPD results of a set of control samples (Examples 1D1-D3) that were etched and treated in steps 2 and 3 but not in step 1. As is evident from Table 1, the samples (Examples 1A and 1B) that only include textured regions with low spatial frequencies exhibit high flicker (i.e., PPD of 7.6% and 5.6%, respectively) and low DOI (i.e., 6.38% and 44.01%, respectively). Furthermore, samples containing only textured regions with high spatial frequencies (Examples 1D1-D3) exhibited low flicker (i.e., PPD from 0.4% to 0.6%) and high DOI (i.e., from 99.35% to 99.79%). Conversely, samples with mixed textured regions containing both low and high spatial frequencies (Examples 1A1-A3 and Examples 1B1-B3) exhibited low flicker (i.e., PPD from 0.7% to 6.2%) and low DOI (i.e., approximately 0%).

[0100] Table 1

[0101]

[0102]

[0103] Now refer to Figure 6C and Figure 6D This embodiment provides the angular reflectivity distributions of the textured regions at low and high spatial frequencies of the anti-glare glass article. Specifically, Figure 6C yes Figure 6A The angular reflectance distribution of the sample shown is... Figure 6A The samples shown have textured regions with low spatial frequencies (Examples 1A and 1B). As from... Figure 6C It is evident that these samples exhibit low DOI (i.e., 6.38% and 44.01%, respectively). Regarding... Figure 6D This curve shows Figure 6B The angular reflectance distribution of the sample shown is... Figure 6B The samples shown have textured regions with high spatial frequencies (Examples 1D1-D3). As from... Figure 6D It is evident that these samples exhibit high DOI (i.e., close to 100%).

[0104] Now refer to Figure 7AThe study provides angular reflectance distributions from -5° to +5° for textured, anti-glare glass samples (Examples 1A1-A3 and 1B1-B3), which exhibit both low-spatial-frequency textured regions and high-spatial-frequency textured regions. Additionally, Figure 7B For the general Figure 7A Angular reflectance distribution magnified to a smaller angular range from -0.5° to +0.5°. As is evident from these figures, the sample with mixed textured regions exhibits a low DOI (i.e., approximately 0%), this mixed textured region containing both low-spatial-frequency and high-spatial-frequency textured regions. Furthermore, the results in Table 1 show that these samples also exhibit low flicker; therefore, the textured, anti-glare glass article of this embodiment exhibits a combination of low flicker (e.g., <3%) and low DOI (e.g., <70%).

[0105] Those skilled in the art will readily understand that when measuring the surface roughness of the aforementioned glass products, the following two ISO standards for surface texture measurement can be used: (1) ISO 4287:1997 "Geometrical Product Specifications (GPS) – Surface texture: Profile Method – Terms, definitions and surface texture parameters", published April 1997, 25 pages; (2) ISO 4288:1996 "Geometrical Products Specifications (GPS) – Surface texture: Profile method – Rules and procedures for the assessment of surface texture", published August 1996, 8 pages (the contents of these documents are incorporated herein by reference for all purposes). A characteristic dimension can be defined as the relevant length (Lc), a measure of length on which patterns can be statistically predicted based on the current position and height (see ISO 4287 and 4288 standards for more details). Furthermore, when measuring the surface roughness of the aforementioned glass articles, specific instruments such as atomic force microscopy (AFM) or Zygo can be selected based on the characteristic size. In practice, an initial microscopic estimate of the characteristic size is typically used to select an appropriate instrument based on its resolution, and this selection is confirmed using the reported relevant length. For example, AFM can be used to measure surface roughness for characteristic sizes from 10 nm to 10 μm. Zygo can be used to measure surface roughness for characteristic sizes of 10 μm and larger. The sampling length is defined as 10 * the characteristic size, and is then used to determine the upper cutoff spatial frequency λc = 1 / (sampling length) and the average surface roughness Ra (see ISO 4287 and 4288 standards for more details).

[0106] Many variations and modifications may be made to the above-described embodiments of this disclosure without substantially departing from the spirit and principles thereof. All such variations and modifications are intended to be covered herein, fall within the scope of this disclosure, and are protected by the following claims.

Claims

1. A glass article comprising: Glass substrate, including thickness and main surface; and Textured areas are defined by the main surface. The textured region comprises a low spatial frequency region and a high spatial frequency region, with the high spatial frequency region superimposed on the low spatial frequency region. The low spatial frequency region contains an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. The average lateral feature size of the low spatial frequency region is 3.5 to 15 times larger than that of the high spatial frequency region.

2. The glass article of claim 1, wherein the textured region comprises a surface roughness (R0) ranging from 10 nm to 1000 nm. a ).

3. The glass article of claim 2, wherein the surface roughness (R) of the textured region is... a The low spatial frequency components (R) contained in this low spatial frequency region a1 ) and the high spatial frequency component (R) in this high spatial frequency region a2 The average surface roughness of the low spatial frequency region is between 50 nm and 1000 nm, and the average surface roughness of the high spatial frequency region is between 10 nm and 200 nm.

4. The glass article as claimed in claim 1 or claim 2, wherein the average lateral feature size of the low spatial frequency region is 5 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

5. The glass article as claimed in claim 1 or claim 2, wherein the average lateral feature size of the low spatial frequency region is 10 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

6. The glass article of claim 1 or claim 2, wherein the average lateral feature size of the low spatial frequency region is 20 μm or greater, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

7. The glass article of claim 1 or claim 2, wherein the glass substrate comprises a composition selected from the group consisting of aluminosilicate glass, borosilicate glass, phosphosilicate glass, soda-lime glass, alkali metal aluminosilicate glass and alkali metal borosilicate glass.

8. The glass article of claim 1 or claim 2, wherein the glass substrate further includes a compressive stress region extending from the main surface to a selected depth.

9. The glass article as claimed in claim 1 or claim 2, wherein the glass article comprises less than 3% flicker and less than 70% image sharpness (DOI) as measured by pixel power distribution (PPD).

10. The glass article of claim 1 or claim 2, wherein the glass article comprises less than 2% flicker and less than 60% image sharpness (DOI) as measured by pixel power distribution (PPD).

11. The glass article as claimed in claim 1 or claim 2, wherein the glass article comprises less than 1% flicker and less than 50% image sharpness (DOI) as measured by pixel power distribution (PPD).

12. The glass article of claim 1 or claim 2, wherein the glass article contains less than 1% flicker as measured by pixel power distribution (PPD).

13. The glass article as claimed in claim 1 or claim 2, wherein the glass article contains a transmission haze of 3% to 30%.

14. The glass article as claimed in claim 1 or claim 2, wherein the glass article comprises less than 3% flicker, less than 40% image sharpness (DOI), and 3% to 30% haze as measured by pixel power distribution (PPD).

15. A glass article comprising: Glass substrate, including thickness and main surface; and Textured areas are defined by the main surface. The textured region comprises a low spatial frequency region and a high spatial frequency region, with the high spatial frequency region superimposed on the low spatial frequency region. The low spatial frequency region contains an average lateral feature size that exceeds the average lateral feature size of the high spatial frequency region. The textured region contains a surface roughness (R) ranging from 10 nm to 1000 nm. a ), The average lateral feature size of the low spatial frequency region is 3.5 to 15 times larger than that of the high spatial frequency region. The average lateral feature size of the low spatial frequency region is 20 μm or larger, and the average lateral feature size of the high spatial frequency region is less than 5 μm.

16. The glass article of claim 15, wherein the glass article comprises less than 3% flicker, less than 40% image sharpness (DOI), and 3% to 30% haze as measured by pixel power distribution (PPD).

17. A method for manufacturing glass articles, comprising the following steps: A first etching is performed on the main surface of the glass substrate using a first etchant to form a textured region with low spatial frequency defined by the main surface; and The main surface of the glass substrate is etched a second time using a second etchant to form a high spatial frequency textured region defined by the main surface and superimposed on the low spatial frequency textured region. The low-spatial-frequency textured region contains an average lateral feature size that exceeds the average lateral feature size of the high-spatial-frequency textured region. The average lateral feature size of the low spatial frequency region is 1.5 to 100 times larger than that of the high spatial frequency region.

18. The method of claim 17, wherein the average lateral feature size of the low spatial frequency region is 3.5 to 15 times larger than the average lateral feature size of the high spatial frequency region.

19. The method of claim 17 or claim 18, wherein the first etchant comprises a sandblasting etchant and a low-pH solution etchant.

20. The method of claim 17 or claim 18, wherein the first etchant comprises hydrochloric acid and a fluoride salt, wherein the fluoride salt comprises one or more salts selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium difluoride, sodium difluoride, and potassium difluoride.

21. The method of claim 17 or claim 18, wherein the second etching is performed at an etching temperature above ambient temperature, and the second etchant is a solution with a pH less than 4.

22. The method of claim 17 or claim 18, wherein the second etchant comprises an acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, citric acid, ascorbic acid, oxalic acid, and acetic acid.

23. The method of claim 17 or claim 18, wherein the second etchant comprises one or more salts comprising polyvalent metal cations.

24. The method of claim 17 or claim 18, wherein the etching temperature of the second etching is from 60°C to 100°C.

25. The method of claim 17 or claim 18, further comprising the following steps: The main surface of the glass substrate is treated with an aqueous solution with a pH greater than 9 at a temperature above ambient temperature, after the first etching step and the second etching step.

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