Coated article with light altering features and method of producing same
阅读说明：本技术 具有光变化特征的涂覆制品及其生产方法 (Coated article with light altering features and method of producing same ) 是由 J·D·格雷格斯基 S·D·哈特 K·W·科齐三世 C·A·考斯克-威廉姆斯 C·A·保尔森 于 2019-01-09 设计创作，主要内容包括：根据本文所述的一个或多个实施方式,涂覆制品可以包括：具有主表面的透明基材,所述主表面包括包含光散射的纹理化表面或粗糙表面；以及布置在透明基材的主表面上且形成空气侧表面的光学涂层,所述光学涂层包括一层或多层材料,所述光学涂层具有大于300nm的物理厚度,其中,涂覆制品展现出约10GPa或更大的最大硬度,这是在空气侧表面上通过布氏压痕计硬度测试沿着约50nm或更大的压痕深度测得的。(According to one or more embodiments described herein, a coated article may comprise: a transparent substrate having a major surface comprising a textured or roughened surface comprising light scattering; and an optical coating disposed on a major surface of the transparent substrate and forming an air-side surface, the optical coating comprising one or more layers of material, the optical coating having a physical thickness greater than 300nm, wherein the coated article exhibits a maximum hardness of about 10GPa or greater, as measured on the air-side surface by a berkovich indenter hardness test along an indentation depth of about 50nm or greater.)
1. A coated article, comprising:
a transparent substrate having a major surface, the major surface comprising a rough surface comprising light scattering;
an optical coating disposed on a major surface of a transparent substrate and forming an air-side surface, the optical coating comprising one or more layers of material, the optical coating having a physical thickness greater than 300 nm;
wherein the coated article exhibits a maximum hardness of about 10GPa or greater as measured on the air-side surface by a Berkovich indenter hardness test along an indentation depth of about 50nm or greater.
2. The coated article of claim 1, wherein the major surface comprises at least one of the following roughnesses: rq of 100nm or more; and (ii) an Ra of 100nm or more.
3. The coated article of claim 2, wherein the optical coating has a physical thickness greater than Ra or Rq of the rough surface.
4. The coated article of any preceding claim, wherein the optical coating has a physical thickness greater than 600 nm.
5. The coated article of any of the preceding claims, further comprising at least one of the following two-sided specular reflectance (SCI-SCE): less than 4.5%, or less than 4%.
6. The coated article of any of the preceding claims, further comprising a one-sided specular reflectance of at least one of: less than about 0.5%, alternatively less than about 0.25%, alternatively less than 0.2%, alternatively less than 0.15%, alternatively less than 0.1%, alternatively as small as the photopic average.
7. The coated article of any of the preceding claims, further comprising a one-sided specular reflectance of at least one of: less than about 0.5% from a near normal angle of incidence up to an angle of incidence of 40 degrees; and less than 3%, less than 1.5%, or less than 1% at 60 degrees of incidence angle.
8. The coated article of any of the preceding claims, further comprising a double-sided diffuse reflectance (SCE) of: greater than about 0.05 or greater than 0.1 and less than or equal to about 0.5 or about 1.0 or about 1.5 or about 2.0 or about 3.0.
9. The coated article of any of the preceding claims, further comprising a double-sided total reflectance (SCI) of less than about 5.5.
10. The coated article of any of the preceding claims, further comprising a and b reflectance color values having absolute values of less than 16, less than 12, less than 10, less than 5, or less than 2.
11. The coated article of any of the preceding claims, further comprising:
the absolute value is a and/or b of at least one of: greater than about 6; from about 10 to about 16; greater than about 16; about 10 to about 20; from about 10 to about 30; from about 10 to about 40; and about 10 to about 50; and
the transmitted haze value on the major surface is at least one of: from about 4% to about 7%, and less than 10%.
12. The coated article of any one of claims 1-10, further comprising:
the absolute value is a and/or b of at least one of: less than 6, less than 5, less than 4, and less than 2; and
the transmitted haze value on the major surface is at least one of: greater than 10%, greater than 20%, greater than 25%, greater than 27%, greater than 40%, greater than 50%, and greater than 60%.
13. The coated article of any of the preceding claims, further comprising at least one of a 20 degree DOI: less than 95, less than 90, less than 80, or less than 70.
14. The coated article of any of the preceding claims, further comprising a 60 degree gloss value of less than 80 or less than 60.
15. The coated article of any of the preceding claims, further comprising at least one of the following total light transmittance: higher than 80%, higher than 90%, higher than 94%.
16. The coated article of any of the preceding claims, further comprising at least one of the following sparkle performance as measured by Pixel Power Deviation (PPD): less than 10%, or less than 5%.
17. The coated article of any of the preceding claims, wherein the article comprises at least one of the following after 1 cycle at a rate of 25 cycles/min under a load of 4kg, after a 150 mesh best scratch test:
the two-sided specular reflectance (SCI-SCE) is: less than 6.0% or less than 5.0%; and/or a change relative to the unworn value of less than 2.0%, less than 1.0%, or less than 0.5%;
the double-sided diffuse reflectance (SCE) is: less than 3.0%, less than 2.0%, less than 1.0%, or less than 0.5%; and/or a change relative to the unworn value of less than 1.0%, less than 0.5%, or less than 0.2%; and
a bilateral total reflectance (SCI) of less than 6.0% or less than 5.0%; the change relative to the unworn value is less than 2.0%, less than 1.0%, less than 0.5%, or less than 0.2%.
18. The coated article of any of the preceding claims, wherein the article comprises at least one of the following after 50 cycles at a rate of 25 cycles/min under a total weight load of 1kg, after taber abrasion testing with 400 mesh kevlar sandpaper:
the two-sided specular reflectance (SCI-SCE) is: less than 7.5%, less than 6.0%, or less than 5.0%; and/or a change relative to the unworn value of less than 3.0%, less than 2.0%, or less than 1.0%;
the double-sided diffuse reflectance (SCE) is: less than 5.0%, less than 3.0%, less than 2.0%, or less than 1.0%; and/or a change relative to the unworn value of less than 3.0%, less than 2.0%, less than 1.0%, or less than 0.5%; and/or
The two-sided total reflectance (SCI) is: less than 8.0%; and/or a change relative to the unworn value of less than 3.0%, less than 2.0%, less than 1.0%, or less than 0.5%.
19. The coated article of any of the preceding claims, further comprising at least one of the following hardness: 12GPa or greater; 14GPa or greater; 16GPa or greater.
20. The coated article of any of the preceding claims, further comprising a hardness of at least 12GPa or greater and an optical coating thickness of greater than 300 nm.
21. The coated article of any of the preceding claims, further comprising a hardness of at least 14GPa or greater and an optical coating thickness of at least 500 nm.
22. The coated article of claim 1, wherein the article transmissive and/or reflective color coordinates in the laa b chromaticity system exhibit, at normal incidence, according to the commission international lighting system light source: a reference point color shift of less than about 10 relative to a reference point, measured on the air side surface, the reference point comprising: color coordinates (a ═ 0, b ═ 0), (a ═ -2, b ═ -2), or the corresponding transmitted or reflected color coordinates of the substrate, where:
when the reference point is a color coordinate (a ═ 0, b ═ 0), pass √ ((a ═ 0)Article of manufacture)2+(b*Article of manufacture)2) Defining a color shift;
when the reference point is a color coordinate (a ═ 2, b ═ 2), pass √ ((a ═ 2)Article of manufacture+2)2+(b*Article of manufacture+2)2) Defining a color shift; and
when the reference point is the color coordinate of the substrate, √ ((a) √ b)Article of manufacture-a*Base material)2+(b*Article of manufacture-b*Base material)2) A color shift is defined.
23. The coated article of claim 1, wherein the coated article has a transmission haze value of about 50% or less.
24. The article of any one of the preceding claims, wherein the substrate comprises an amorphous substrate or a crystalline substrate.
25. The coated article of any of the preceding claims, wherein the coated article has an average photopic transmission of about 50% or greater.
26. An electronic device comprising the coated article of any of the preceding claims.
Background
The present disclosure relates to coated articles and methods of making the same, and more particularly, to coated articles having durable and/or scratch-resistant optical coatings on transparent substrates.
Overlay articles are commonly used to protect critical devices within electronic products, to provide user interfaces for input and/or display, and/or to provide many other functions. Such products include mobile devices such as smart phones, mp3 players, and tablet computers. Covering articles also include construction articles, transportation articles (e.g., articles for vehicular applications, trains, aircraft, ships, etc.), electrical articles, or any article requiring partial transparency, scratch resistance, abrasion resistance, or a combination thereof. These applications typically require scratch resistance and robust optical performance characteristics in terms of maximum light transmission and minimum reflectivity. In addition, some overlay applications require that the color exhibited or perceived in reflection and/or transmission does not change appreciably with changes in viewing angle. This is because, in display applications, if the reflected or transmitted color changes to an appreciable extent as the viewing angle changes, the user of the product will perceive the color or brightness change of the display, which will reduce the sensory quality of the display. In other applications, the change in color may negatively impact aesthetic or other functional requirements.
The optical performance of the cover article can be improved by the use of various anti-reflective ("AR") coatings; the known antireflective coatings are however susceptible to wear or abrasion. Such wear would compromise any optical performance improvement achieved by the antireflective coating. For example, optical filters are typically fabricated from multiple coatings having different refractive indices, and are fabricated from light-transmissive dielectric materials (e.g., oxides, nitrides, and fluorides). Most common oxides for such filters are wide bandgap materials that do not have the mechanical properties, such as hardness, required for use in mobile devices, building articles, transportation articles, or electrical articles.
Wear damage may include sliding contact back and forth from opposing objects (e.g., fingers). In addition, abrasion damage can generate heat, which can degrade chemical bonds in the film material and cause flaking and other types of damage to the cover glass. Since wear damage is typically experienced over a longer period of time rather than in a single event causing scratching, the coating material undergoing wear damage may also oxidize, which may further degrade the durability of the coating.
Known antireflective coatings are also susceptible to scratch damage, and are generally more susceptible to scratch damage than the underlying substrate upon which such coatings are disposed. In some cases, a majority of such scratch damage includes micro-ductile scratches, which typically include a single groove in the material having a depth of about 100nm to about 500nm and an extended length. Micro-ductile scratches may be caused by other types of visible damage, such as subsurface cracking, frictional cracking, chipping, and/or abrasion. Evidence suggests that most of these scratches and other visible damage are due to sharp contact that occurs in a single contact event. Once a significant scratch occurs on the cover substrate, the appearance of the article is degraded because the scratch causes an increase in light scattering, which can cause a significant reduction in the brightness, transparency, and image contrast of the display. Significant scratches can also affect the accuracy and reliability of articles that include touch sensitive displays. Single event scratch damage can be contrasted with wear damage. Single event scratch damage is not caused by multiple contact events, such as reciprocating sliding contact with hard opposing objects (e.g., sand, gravel, and sandpaper), which also typically do not generate heat (which can degrade chemical bonds in the membrane material and cause flaking and other types of damage). Furthermore, since single event scratches do not typically cause oxidation or involve the same conditions that lead to wear damage, solutions for preventing wear damage are also not generally available for preventing scratches. In addition to this, known scratch and abrasion damage solutions often compromise optical properties.
Roughened or textured surfaces with light scattering "anti-glare" functionality have been fabricated for display screens. These surfaces increase the display readability in ambient lighting by diffusing or blurring the reflected image and by reducing specular reflection. Thin (<300nm) antireflection coatings have been added to these types of textured surfaces to combine light scattering (from the textured surface) and interference-based antireflection effects (from the coating). These types of coatings typically suffer from low scratch resistance and high scratch visibility.
Recently, high hardness antireflective coatings with high scratch resistance and low scratch visibility have been validated. See, for example: US patents 9,079,802, 9,359,261, 9,366,784, 9,335,444 and 9,726,786, and yet unlicensed US publications US2015/0322270 and US 2017/0307790. These coatings typically include thicknesses of >500nm (and in some cases, greater than 1000, greater than 1500, or greater than 2000nm), to achieve a combination of high hardness, high scratch resistance, low reflectivity, and low color shift that are beneficial for display applications.
Disclosure of Invention
It is shown herein that thicker optical scratch-resistant coatings can be uniformly deposited onto textured anti-glare surfaces without interfering with light scattering from the surface texture or the controlled color anti-reflection effect from the optical coating. Furthermore, advantageous properties are obtained. In particular, the ability to hide scratches and suppress ambient reflections is maximized by the combination of a light scattering surface with a low reflectivity optical coating.
Described herein is the combination of a textured light-scattering chemically strengthened glass surface with a uniform color controlled low reflectivity optical hard coating. The high hardness minimizes the formation of scratches. The low reflectivity and light scattering together act to increase display readability, reduce glare, or minimize eye fatigue. Light scattering surfaces (light-altering features) also provide a secondary scratch hiding mechanism, as the light scattering background helps hide scattered light from certain conventional surface scratches and associated types of breakage. The combination of light scattering and low reflectivity features minimizes glare and maximizes display readability, apparent color gamut, and/or apparent brightness, particularly in outdoor environments.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the various embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings. For example, various features may be combined according to the following embodiments.
Drawings
It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, 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 operations of the various embodiments, in which:
FIG. 1 is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 2A is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 2B is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 3 is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 4 is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 5 is a cross-sectional side view of a coated article according to one or more embodiments described herein;
FIG. 6 is a plot of refractive index as a function of distance in the coated article of FIG. 5 according to one or more embodiments described herein;
FIGS. 7A-7D show exemplary BaF on a glass substrate according to one or more embodiments described herein2Atomic force microscopy of the coating;
FIGS. 8A-8D show BaF on a glass substrate according to one or more embodiments described herein2Exemplary SiN deposited on overcoatxAtomic force microscopy of the coating;
FIG. 9 shows a graph of total transmittance as a function of wavelength for an exemplary coating according to one or more embodiments described herein;
FIG. 10 shows a plot of specular reflectance as a function of wavelength for an exemplary coating according to one or more embodiments described herein;
11A and 11B are atomic force microscope images of a substrate surface having light altering features thereon;
FIGS. 12A and 12B are atomic force microscope images of the substrate surface of FIGS. 11A and 11B, respectively, with an optical coating disposed thereon, according to one or more embodiments described herein;
FIG. 13A is a graph of Young's modulus (in GPa, left-side y-axis) and hardness (in GPa, right-side y-axis) of a substrate having light-altering features thereon, respectively, versus displacement (in nm, x-axis) into the surface;
FIG. 13B is a graph of Young's modulus (in GPa, left-side y-axis) and hardness (in GPa, right-side y-axis), respectively, of a substrate having a light altering feature and an optical coating thereon, according to one or more embodiments described herein, versus displacement (in nm, x-axis) into the surface;
FIG. 14 is a graph of first surface reflectance (in%, y-axis) versus wavelength (in nm, x-axis) for a substrate (including those having a light-altering feature and an optical coating disposed thereon) according to one or more embodiments described herein;
FIG. 15 is a graph of transmittance (in%) versus wavelength (in nm, x-axis) of a substrate (including those having a light-altering feature and an optical coating disposed thereon) according to one or more embodiments described herein;
FIG. 16 is a graph of the color coordinates of light (color reflected from
FIG. 17 is a graph of the color of light (6 degree angle of incidence, color of dual surface transmission under a D65 light source) for a substrate (including those having light altering features and optical coatings disposed thereon) according to one or more embodiments described herein;
18A and 18B are images of a good scratch resistance test of a glass substrate and a glass substrate having both a light-altering feature and an optical coating disposed thereon, respectively, according to one or more embodiments described herein;
19A and 19B are images of a Taber abrasion test of a glass substrate and a glass substrate having both a light-altering feature and an optical coating disposed thereon, respectively, according to one or more embodiments described herein;
FIG. 20 is a plot of first surface specular reflectance (in%, y-axis, 6 degree angle of incidence) versus wavelength (in nm, x-axis) for exemplary articles having various AG (anti-glare) haze levels according to one or more embodiments described herein;
FIG. 21 is a plot of first surface specular reflectance (in%, y-axis, 40 degree angle of incidence) versus wavelength (in nm, x-axis) for exemplary articles having various levels of AG haze according to one or more embodiments described herein;
FIG. 22 is a plot of first surface specular reflectance (in%, y-axis, 60 degree angle of incidence) versus wavelength (in nm, x-axis) for exemplary articles having various levels of AG haze according to one or more embodiments described herein;
FIG. 23 is a graph of light color coordinates (various angles of incidence,
FIG. 24 is a graph of gloss (measured at 60 degrees, in y-axis) versus haze (in% in x-axis) for substrates (including those having light altering features and optical coatings disposed thereon) according to one or more embodiments described herein;
FIG. 25 is a graph of distinctness of image (DOI) (20 degree incident measurement in y-axis) versus haze (in% in x-axis) for substrates (including those having light altering features and optical coatings disposed thereon) according to one or more embodiments described herein; and
fig. 26 is a plot of Pixel Power Deviation (PPD) (in%, along the y-axis) versus haze (in%, along the x-axis) for substrates (including those having light altering features and optical coatings disposed thereon) according to one or more embodiments described herein.
Embodiment 1: a coated article, comprising:
a transparent substrate having a major surface comprising a textured or roughened surface that includes light scattering;
an optical coating disposed on a major surface of a transparent substrate and forming an air-side surface, the optical coating comprising one or more layers of material, the optical coating having a physical thickness greater than 300 nm;
wherein the coated article exhibits a maximum hardness of about 10GPa or greater as measured on the air-side surface by a Berkovich indenter hardness test along an indentation depth of about 50nm or greater.
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