TW202011051A - Hybrid gradient-interference hardcoatings - Google Patents

Abstract

The present disclosure describes embodiments directed to durable and scratch resistant articles that include an optical coating that includes a gradient portion. In some embodiments, an article comprises: a substrate comprising a first major surface; and an optical coating disposed over the first major surface. The optical coating comprises: a second major surface opposite the first major surface; a thickness in a direction normal to the second major surface; and a first gradient portion. A refractive index of the optical coating varies along a thickness of the optical coating between the first major surface and the second major surface. The difference between the maximum refractive index of the first gradient portion and the minimum refractive index of the first gradient portion is 0.1 or greater. The absolute value of the slope of the refractive index of the first gradient portion is 0.1/nm or less everywhere along the thickness of the first gradient portion. The article exhibits an average single-surface reflectance of 15 % to 98% over the wavelength range 400 nm - 700 nm, measured at the second major surface. The article also exhibits a maximum hardness in the range from about 10 GPa to about 30 GPa, wherein maximum hardness is measured on the second major surface by indenting the second major surface with a Berkovich indenter to form an indent comprising an indentation depth of about 100 nm or more from the surface of the second major surface. Refractive index "slope" is measured along the thickness direction over a refractive index change of 0.04.

Description

Mixed gradient interference hard coating

The present disclosure relates to durable and scratch-resistant articles and methods of making them, and more specifically, to articles having an optical coating that exhibits abrasion resistance and scratch resistance. The optical coating has a gradient portion, but still exhibits the optical characteristics of a multilayer interference stack.

Multilayer interference stacks are known to be susceptible to wear or wear. Such wear can compromise any improvement in optical properties achievable with multilayer interference stacks. For example, optical filters are often made of multi-layer coatings with different refractive indices and made of optically transparent dielectric materials (such as oxides, nitrides, and fluorides). Typical oxides used in such optical filters are mostly band-gap materials that do not possess the mechanical properties, such as hardness, required for mobile devices, construction products, transportation products, or electrical products . Nitride and diamond-like coatings have high hardness values, but such materials do not have the required transmission for applications.

Wear damage can include reciprocating sliding contact from opposing objects (eg, fingers). In addition, wear damage can generate heat, leading to degradation of the chemical bonds of the membrane material, and causing peeling of the cover glass and other types of damage. Since wear damage usually lasts longer than the single event that caused scratches, the coating material damaged by wear will also oxidize and further reduce the durability of the coating.

It is known that multilayer interference stacks are also prone to scratching and are often more prone to scratching than the underlying substrate provided with a coating. In some cases, the obvious scratches include microductile scratches, which usually include a single groove in the material and have an extension length and a depth of about 100 nm to about 500 nm. Slight scratches may be accompanied by other types of visible damage, such as subsurface cracking, friction cracking, chipping, and/or wear. Evidence indicates that most scratches and other visible damage are caused by sharp contact that occurs in a single contact event. Once obvious scratches appear, the appearance of the product deteriorates, because the scratches will cause increased light scattering, resulting in a significant decrease in optical properties. A single event of scratch damage can be compared to wear damage. Single event scratching is not caused by multiple contact events, such as hard opposing objects (such as sand, gravel, and sandpaper) sliding back and forth, usually does not generate heat, which causes the chemical bond of the membrane material to degrade and cause peeling and other damage Types of. In addition, a single event scratches will not cause oxidation or involve the same conditions that cause wear damage, so the solutions commonly used to prevent wear damage cannot avoid scratches. Furthermore, known scratch and wear damage solutions often compromise optical properties.

In a multilayer interference stack (which has a sharp interface between multiple layers of the stack), such an interface may be the weak point of the stack's ability to resist mechanical damage.

Therefore, there is a need for new optical coatings and methods of making the same, which are resistant to abrasion, scratches, and have improved optical properties, as well as improved mechanical properties compared to multilayer interference stacks.

The present disclosure describes embodiments involving durable and scratch-resistant articles that include an optical coating that includes a gradient portion.

In some embodiments, the article includes: a substrate including a first major surface; and an optical coating disposed above the first major surface. The optical coating includes: a second major surface, relative to the first major surface; a thickness, in a direction perpendicular to the second major surface; and a first gradient portion. The refractive index of the optical coating varies along the thickness of the optical coating between the first main surface and the second main surface. The difference between the maximum refractive index of the first gradient part and the minimum refractive index of the first gradient part is 0.1 or more. At every location along the thickness of the first gradient portion, the absolute value of the slope of the refractive index of the first gradient portion is 0.1/nm or less. The article exhibits: an average single surface reflectivity of 15% to 98% in one of the wavelength ranges 400 nm to 700 nm measured at the second main surface. The product also exhibits a maximum hardness in the range from about 10 GPa to about 30 GPa, wherein the maximum hardness is measured on the second main surface by forming an indentation by pressing into the second main surface with a Berkovich indenter, The indentation includes an indentation depth of about 100 nm or more from the surface of the second main surface. Within the range of 0.04 refractive index changes, the refractive index "slope" is measured along the thickness direction.

In some embodiments, for any of the embodiments described herein, the difference between the maximum refractive index of the first gradient portion and the minimum refractive index of the first gradient portion is 0.3 or greater.

In certain embodiments, for any embodiment described herein, the article exhibits an average transmittance of 5% to 90% as measured at the second major surface.

In certain embodiments, for any embodiment described herein, the absolute value of the slope of the refractive index of the optical coating is 0.02/nm or less at each location along the thickness of the first gradient portion, or 0.012/nm or less.

In certain embodiments, for any of the embodiments described herein, the absolute value of the slope of the refractive index of the optical coating is 0.001/nm or greater at each location along the thickness of the first gradient portion, or 0.005/nm or more.

In certain embodiments, for any of the embodiments described herein, the optical coating further includes a high hardness portion. The thickness of the high-hardness portion is 200 nm or more, or 1000 nm or more. The average refractive index in the high-hardness portion is 1.6 or more. The maximum hardness of the high-hardness portion is 10 GPa or greater, wherein the maximum hardness is measured by pressing the thick high-hardness portion with a Berkovich indenter to form an indentation, the indentation including about 100 nm or more Indentation depth.

In some embodiments, for any of the embodiments described herein, between 95% or more of the thickness of the high hardness portion, the maximum refractive index of the high hardness portion and the minimum refractive index of the high hardness portion The difference is 0.05 or less.

In certain embodiments, for any of the embodiments described herein, the difference between the maximum refractive index of the high hardness portion and the minimum refractive index of the high hardness portion is 0.05 or smaller.

In some embodiments, as far as any of the embodiments described herein, in the embodiments of any paragraph in the Summary of the Invention, the optical coating is along the direction of the thickness from the second major surface toward the first major surface, according to The sequence includes: the first gradient portion; and the high hardness portion in contact with the first gradient portion. Where the high hardness portion contacts the first gradient portion, the difference between the refractive index of the high hardness portion and the maximum refractive index of the first gradient portion is 0.05 or less.

In some embodiments, for any of the embodiments described herein, the optical coating further includes a second gradient portion, the second gradient portion being disposed between the high hardness portion and the substrate. The second gradient part is in contact with the high hardness part. The difference between the maximum refractive index of the second gradient part and the minimum refractive index of the second gradient part is 0.05 or more. At each location along the thickness of the second gradient portion, the absolute value of the slope of the refractive index of the optical coating is 0.1/nm or less.

In some embodiments, as with any of the embodiments described herein, the refractive index of the first gradient portion increases monotonically along the thickness in a direction away from the second major surface. The optical coating further includes a multi-layer interference stack that includes discontinuous layers that are disposed between the high-hardness portion and the substrate.

In some embodiments, as with any of the embodiments described herein, the refractive index of the first gradient portion increases monotonically along the thickness in a direction away from the second major surface. The optical coating further includes a second gradient portion that fluctuates across the thickness of the gradient portion as a function of distance from the substrate.

In some embodiments, in the case of any of the embodiments described herein, the optical coating, along the thickness from the second major surface toward the first major surface, in sequence includes: a multi-layer interference stack, including discrete layers ; The high-hardness portion is in contact with the multilayer interference stack; and the first gradient portion is in contact with the high-hardness portion. The high hardness portion is in contact with the first gradient portion. The difference between the refractive index of the high-hardness portion and the maximum refractive index of the first gradient portion is 0.05 or less. The refractive index of the first gradient portion monotonously decreases along the thickness in a direction away from the second main surface.

In some embodiments, for any of the embodiments described herein, the optical coating consists only of the first gradient portion, the high hardness portion, and the multilayer interference stack. The optical coating directly contacts the substrate, and the second main surface is the outermost surface.

In some embodiments, for any of the embodiments described herein, the optical coating consists only of the first gradient portion, the high hardness portion, and the second gradient portion. The optical coating directly contacts the substrate, and the second main surface is the outermost surface.

In certain embodiments, for any of the embodiments described herein, the absolute value of the slope of the refractive index of the optical coating is 0.1/nm or less at each point in the optical coating.

In some embodiments, as far as any of the embodiments described herein, when measured on the second major surface, the article exhibits a single-sided reflection color range for all viewing angles from 0 to 60 degrees, the single The side reflection color range includes all a* points with a value of 5 or less.

In some embodiments, as far as any of the embodiments described herein, when measured on the second major surface, the article exhibits a single-sided reflection color range for all viewing angles from 0 to 60 degrees, the single The side reflection color range includes all b* points with a value of 5 or less.

In some embodiments, as far as any of the embodiments described herein, when measured on the second major surface, the article exhibits a single-sided reflection color range for all viewing angles from 0 to 60 degrees, the single The side reflection color range includes all a* points and all b* points with a value of 5 or less.

In some embodiments, as far as any of the embodiments described herein, when measured on the second major surface, the article exhibits a single-sided reflection color range for all viewing angles from 0 to 90 degrees, the single The side reflection color range includes all a* points and all b* points with an absolute value of 10 or less.

In some embodiments, as far as any of the embodiments described herein, when measured on the second major surface, the article exhibits a single-sided reflection color range for all viewing angles from 0 to 10 degrees, the single The side reflection color range includes at least one a* point or b* point with a value of 20 or more.

In certain embodiments, for any of the embodiments described herein, the article exhibits a maximum visible light reflectance of between 30% and 80%.

In certain embodiments, for any of the embodiments described herein, the article exhibits an average apparent reflectance between 15% and 50%.

In some embodiments, for any of the embodiments described herein, the optical coating is disposed directly on the first major surface of the substrate.

In certain embodiments, for any of the embodiments described herein, the article exhibits an average transmittance or average reflectance, which includes an average fluctuation amplitude of 20 percentage points or less in the optical wavelength range.

In some embodiments, for any of the embodiments described herein, the optical coating includes a thickness ranging from about 0.5 µm to about 3 µm.

In certain embodiments, for any embodiment described herein, the cumulative thickness of any portion of the optical coating between the high hardness portion and the second major surface is 200 nm or less, wherein the first The two main surfaces contain RI of 1.6 or less.

In certain embodiments, with respect to any of the embodiments described herein, the article includes a maximum hardness ranging from about 12 GPa to about 30 GPa or about 16 GPa to about 30 GPa, wherein by pressing a Berkovich indenter The two main surfaces are used to form an indentation to measure the maximum hardness. The indentation includes an indentation depth of about 100 nm or more from the surface of the second main surface.

In certain embodiments, for any of the embodiments described herein, the optical coating includes a composition gradient that includes at least two of Si, Al, N, and O.

In some embodiments, for any embodiment described herein, the gradient included in the optical coating is selected from at least one of the following: a porosity gradient, a density gradient, and an elastic modulus gradient.

In certain embodiments, with respect to any of the embodiments described herein, the article further includes: a first optional layer in contact with the first major surface; and a second optional layer in contact with the second major surface.

In certain embodiments, for any of the embodiments described herein, the article is a sunglasses lens.

In some embodiments, for any of the embodiments described herein, the article is a scratch-resistant mirror.

In certain embodiments, for any of the embodiments described herein, the article is a lens incorporated into eyeglasses.

In some embodiments, with respect to any of the embodiments described herein, the article is part of a housing or cover of a consumer electronic product. The consumer electronic product includes: a housing having a front surface, a rear surface, and side surfaces; electronics The components are provided at least partially within the housing. The electronic components include at least one controller, memory, and display provided on or near the front surface of the housing; and a cover plate disposed above the display.

In some embodiments, for any of the embodiments described herein, a method of forming an article includes the steps of: obtaining a substrate including a first major surface and including an amorphous or crystalline substrate; on the first major surface An optical coating is provided. The optical coating includes a second main surface and a thickness, the second main surface is opposite to the first main surface, and the thickness is in a direction perpendicular to the second main surface; and at least along the thickness of the optical coating A first gradient portion generates a refractive index gradient. The refractive index of the optical coating varies along the thickness of the optical coating between the first main surface and the second main surface. The difference between the maximum refractive index of the first gradient part and the minimum refractive index of the first gradient part is 0.1 or more. At every location along the thickness of the first gradient portion, the absolute value of the slope of the refractive index of the first gradient portion is 0.1/nm or less. The product exhibited an average single surface reflectivity of 15% to 98% in the wavelength range of 400 nm to 700 nm, measured at the second major surface. The product also exhibits a maximum hardness in the range from about 10 GPa to about 30 GPa, wherein the maximum hardness is measured by pressing the Berkovich indenter into the second main surface to form an indentation to measure the maximum hardness on the second main surface. Contains an indentation depth of approximately 100 nm or greater from the surface of the second major surface. Measure the "slope" of the refractive index along the thickness in the range of 0.04 refractive index change.

In some embodiments, for any embodiment described herein, generating a refractive index gradient includes changing at least one of the composition and porosity of the optical coating along the thickness of the optical coating.

In some embodiments, for any embodiment described herein, the optical coating is disposed on the first major surface by a physical vapor deposition sputtering process.

Additional features and advantages will be set forth in the following detailed description, and for those with ordinary knowledge in the technical field to which this case belongs, to some extent they can immediately be understood from their descriptions, or can be understood by practicing the embodiments described herein , Including the subsequent detailed description, patent application scope, and accompanying drawings.

It should be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide a summary or framework for understanding the nature and characteristics of the scope of patent applications. The accompanying drawings are included to provide a further understanding and the accompanying drawings are incorporated into and form part of this specification. The drawings illustrate one or more embodiments, and together with the description serve to explain the principles and operations of various embodiments.

Different embodiments will now be described in detail, and examples of the embodiments are depicted in the drawings.

For certain applications, specific optical properties, including specific reflectance and optional transmission properties, may also be required in the hard coating, which also provides high hardness and scratch resistance. These applications may include the outside of glasses, sunglasses, RF transparent back covers or cases for smartphones and similar devices, smartphone covers, smart watches, head-up display systems, car windows, mirrors, display covers, touch Control screen and display surfaces, architectural glass and surfaces, and other decorative, optical, display or protective applications.

Existing hard coatings include a "discrete layer" multilayer design that uses optical interference effects, and a "gradient" design that gradually changes in refractive index. Previous discontinuous layer designs are usually characterized by a sudden change in the refractive index across the interface, for example, the change in the refractive index across the interface or transition zone (thickness less than 2nm, less than 1nm, or even less than 0.5nm) is 0.2 or More, and in some cases 0.4 or more.

Discontinuous layers may be more prone to certain mechanical failure modes, such as delamination, chipping, or spalling of layers due to low adhesion energy, stress, or atomic/molecular bond breakage between different materials at the abrupt interface. Under certain test conditions using "gradient" films with gradual changes in composition (resulting in gradual changes in refractive index), improved levels of mechanical properties have been observed. Xianxin, the composition gradient can improve the cohesion and adhesion of the coating structure, thereby improving the resistance to scratches and damage under certain conditions. Sub-wavelength characteristics and interference effects associated with discontinuous layers are often required to accurately control the reflection and transmission spectra in order to use a material system (eg, SiO ₂ ) with a minimum refractive index of about 1.45 in air. Gradient part

In some embodiments, a gradient approach (optionally combined with an interference layer approach) is used to create the optical hard coat. It is believed that under certain conditions, the presence of one or more gradient portions may provide improved resistance to scratches and damage. In certain preferred embodiments, the materials forming the gradient portion (and optionally all portions of the optical coating) are completely dense, that is, they are non-porous or have a porosity or pore volume of less than 10%, less than 5% or even less than 1% of the total volume of said part.

The refractive index of the materials described herein is usually related to the mechanical properties of the material (such as the hardness of the material). Therefore, a sudden change in refractive index means a sudden change in hardness, and may also cause a sudden change in stress, thermal expansion, atomic bond arrangement, and other factors that can affect mechanical properties. Xianxin, the abrupt interface between two materials with significantly different refractive indices may be the weak point of the optical coating's ability to resist mechanical damage. However, multilayer interference stacks rely on such sudden changes to obtain the desired optical properties.

Relative to the abrupt interface, a compositionally graded interface or "gradient portion" can be used for the transition between different refractive indices. Xianxin, compared with the abrupt interface, the gradient part can impart mechanical robustness, including scratch resistance and damage resistance. The gradient part is characterized by a gradual change in the refractive index. For example, some or all of the refractive index transition zone in the coating structure is characterized by an absolute (positive or negative) value of the refractive index "slope" of 0.1/nm or less (meaning that the coating thickness per nm Refractive index change less than 0.1), 0.05/nm or less (or less than about 0.5 per 10 nm), 0.02/nm or less (or less than about 0.2 per 10 nm), 0.016/nm or less, 0.012/nm or less , Or even 0.01/nm or less (less than about 0.1 per 10 nm).

In some embodiments, the gradient of the gradient of the refractive index is 0.001 or greater, 0.002 or greater, or 0.005 or greater.

As used herein, the refractive index "slope" can be used to describe how fast the refractive index changes as a function of position along the film thickness. The slope of the refractive index can be calculated by dividing the change in the refractive index by the distance at which the change occurs. In optical coatings, the refractive index is usually constant in the direction perpendicular to the thickness direction of the coating, and the refraction is measured relative to the change in the distance in the direction of the coating thickness (eg, thickness direction 126 in Figure 1) Coefficient slope.

The refractive index gradient can be realized as a continuous change in the refractive index, or as a series of small orders of the refractive index. As far as the order size is small enough, it is expected that the optical and mechanical properties are the same as the smooth gradient with no order of refractive index. However, if the slope is measured at a sufficiently small distance interval including the refractive index order, while excluding most of the distance between the orders, the small order of the refractive index may have a locally high refractive index slope. In order to avoid such anomalies caused by the local measurement of the slope at small distance intervals at the precise position of the small refractive index, the refractive index slope described herein can be measured and calculated at discrete refractive index intervals. Unless otherwise specified, the slope of the refractive index discussed in this article is measured and calculated at a refractive index interval of 0.04. In other words, the slope of the refractive index is 0.04 divided by the distance the refractive index changes by 0.04. When calculating the slope of the refractive index at a step size of 0.04 or less, this method causes the distance between the steps of the refractive index to be considered. In some embodiments, the refractive index slope can be calculated on the following refractive index intervals: 0.02, 0.03, 0.04, 0.05, or 0.06.

When the slope of the refractive index is zero or close to zero over a relatively large distance, the above method of calculating the slope of the refractive index may not work because there is no refractive index interval of 0.04. Therefore, if there is no refractive index interval of 0.04 at a distance of 100 nm or greater, the slope of the refractive index can be calculated at a distance of 100 nm. In other words, in this case, the slope of the refractive index is the change in the refractive index that occurs at 100 nm (less than 0.04) divided by 100 nm.

The gradient portion may have a refractive index that increases, decreases, or fluctuates in thickness across the gradient portion as a function of distance from the substrate. Such an increase or decrease in the refractive index may be monotonic.

In some embodiments, in order for the gradient portion to have a significant effect on the optical characteristics of the article, the difference between the maximum refractive index of the first gradient portion and the minimum refractive index of the first gradient portion should be 0.05 or greater, 0.1 Or greater, 0.3 or greater, or 0.4 or greater. In some embodiments, the monotonically changing endpoints of the refractive index forming the single gradient portion or multiple gradient portions may include at least one of the following refractive index endpoints: higher than 1.65, higher than 1.7, higher than 1.8, or even higher than 1.9 , And has another endpoint of the refractive index: below 1.6, below 1.55, or even below 1.5. Thick high hardness part

In some embodiments, in addition to the gradient portion, the optical coating contains a thick high hardness portion. In such a case, the scratch resistance can be improved by thick (eg, 200 nm to 5000 nm thick) high hardness portions. In some embodiments, the thickness of the soft material above the thick high-hardness portion is limited. For example, a lower hardness or low refractive index material (eg, SiO ₂ ) at 300 nm or thinner, 200 nm or thinner, or even 100 nm or thinner may be located above the thick hard layer of the hard-coated article (ie, disposed at (Facing outward or on the user's surface). The amount of lower hardness or low refractive index material located above the thick hard layer may be zero, or may be 1 nm or more.

As long as the refractive index and hardness standards described herein are met, the thick high-hardness portion need not be a true single material or single layer. For example, a thick hard layer may include multiple thin layers or nanolayers, such as in a "superlattice" structure, or other hard layer structures that include multiple materials, compositions, or structural layers or gradients. Without being limited by theory, in a superlattice structure, the stacking of sufficiently thin layers of different materials can produce a unique microstructure, so that the superlattice structure has optical and mechanical properties similar to a thick layer of a single material, and has more than The hardness of the material in each thin layer. An example structure is disclosed in WO 2016/138195, which is incorporated herein by reference in its entirety.

The thick high-hardness portion may have the following average refractive index: 1.6 or greater, 1.7 or greater, or 1.8 or greater. These refractive indexes usually correspond to the selection of high hardness materials. The high hardness portion may have the following indentation hardness: 10 GPa or greater, 12 GPa or greater, 14 GPa or greater, GPa or greater, 18 GPa or greater, or 20 GPa or greater, or between 10 Between 30 GPa.

The thick high-hardness part can have the following physical thickness: 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1200 nm, 1400 nm, 1600 nm, 1800 nm, 2000 nm, 2500 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, 10000 nm, and all ranges and sub-ranges in between.

When measured by the Berkovich indenter hardness test, the thick high hardness layer may have the following maximum hardness: about 10 GPa or greater, about 12 GPa or greater, about 15 GPa or greater, about 18 GPa or greater, or About 20 GPa or greater. To characterize the hardness, the thick high-hardness portion can be deposited as a single layer.

In some embodiments, a thin soft layer can be bonded to a thick high-hardness portion. For example, for a thickness of 95% or more of the high-hardness portion, the maximum refractive index and the minimum refractive index may be within 0.05 of each other. However, the thickness of 5% of the high hardness portion may have a lower refractive index. In this case, this lower refractive index (and correspondingly softer material) can be buried deep enough in the optical coating so that it does not affect the overall structural properties much. However, it is preferable to avoid such softer materials in thick high-hardness portions. For example, the maximum refractive index and the minimum refractive index are each within 0.05 of each other in the thick high-hardness portion.

In some embodiments, the thick high hardness portion may have a relatively constant (and high) refractive index. For example, with respect to the thickness of 95% of the thick high-hardness portion, or each place within the thick high-hardness portion, the maximum refractive index and the minimum refractive index may be within 0.05 of each other. In some embodiments, the refractive index in the thick high-hardness portion may have a gradient, and the difference between the maximum refractive index and the minimum refractive index in the thick high-hardness portion may exceed 0.05. Limited or unobtrusive interface in hard coating

In some embodiments, the optical coating has a limited or non-obtrusive interface in addition to combining the gradient portion and the high hardness portion. The abrupt interface occurs at a short distance where the refractive index suddenly changes. Xianxin, such an abrupt interface may be a weak point that reduces the mechanical properties. For example, by using gradient sections and thick high-hardness sections in the optical coating instead of multilayer interference stacks, and by matching coefficients at the junctions between different sections in the optical coating, abrupt interfaces can be avoided .

In some embodiments, there may be an abrupt interface, but any abrupt interface is buried under the thick high hardness portion. The gradient portion may exist above the thick high hardness portion. Xianxin, the thick high hardness part can protect any underlying layer from mechanical damage, so that the abrupt interface existing under the thick high hardness part has little or no harmful effect on the mechanical properties.

In some embodiments, abrupt interfaces are completely avoided in the optical coating. The optical coating consists only of a gradient portion, a thick high hardness portion, and optionally a thin (eg, <200 nm) low refractive index portion, which has a constant coefficient. Xianxin, the lack of abrupt interfaces enhances the mechanical properties. For example, the absolute value of the slope of the refractive index of the optical coating may be 0.1/nm or less, 0.05/nm or less, 0.02/nm or less, 0.016/nm or Smaller, 0.012/nm or smaller, or even 0.01/nm or smaller.

In some embodiments, abrupt interfaces are avoided at the interface between the gradient portion and/or the thick high hardness portion. For example, when moving from one part across the interface to another, the difference in refractive index at such an interface may be 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less , 0.01 or less, or 0.005 or less. Reflectivity

In some embodiments, even if there is no abrupt interface in the optical coating, the optical hard coating using the gradient method still uses the optical interference effect to generate the optical coating, the optical coating has optical properties, such as usually interferes with multiple layers Stack-related reflectivity.

Specifically, when measured on the second major surface, one or more surfaces of the hard-coated article or one or more interfaces of the hard coat layer may have an average of 15% to 99% in the wavelength range of 400 nm to 700 nm Reflectivity. The average reflectance can be: 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% , 90%, 95%, 98%, 99%, and all ranges and subranges in between. These reflectance values can represent the reflectance of a single surface product at a wavelength of 550 nm, the average reflectance from 500 to 600 nm, the average reflectance from 450 to 650 nm, the average reflectance from 420 to 680 nm, and the average from 400 to 700 nm The average reflectance of wavelength, or the average reflectance of bright vision. Unless otherwise specified, the reflectance described herein is the average reflectance in the wavelength range of 400 nm to 700 nm. These same reflectance values listed above may also represent the maximum reflectance in the visible light range of 400 to 700 nm, rather than the average reflectance.

In certain embodiments, for any of the embodiments described herein, the article exhibits a maximum visible light reflectance between 30% and 80%. In certain embodiments, for any of the embodiments described herein, the article exhibits an average bright-view reflectance between 15% and 50%.

Surprisingly, these reflectances can be achieved using hard coatings incorporating gradient portions. Even more surprisingly, these reflectances can be achieved using a hard coating that does not have any abrupt interfaces, that is, the entire hard coating is a thick, high hardness with one or more gradient portions of full density and low or no porosity Partial or thin (eg, <200nm) low refractive index part. These low reflectance values are surprising because for hard coatings, multilayer interference stacks with abrupt interfaces are often used to produce reflectance in this range.

As used herein, the term "transmittance" is defined as the percentage of incident optical power within a specific wavelength range that penetrates a material (eg, an article, substrate, or optical film or portion of the same). The term "reflectivity (reflectivity)" is similarly defined as the percentage of incident optical power reflected from a material (eg, article, substrate, or optical film, or part of the same) within a specific wavelength range. A specific line width can be used to measure transmittance and reflectance. In one or more embodiments, the spectral resolution of the characteristics of transmission and reflection is less than 5 nm or 0.02 eV. Unless otherwise specified, reflectance and transmittance are measured at near normal incidence. Transmittance

In some embodiments, optical hard coatings that use a gradient approach still utilize the optical interference effect to produce specific reflectance and transmittance characteristics in the article. Although the optical coating lacks an abrupt interface, the single surface reflectance described above can be obtained together with the specific transmittance.

Specifically, the hard coated product may have the following overall product average transmittance: 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, and all ranges and sub-ranges therebetween, the values apply to one or more optical wavelengths specified for the above reflectance range. Unless otherwise specified, the transmittances described herein are average transmittances in the wavelength range of 400 nm to 700 nm.

Surprisingly, these transmittances and reflectances can be achieved using hard coatings containing gradient portions. More surprisingly, these transmissions can be achieved using a hard coating that does not have any abrupt interfaces (ie, the entire hard coating is one or more gradient parts, thick high hardness parts, or thin low refractive index parts) Rate and reflectivity. Because multilayer interference stacks with abrupt interfaces are commonly used to produce such combinations, it is surprising that these reflection and transmission characteristics combined with high hardness and/or scratch resistance. Overall optical coating thickness

The physical thickness of the optical coating 120 may range from about 0.1 µm to about 5 µm. In some examples, the physical thickness of the optical coating 120 may be in the following ranges: from about 0.01 µm to about 0.9 µm, from about 0.01 µm to about 0.8 µm, from about 0.01 µm to about 0.7 µm, from about 0.01 µm To about 0.6 µm, from about 0.01 µm to about 0.5 µm, from about 0.01 µm to about 0.4 µm, from about 0.01 µm to about 0.3 µm, from about 0.01 µm to about 0.2 µm, from about 0.01 µm to about 0.1 µm, From about 0.02 µm to about 1 µm, from about 0.03 µm to about 1 µm, from about 0.04 µm to about 1 µm, from about 0.05 µm to about 1 µm, from about 0.06 µm to about 1 µm, from about 0.07 µm to About 1 µm, from about 0.08 µm to about 1 µm, from about 0.09 µm to about 1 µm, from about 0.1 µm to about 1 µm, from about 0.1 µm to about 2 µm, from about 0.1 µm to about 3 µm, from About 0.1 µm to about 4 µm, from about 0.1 µm to about 5 µm, from about 0.2 µm to about 1 µm, from about 0.2 µm to about 2 µm, from about 0.2 µm to about 3 µm, from about 0.2 µm to about 4 µm, from about 0.2 µm to about 5 µm, from about 0.3 µm to about 5 µm, from about 0.4 µm to about 5 µm, from about 0.5 µm to about 10 µm, from about 0.6 µm to about 3 µm, from about 0.7 µm to about 2 µm, from about 0.8 µm to about 1 µm, or from about 0.9 µm to about 1 µm, and all ranges and subranges therebetween. Other thicknesses may also be applicable. Materials and processes for hard coating

In some embodiments, the coating structure may include a hard oxide, nitride, or oxynitride layer, optionally combined with a metal layer. Preferred hard coating materials include: AlN _x , SiN _x , SiO _x N _y , AlO _x N _y , Si _u Al _v O _x N _y , SiO ₂ , Al ₂ O ₃ , and mixtures of the aforementioned components, It has an intermediate value of refractive index and hardness representing the combination/mixing characteristics of these materials.

In certain embodiments, metal mode sputtering may be used to deposit the hard coat layer. In the metal mold sputtering, the sample is fixed to the moving surface, the metal sputtering source sequentially passes through the moving surface (as step one), and then the plasma source passes through the moving surface (as step two). The plasma source may contain oxygen and nitrogen. Step 1 and step 2 are repeated multiple times to deposit a thick film composed of a metal layer that reacts with oxygen or nitrogen to form a hard oxide, nitride, or oxynitride layer.

During the metal mold sputtering process, when the samples are in front of the metal source, they are coated with a thin layer of metal. The thickness of the metal deposited during one pass in front of the metal source depends on the metal deposition rate and the length of time the sample spends in front of the metal source. When the sample then moves to the plasma source location, the thin metal layer reacts with the plasma to form a thin film of metal nitride and/or metal oxide. The degree or integrity of the chemical reaction that forms a metal nitride or oxide depends on the chemical activity of the reactive nitrogen and oxygen species, the chemical activity of the metal surface, and the length of time the sample spends in front of the plasma source.

For example, the sample can be mounted on a cylindrical barrel with the axis of the barrel oriented vertically. The diameter and rotation rate of the barrel (sometimes measured in revolutions per minute) determine the speed at which the sample moves on the metal and plasma source. The cylindrical barrel is contained in a vacuum chamber containing a sputtering source (metal source) and an inductively coupled plasma (ICP) source. The column rotates around its axis to move the sample through the metal source and the plasma source in a sequential and repeating manner.

The sputtering source rate is determined by the processing parameters, which include gas flow rate, chamber pressure, the distance between the sample and the magnetron source, the power applied to the sputtering source, the shape and size of the sputtering source, and other characteristics. The chemical activity of the plasma components can be quantified by actinometry or electrical detection. These measurements can quantify plasma density, electron potential, and ion and electron temperature distribution. However, these may be laborious measurements and are usually not performed. Conversely, ICP plasma is generally described by the coil size, power to the coil, and gas flow to the coil area.

Using a deposition chamber manufactured by OptoRun (a company), the films described herein were deposited by metal mold sputtering. The barrel diameter is about 1650 mm and the rotation speed is 80 rpm. The chamber pressure is about 2 mTorr. We use dual rotatable cylindrical magnetron targets with a length of about 850 mm and a diameter of about 180 mm. The sputtering surface of the target consists of silicon and/or aluminum. The magnet of the magnetron generates a magnetic field strength of about 500 Gauss on the surface of the target. Power is applied to the magnetron pair in alternating current (AC) mode, powered by a Huttinger (a company) power supply operating in intermediate frequency mode. During half of the AC cycle in the intermediate frequency mode, one magnetron cylinder is powered as a cathode (negative charge), and the other magnetron cylinder is powered as an anode (positive charge). The projection distance from the surface of the magnetron to the surface of the sample is about 100 mm. The reactor uses four flat spiral flat coils for ICP, located at the corners of the square array. Each of the four coils is composed of about 2 turns of a copper coil with a diameter of about 12 mm, and has a diameter of about 400 mm. The coil is customized by OptoRun (a company).

The SiN and SiON processes used for the data in this application use the set of conditions specified in the table below. Table 1

Other processes can produce SiN _x and SiO _x N _y , wherein the materials produced by their other processes can have the characteristics claimed in this application. Other processes that can produce SiN _x and SiO _x N _y films include: reactive sputtering, evaporation techniques (eg, electron beam evaporation), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD) , Atomic Layer Deposition (ALD), plating technology (eg, electroplating) and wet chemical deposition technology (eg, sol-gel).

It was found that the hardness and refractive index values provided for the sputtering process conditions of high hardness SiN _x , SiO _x N _y and Si _u Al _v O _x N _y are substantially consistent with the high hardness AlO _x N _y , which is further described in US Patent No. US No. 9,335,444, this US patent is incorporated herein by reference in its entirety. These high-hardness materials are characterized by a single-layer film hardness of >16, >18, and >20 measured on a single-layer film with a thickness of 500-5000 nm on a glass substrate (where the glass substrate has a hardness of ~7 GPa) , Or from 16 GPa to 25 GPa. In general, these high-hardness materials also have the following characteristics: a refractive index (n) value of about 1.85 to 2.1 (measured at 550 nm); and measured at a wavelength of 400 nm, less than about 1 e-2, less than 5 e-3, less than 1e-3 or even less than 5e-4 composite refractive index (absorption coefficient, k) value. Measure K at 400 nm for higher sensitivity, and usually return n at 550 nm. Generally speaking, all these high hardness materials can be manufactured from reactive sputtering, metal-mode reactive sputtering and PECVD at process temperatures below 400C or even below 300C.

It has been found that when properly adjusted to achieve the desired combination of hardness, refractive index, film stress, and low optical absorption, "AlON", "SiON", and "SiAlON" components are essential in the optical design disclosed herein Interchangeable. The preferred thin film deposition process is reactive sputtering or metal mold sputtering, but other processes such as PECVD can also be used to make the coating of the present disclosure. For the purpose of this disclosure, single-layer and multi-layer films of AlO _x N _y , SiO _x N _y and Si _u Al _v O _x N _y can be manufactured by reactive sputtering and metal mold sputtering, and they The hardness and optical properties are adjusted to achieve the desired range. Suitable manufacturing processes are described, for example, in US Patent No. US 9,335,444, which is incorporated herein by reference in its entirety. The measured optical properties of these coatings can be used in thin film design simulations to produce molding examples of the present disclosure.

The optical layer (which may be a hard layer or a softer layer) may also include additional materials known in the field of thin film technology, such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , HfO ₂ , Known in the technical field to which this case belongs, and mixtures, layered structures, and combinations of the foregoing. application

In some embodiments, applications include display covers, touch screens, smart phone housing components, such as cover elements or back plates (eg, hard-coated glass or glass ceramics), sunglasses exterior, and scratch protection mirror.

Different substrates can be used for different applications. The molding example herein uses Corning Glass Code 5318, which is commercially available from Corning Corporation of Corning, New York, USA. It should be understood that alternative substrates can also be used as substrates for these coating designs. Non-limiting examples include: transparent non-absorbent glass (such as Gorilla glass), partially absorbent ophthalmic glasses, such as Corning Grey 17 (glass code 82524), or glass ceramics (such as chemically strengthened black glass) ceramics). These different substrate options maintain substantially the same first surface reflectivity and reflected color values (and the transmittance value will vary greatly by the choice of substrate). In the example of a black glass ceramic substrate, the total product transmittance may be less than 10% or less than 1%. In the case of a transparent non-absorbent substrate, the transmittance will be close to 100-% reflectivity of the coating (1 ^st surface), or 100-4-% reflectivity of the coating (the latter from the backside of the transparent glass substrate, The uncoated surface is considered to have a reflectivity of 4%). Absorption and metal layer

In certain embodiments, the hard coat design described herein can incorporate a metal layer or an absorber layer. Absorbent layers are particularly useful in sunglasses applications, which are intended to minimize the reflectivity on the user side of the coated article. In such cases, it may be preferable to position the absorbent material on the user side of the hard coat, such as an absorbent glass substrate facing the user's eyes, and a reflective or colored hard coat on the outward-facing surface of the article , For reflectivity and scratch resistance towards the external environment. In the case of incorporating a single-sided absorbent article structure, the reflection from both sides of the article may vary due to the absorbent. In such cases, unless otherwise indicated, the reflectance values quoted here will apply to the environment-facing surface, the hard-coat surface, or between the environment and the hard-coat/reflective layer with a low absorption level surface. In some embodiments, the absorber layer may be located between the hard coat layer and the substrate. In certain embodiments, it may be desirable to exclude metal from the stack, as in the examples described below, to maximize adhesion and scratch resistance. Placement of optical coatings on specific products

In some embodiments, since both sides of the glasses or sunglasses may be subject to wear, especially during cleaning, it may be desirable to place an anti-scratch coating on both sides of the glasses or sunglasses lenses. In the case of absorbing sunglasses or spectacle lenses, it is often desirable to place a higher reflectivity scratch resistant coating on the outer surface of the sunglasses, and on the inner (facing the user's eye) surface of the lens of the sunglasses Low-reflectivity or anti-reflective scratch-resistant coating. For example, the coating on the outer (front) surface of the lens may have an average reflectance as described herein. The inner (rear) surface of the lens can have a hard coating that can use any suitable optical coating to have a clear visual reflectance of less than 2%. Suitable examples are described in US Patent No. US 9,335,444, which is incorporated herein by reference in its entirety. WO2016018490 and WO2014182639 are incorporated herein by reference in their entirety.

In certain embodiments, when the scratch-resistant coating is placed on both sides of spectacles or sunglasses lenses, the surfaces on both sides are endowed with high hardness and scratch resistance. In these examples, it may be preferable to place a low-reflectivity coating (eg, <4% clear visual average reflectivity) on the inner surface of the sunglasses, and a high-reflective coating (eg, >6% The average visual reflectance of) is placed on the outer surface. In this case, the order of the elements may be: 1) the user's eyes; 2) a low-reflectivity coating; 3) an absorbing glass substrate; 4) a high-reflectivity coating; 5) the sun or the surrounding environment. The low reflectance coating may be, for example, any suitable optical coating. Suitable examples are described in US Patent No. US 9,335,444, which is incorporated herein by reference in its entirety. The high reflectivity coating may be, for example, the coating described herein.

In eyewear applications, as opposed to sunglasses, it is preferable to use a low-reflectivity scratch-resistant coating on both sides of a transparent (non-absorbent glass substrate). In other cases, the use of a single scratch-resistant coating (most likely on the outward-facing surface of the glasses or sunglasses) will be more cost-effective.

In certain embodiments, the coatings described herein may also be useful for automotive glass applications, such as side windows or skylights or lamp housings. The coating can provide a low-reflectivity scratch-resistant coating with high scratch resistance and weather resistance.

In display cover and touch screen applications, it is generally preferred to place the optical hard coating on the user-facing/exposed surface of the display or screen, but in some such applications, it may be desirable to place the coating Different coatings are provided on both sides of the display cover, or optionally on both sides of the display cover. For example, a low-cost, low-hardness anti-reflective coating can be placed on the back side of the display cover to protect it from scratches caused by its position, and can be implemented as disclosed The high-hardness anti-reflection coating of the example is placed on the user-facing side of the front of the display cover. parameter

Parameters that can be considered or specified based on this disclosure include the following:

-Hardness of coated products and coated surfaces.

-Fraction of softer (usually lower refractive index) materials in the coating stack.

-The total amount (thickness) of the softer materials in the coating stack.

-The total amount (thickness) of the softer material on the exposed (away from the substrate) side of the thickest high hardness (high coefficient) layer.

-Maximum reflectance in the visible range.

-The average reflectance in the visible range (eg, the average reflectance in clear vision).

-Transmittance in the visible range (combined with absorptive material or substrate or not combined with absorptive material or substrate).

-Reflected color and color shift at optical incidence angle.

-Transmission color and color shift at optical incidence angle. Product structure

Referring to FIG. 1, the article 100 according to one or more embodiments may include a substrate 110 and an optical coating 120, and the optical coating 120 is disposed on the substrate. The substrate 110 includes opposed major surfaces 112, 114 and opposed minor surfaces 116, 118. The optical coating 120 shown in FIG. 1 is disposed on the main surface 112; however, in addition to the optical coating 120 being disposed on the main surface 112, the optical coating 120 may be additionally or alternatively disposed on the main surface 114 and And/or one or both of the opposing subsurfaces. The optical coating 120 forms an outer surface 122. Surface 112 may also be referred to herein as a "first major surface", and surface 122 may also be referred to herein as a "second major surface."

As shown, the optical coating 120 includes opposing major surfaces 122, 124 that are parallel to the opposing major surfaces 112, 114 and perpendicular to the thickness direction 126 of the optical coating 120.

The thickness of the optical coating 120 may be about 1 μm or more, while still providing articles exhibiting the optical properties described herein. In some examples, the thickness of the optical coating 120 may range from about 1 µm to about 20 µm (eg, from about 1 µm to about 10 µm, or from about 1 µm to about 5 µm). Measured by cross-sectional scanning electron microscope (SEM), by transmission electron microscope (TEM), or by optical ellipsometry (eg, by n & k analyzer), or by thin-film reflectometer The thickness of the thin-film element (eg, scratch-resistant layer, optical film layer, etc.). For multilayer devices (eg, layers of optical film stacks), thickness measurement is preferably performed by SEM or TEM. Unless otherwise specified, the thickness is measured using ellipsometry.

Article 100 may also include one or more optional layers 170, 180. For example, the optional layer 170 may be an adhesive layer, a crack mitigation layer, and the optional layer 180 may be an easy-to-clean layer. The optional layers 170 and 180 are optional and need not be included in the article 100. Although the optional layers 170, 180 are omitted in the drawings other than FIG. 1, they may exist in the embodiments of the other drawings as the case may be.

As used herein, the term "layer" may include a single layer or may include one or more sublayers. Such sub-layers can directly contact each other. The sub-layer may be composed of the same material or two or more different materials. In one or more alternative embodiments, interlayers with different materials of sub-layers are interposed therebetween. In one or more embodiments, the layer may include one or more continuous and uninterrupted layers, and/or one or more discontinuous and intermittent layers (ie, layers formed of different materials adjacent to each other) . The layer or sublayer can be formed by any method known in the technical field to which this case belongs, including discrete deposition or continuous deposition processes. In one or more embodiments, the layer may be formed using only a continuous deposition process or only a discrete deposition process.

As used herein, the term "setting" includes applying, depositing, and/or forming a material onto a surface using any method known in the technical field to which this case pertains. The materials provided can constitute the layers as defined above. The phrase "set on" includes the case where the material is formed to the surface so that the material directly contacts the surface, and also includes the case where the material is formed on the surface and one or more intermediary materials are located between the set material and the surface. The intermediary material may constitute the layer as defined above.

As shown in FIG. 2, the article 200 includes an optical coating 120, and the optical coating 120 includes a first gradient portion 130. Figure 2 illustrates a general embodiment, where the optical coating may or may not include the additional layer 125. The additional layer 125 may be a gradient portion, a thick high hardness portion, a multi-layer interference stack, or other optical coating components. There may be more or fewer additional layers 125 than shown in FIG. 2. The first gradient portion 130 may be located at any position in the optical coating 120, including a position in contact with one or both of the opposing main surfaces 122, 124.

As shown in FIG. 3, the article 300 includes an optical coating 120 that includes both the first gradient portion 130 and the thick high hardness portion 140. Referring to FIG. 2, FIG. 3 illustrates the additional layer 125 which may or may not exist, and may be the same type of layer as the additional layer 125 of FIG. 2. Each of the first gradient portion 130 and the thick high hardness portion 140 may be located at any position in the optical coating 120, including a position in contact with one of the opposing major surfaces 122, 124.

FIG. 4 shows a product 400 according to an embodiment, in which the thick high-hardness portion 140 and the first gradient portion 130 are stacked on the substrate 110 in this order to form the optical coating 120 without an intermediate layer, and the optical coating There are no additional layers 125 in 120. FIG. 5 shows a product 500 of an embodiment, in which an optical coating 120 is formed by stacking a second gradient portion 150, a thick high hardness portion 140, and a first gradient portion 130 on the substrate 110 in this order, without an intermediate Layer, and there is no additional layer 125 in the optical coating 120. In some embodiments, the structure of FIG. 5 may have a refractive index that monotonically increases in a direction in which the thickness moves from surface 122 toward surface 112. In some embodiments, the refractive index of the second gradient portion decreases monotonously in the same direction. As used herein, "monotonically increase" means that the refractive index rises or remains constant as a function of distance, but does not decrease. As used herein, "monotonically decrease" means that the refractive index decreases or remains constant as a function of distance, but does not increase. Examples 1 to 3 each include a gradient portion, which is an example of the monotonic function described in this paragraph. Multilayer interference stack

In some embodiments, the additional layer 125 may include one or more multilayer interference stacks. FIG. 6 depicts an example article 600 that includes a multilayer interference stack 610. In the embodiment of FIG. 6, the optical coating 120 is composed of a multilayer interference stack 610, a thick high-hardness portion 140, and a first gradient portion 130 stacked on the substrate 110 in this order. In one or more embodiments, the multilayer interference stack 610 may include a period 620 that includes two or more layers. In one or more embodiments, the two or more layers may be characterized as having different refractive indexes from each other. In some embodiments, the section 620 includes a first low RI layer 622 and a second high RI layer 624. The difference in refractive index between the first low RI layer and the second high RI layer may be about 0.01 or greater, 0.05 or greater, 0.1 or greater, or even 0.2 or greater.

As shown in FIG. 6, the multilayer interference stack 610 may include a plurality of sections 620. The single section includes a first low RI layer 622 and a second high RI layer 624, such that when a plurality of sections are provided, the first low RI layer 622 (designated as "L" for description) and the second high RI layer 624 ( Designated as "H" for illustration) alternating in the following layer order: L/H/L/H or H/L/H/L, making the first low RI layer and the second high RI layer appear along the multilayer interference stack 610 The thickness of the solids alternates. In the example of FIG. 6, the multilayer interference stack 610 includes three sections. In some embodiments, the multilayer interference stack 610 may include up to 25 sections. For example, the multilayer interference stack 610 may include from about 2 to about 20 sections, from about 2 to about 15 sections, from about 2 to about 10 sections, from about 2 to about 12 sections, From about 3 to about 8 sections, from about 3 to about 6 sections.

The multilayer interference stack may also include other layers, such as a layer with a high or low refractive index different from the refractive index of the first low RI layer 622 and the second high RI layer 624, or a layer with a medium refractive index. As used herein, the terms "low RI", "high RI", and "medium RI" refer to RI values relative to each other (eg, low RI <medium RI <high RI). In one or more embodiments, the term "low RI" used with the first low RI layer or the third layer includes a range from about 1.3 to about 1.6. In one or more embodiments, the term "high RI" used with the second high RI layer or the third layer includes a range from about 1.6 to about 2.5 (eg, about 1.85 or greater). In some embodiments, the term "medium RI" used with the third layer includes a range from about 1.55 to about 1.8. In some cases, the ranges of low RI, high RI, and medium RI may overlap; however, in most cases, the RI of a particular multilayer interference stack 610 has a general correlation: low RI <medium RI <high RI.

Exemplary materials suitable for multilayer interference stack 610 include: SiO ₂ , Al ₂ O ₃ , GeO ₂ , SiO, AlO _x N _y , AlN, SiN _x , SiO _x N _y , Si _u Al _v O _x N _y , Ta _{2 O 5, Nb 2 O 5} , TiO 2, ZrO 2, TiN, MgO, MgF 2, BaF 2, CaF 2, SnO 2, HfO 2, Y 2 O 3, MoO 3, DyF 3, YbF 3, YF 3 , CeF ₃ , polymer, fluoropolymer, plasma polymerized polymer, siloxane polymer, hemisiloxane, polyimide, fluorinated polyimide, polyether amide imide, polyether sulfone , Polystyrene, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic polymer, urethane polymer, polymethyl methacrylate, the following description is suitable for scratch resistance Other materials of the layer, and other materials known in the technical field to which this case belongs. Some examples of materials suitable for the first low RI layer include: SiO ₂ , Al ₂ O ₃ , GeO ₂ , SiO, AlO _x N _y , SiO _x N _y , Si _u Al _v O _x N _y , MgO, MgAl _{2 O 4, MgF 2, BaF} 2, CaF 2, DyF 3, YbF 3, YF 3 , and CeF _3. The nitrogen content of the materials used in the first low RI layer can be minimized (eg, in materials such as Al ₂ O ₃ and MgAl ₂ O ₄ , or, for example, compared to SiO _x used to form high coefficient materials N _y , SiO _x N _y used to form low coefficient materials will generally have a lower nitrogen content). Some examples of materials suitable for the second highest RI layer include: Si _u Al _v O _x N _y , Ta ₂ O ₅ , Nb ₂ O ₅ , AlN, Si ₃ N ₄ , AlO _x N _y , SiO _x N _y , HfO ₂ , TiO ₂ , ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , MoO ₃ and diamond-like carbon. The oxygen content of the material used for the second high RI layer and/or the scratch resistant layer can be minimized, especially in SiN _x or AlN _x materials. The AlO _x N _y material can be regarded as oxygen-doped AlN _x , that is, the material may have an AlN _x crystal structure (eg, oxygen vacancy (wurtzite)) but not necessarily an AlON crystal structure. Exemplary preferred AlO _x N _y high RI materials may include: from about 0 atomic% to about 20 atomic% oxygen, or from about 5 atomic% to about 15 atomic% oxygen; also including 30 atomic% to about 50 Atomic percent nitrogen. Exemplary preferred Si _u Al _v O _x N _y high RI materials may include: from about 10 atomic% to about 30 atomic %, or from about 15 atomic% to about 25 atomic% silicon; from about 20 atomic% to About 40 atomic %, or from about 25 atomic% to about 35 atomic% aluminum; from about 0 atomic% to about 20 atomic %, or from about 1 atomic% to about 20 atomic% oxygen; and from about 30 atomic% Up to about 50 atomic% nitrogen. Exemplary preferred SiO _x N _y high RI materials may include: from about 30 atomic% to about 60 atomic %, or from about 40 atomic% to about 50 atomic% silicon; from about 0 atomic% to about 25 atomic% , Or from about 1 atomic% to about 25 atomic %, or from about 6 atomic% to about 18 atomic% oxygen; and from about 30 atomic% to about 60 atomic% nitrogen. Exemplary preferred SiN _x high RI materials may include: from about 30 atomic% to about 60 atomic %, or from about 40 atomic% to about 50 atomic% silicon; and from about 30 atomic% to about 70 atomic% nitrogen. The aforementioned materials can be hydrogenated to about 30% by weight. The hardness of the second high RI layer and/or the scratch resistant layer can be specifically characterized. In some embodiments, the maximum hardness of the second high RI layer and/or the scratch resistant layer measured by the Berkovich indenter hardness test may be about 10 GPa or greater, about 12 GPa or greater, about 15 GPa Or greater, approximately 18 GPa or greater, or approximately 20 GPa or greater. In some cases, the second high RI layer material can be deposited as a single layer and can be characterized as a scratch-resistant layer, and this single layer can have a thickness from about 500 nm to about 2000 nm for reproducible hardness determination .

The physical thickness of the multilayer interference stack 610 may range from about 100 nm to 1000 nm. In some cases, the physical thickness of the multilayer interference stack 610 may be 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, and all ranges in between and Subrange. In some embodiments, the multilayer interference stack 610 disposed between the substrate 110 and the thick high-hardness portion, as shown in FIG. 6, for example, preferably has a thickness of 100 to 500 nm. In some embodiments, the multilayer interference stack disposed above the substrate 110 preferably has a thickness of 100 to 1000 nm.

In some embodiments, any multilayer interference stack 610 present in the optical coating 120 is disposed below the thick high-hardness portion 140, that is, between the thick high-hardness portion 140 and the substrate 110. Without being bound by theory, the thick high RI layer with high hardness effectively shields the underlying layer (or the layer between the thick RI layer and the substrate), thereby reducing the abrupt interface of the multilayer interference stack 610 to the product 600 The mechanical weakening effect caused by the characteristics. Placement and thickness of soft materials

In some embodiments, the thickness of any soft material in the optical coating 120 may be minimized and/or disposed in certain ways.

In embodiments, it may be beneficial to quantify the amount or thickness of low refractive index (also known as low coefficient) materials in the coating design. Low coefficient materials (generally defined as those having a refractive index less than about 1.6) are also generally lower hardness materials. Without being bound by theory, low RI materials are usually lower hardness materials, because the nature of atomic bonding and electron density affect both the refractive index and the hardness. Therefore, it is desirable to minimize the amount of low-coefficient materials in the coating design, but usually a certain amount of low-coefficient materials is needed to efficiently tailor the reflectivity and color targets. In the design description, the absolute thickness and fraction of the coating thickness are used to represent the thickness and fraction of the low-coefficient material (understandable as a lower hardness material in the examples). It may be beneficial to quantify the total amount of low coefficient material in the overall coating and the amount of low coefficient material above the thickest high hardness coating in the coating design. The thickest high hardness layer in the coating design protects the layers below it from scratches and damage, meaning that the low coefficient layer above the thickest high hardness layer is most susceptible to scratches and other types of damage. As noted above, the thickest high-hardness layer need not be a single monolithic material, but can form a superlattice or other layered structure including multiple layers or materials, provided that the thick high-hardness layer forms the one with the maximum hardness For monolithic or "composite" areas, the maximum hardness is higher than the maximum hardness of the entire coating stack.

In certain embodiments, the total thickness of the "soft" material (eg, SiO ₂ or mixed materials with a refractive index less than about 1.6) above the thick high-hardness portion is preferably limited to less than about 200 nm and less than about 150 nm , Less than about 120 nm or even less than 100 nm. Such minimization of the soft material above the thick hard layer can lead to high product hardness and high scratch resistance. When measured using the Berkovich nanoindentation test, the hardness of the product at an indentation depth from 100 to 500 nm can be greater than 10 GPa, greater than 12 GPa, greater than 14 GPa, or greater than 16 GPa.

In certain embodiments, the amount of low RI material in the optical coating can be minimized. Expressed as the physical thickness fraction of the optical coating 120, the low RI material may include less than about 60%, less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, or less than about 5 % Of the physical thickness of the optical coating. Low RI materials may contain more than zero% or more than 1% of the physical thickness of the optical coating. Alternatively or additionally, the amount of low RI material can be quantified as the total amount of low RI material disposed above the thickest high RI layer in the optical coating (ie, on the opposite side of the substrate, user side, or air side) The total thickness of the solid. Without being bound by theory, a thick high RI layer with high hardness effectively shields the underlying layer (or the layer between the thick RI layer and the substrate) from many or most scratches. Therefore, the layer disposed above the thickest high RI layer can have a particularly large impact on the scratch resistance of the overall product. This is particularly relevant when the thickest high RI layer has a physical thickness greater than about 400 nm and has a maximum hardness greater than about 12 GPa as measured by the Berkovich indenter hardness test. The amount of low RI material disposed on the thickest high RI layer (ie, on the opposite side of the substrate, user side, or air side) may have less than or equal to about 300 nm, less than or equal to about 200 nm, less than or equal to about A thickness of 150 nm, less than or equal to about 120 nm, less than or equal to about 110 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 25 nm, 20 nm, 15 nm or less than or equal to about 12 nm. The amount of low RI material disposed on the thickest high RI layer (ie, on the opposite side of the substrate, user side, or air side) may have a thickness greater than or equal to about 0 nm or 1 nm. Optional layer (Optional layer)

Some embodiments may include optional layers, such as optional layers 170 and 180. The topmost air side layer, such as optional layer 180, may contain a low-friction coating, an oleophobic coating, or an easy-to-clean coating. Exemplary low friction layers may include silane, fluorosilane, or diamond-like carbon. Such materials (or one or more layers of the optical coating) may exhibit a coefficient of friction of less than 0.4, less than 0.3, less than 0.2, or even less than 0.1.

In one or more embodiments, the optional layer 180 may include an easy-to-clean coating. An example of a suitable easy-to-clean coating is described in US Patent Application No. 13/690,904 filed on November 30, 2012, with the name "PROCESS FOR MAKING OF GLASS ARTICLES WITH OPTICAL AND EASY-TO-CLEAN COATINGS", published No. US20140113083A1, which is incorporated herein by reference in its entirety. The easy-to-clean coating may have a thickness ranging from about 5 nm to about 50 nm, and may include known materials such as fluorinated silane. In certain embodiments, the easy-to-clean coating may have a thickness ranging from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 25 nm, from about 1 nm to About 20 nm, from about 1 nm to about 15 nm, from about 1 nm to about 10 nm, from about 5 nm to about 50 nm, from about 10 nm to about 50 nm, from about 15 nm to about 50 nm, from From about 7 nm to about 20 nm, from about 7 nm to about 15 nm, from about 7 nm to about 12 nm, or from about 7 nm to about 10 nm, and all ranges and subranges therebetween. Measuring hardness

The widely accepted practice of nanoindentation is used to determine the hardness and Young's modulus values of film coatings and articles as described herein. See: Fischer-Cripps, AC, "Critical Review of Analysis and Interpretation of Nanoindentation Test Data", Surface & Coatings Technology, 200, 4153 – 4165 (2006) (hereinafter referred to as "Fischer-Cripps"); and Hay, J ., Agee, P and Herbert, E., "Continuous Stiffness measurement During Instrumented Indentation Testing", Experimental Techniques, 34 (3) 86 – 94 (2010) (hereinafter referred to as "Hay"). For coatings, hardness and modulus are usually measured as a function of indentation depth. As long as the coating has a sufficient thickness, the properties of the coating can be isolated from the resulting response curve. It should be recognized that if the coating is too thin (eg, less than ~500 nm), the coating characteristics may not be completely isolated because the coating characteristics may be affected by the proximity of substrates that may have different mechanical characteristics. Please see Hay. The method used to report the characteristics described herein may represent the coating itself. The procedure is to measure the hardness and modulus against the indentation depth (depth close to 1000 nm). In the case where the hard coat layer is on a softer glass, the response curve will exhibit the maximum level of hardness and modulus at a relatively small indentation depth (less than or equal to about 200 nm). At deeper indentation depths, both the hardness and modulus will gradually decrease as the response is affected by the softer glass substrate. In this case, take the hardness and modulus of the coating that are related to the area exhibiting the maximum hardness and modulus. In the case where the soft coating is located on a harder glass substrate, the coating properties will be indicated by the lowest hardness and modulus level that occurs at a relatively small indentation depth. At the deeper indentation depth, due to the effect of harder glass, the hardness and modulus will gradually increase. These distributions of hardness and modulus versus depth can be obtained using the traditional Oliver and Pharr methods (as described by Fischer-Cripps), or by a more efficient continuous rigid method (see Hay). Using the nanoindentation method as described above, the elastic modulus and hardness values reported for this type of film are measured at the tip of a Berkovich diamond indenter.

The optical coating 120 and the article 100 can be described in terms of the hardness measured by the Berkovich indenter hardness test. As used in this article, the "Berkovich Indenter Hardness Test" includes using a diamond Berkovich indenter to press into the surface of the material to measure the hardness of the material on the surface. The Berkovich indenter hardness test includes pressing a diamond Berkovich indenter into the main surface 122 of the product or the surface of the optical coating 120 (or the surface of any one or more layers in a multilayer interference stack) to form an indentation depth of from about 50 nm Indentation in the range of up to about 1000 nm (or the entire thickness of the multilayer interference stack or layer, whichever is thinner), and the entire indentation depth range or section along this indentation depth (eg, from about 100 nm to about 600 nm) The maximum hardness of the indentation is measured. This is usually based on Oliver, WC, Pharr, GM, "An improved technology for determining hardness and elastic modulus using load and displacement sensing indentation experiments", J . Mater. Res. , Vol. 7, No. 6, 1992, 1564-1583" and Oliver, WC, Pharr, GM, "Measurement of Hardness and elastic modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology", J . Mater. Res ., Vol. 19, No. 1, 2004, 3-20". As used herein, hardness refers to maximum hardness, not average hardness. Unless otherwise specified, the hardness values provided herein refer to the values measured by the Berkovich indenter hardness test.

Generally, in nanoindentation measurement methods for coatings that are harder than the underlying substrate (for example, using a Berkovich indenter), the measured hardness initially appears to increase due to the formation of a plastic zone at a shallow indentation depth, and then The deeper indentation depth increases to the maximum value or horizontal top. Subsequently, at deeper indentation depths, the hardness begins to decrease due to the influence of the underlying substrate. The use of substrates with greater hardness than the coating has the same effect; but at deeper indentation depths, the hardness increases due to the influence of the substrate below.

The indentation depth range and the hardness value under certain indentation depth ranges can be selected to identify the specific hardness response of the optical film structure and its layers without being affected by the underlying substrate. When measuring the hardness of the optical film structure (when placed on the substrate) with a Berkovich indenter, the permanent deformation zone (plastic zone) of the material is related to the hardness of the material. During indentation, the elastic stress field extends beyond the permanent deformation zone. As the indentation depth increases, the apparent hardness and modulus are affected by the interaction of the stress field with the underlying substrate. The influence of the substrate on the hardness occurs at a deeper indentation depth (ie, generally at a depth greater than about 10% of the thickness of the optical film structure or layer). Furthermore, what is more complicated is that the hardness response requires a certain minimum load to form full plasticity during the pressing process. Before reaching a certain minimum load, the hardness generally shows an increasing trend.

At small indentation depths (which can also be characterized as small loads) (eg, up to about 50 nm), the apparent hardness of the material appears to correspond to a substantial increase in indentation depth. This small indentation depth system does not represent the true hardness measurement, but reflects the formation of the above-mentioned plastic zone, which is related to the limited radius of curvature of the indenter. At the depth of the intermediate indentation, the apparent hardness is close to the maximum. At deeper indentation depths, as the indentation depth increases, the substrate effect becomes more pronounced. Once the indentation depth exceeds 30% of the thickness of the optical film structure or layer thickness, the hardness begins to decrease sharply.

In some embodiments, the optical coating 120 may exhibit about 10 GPa or greater, or about 11 GPa or greater, or about 12 GPa or greater (eg, 14 GPa or greater, 16 GPa or greater, 18 GPa or greater, 20 GPa or greater) hardness. The hardness of the optical coating 120 can reach about 20 GPa, 30 GPa, or 50 GPa. When measured on the outer surface 22 by the Berkovich indenter hardness test, the article 100 including the optical coating 120 and any additional coatings as described herein may exhibit approximately 10 GPa or greater, or 11 GPa or greater, or approximately 12 GPa or more (eg, 14 GPa or more, 16 GPa or more, 18 GPa or more, 20 GPa or more), and about 50 GPa or less (eg, about 40 GPa or less, or Hardness of about 30 GPa or less). The hardness of the optical coating 120 can reach about 20 GPa, 30 GPa, or 50 GPa. The optical coating 120 and/or article 100 is along about 50 nm or more or about 100 nm or more (eg, from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm) The depth can show the hardness value of this measurement. In one or more embodiments, the hardness exhibited by the article is greater than the hardness of the substrate (the hardness of the substrate can be measured on the opposite surface of the outer surface).

As measured by the Berkovich indenter hardness test, the optical coating 120 may have at least one layer having a hardness (measured on the surface of this layer, such as the surface of the thick high hardness portion 140) of about 12 GPa or greater , About 13 GPa or more, about 14 GPa or more, about 15 GPa or more, about 16 GPa or more, about 17 GPa or more, about 18 GPa or more, about 19 GPa or more, About 20 GPa or more, about 22 GPa or more, about 23 GPa or more, about 24 GPa or more, about 25 GPa or more, about 26 GPa or more, or about 27 GPa or more ( Up to about 50 GPa). According to the measurement of the Berkovich indenter hardness test, the hardness of this layer can range from about 18 GPa to about 21 GPa. The at least one layer is along about 50 nm or more or 100 nm or more (eg, from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm) These measured hardness values.

In one or more embodiments, when a Berkovitch indenter is pressed into the outer surface 122 and measured on the outer surface 122, the optical coating 120 or individual layers within the optical coating may exhibit about 75 GPa or greater, about 80 GPa or greater or about 85 GPa or greater modulus of elasticity. The optical coating 120 or individual layers within the optical coating may exhibit an elastic modulus of about 500 GPa or less. These modulus values can represent the modulus measured very close to the outer surface, for example, at an indentation depth of 0 nm to about 50 nm, or can represent a deeper indentation depth (for example, from about 50 nm to about 1000 nm ) Modulus measured at the location.

In certain embodiments, the article contains a maximum hardness within the range described herein for optical coatings. For example, in some embodiments, the article contains a maximum hardness in the range from about 12 GPa to about 30 GPa, or in the range from about 16 GPa to about 30 GPa, wherein by pressing with a Berkovich indenter The second main surface is inserted to form an indentation (the indentation includes an indentation depth of about 100 nm or more from the surface of the second main surface), and the maximum hardness is measured on the second main surface. Chemical nomenclature

As used in this article, the “AlO _x N _y ”, “SiO _x N _y ”and “Si _u Al _x O _y N _z ” materials in this disclosure include various aluminum oxynitride, silicon oxynitride and silicon aluminum oxynitride materials, As those of ordinary skill in the technical field to which this disclosure belongs understand, these materials are described according to certain numerical values and ranges of the subscripts "u", "x", "y", and "z". In other words, the "whole number formula" description is usually used to describe solids, such as Al ₂ O ₃ . The equivalent "atomic fraction formula" description is also often used to describe solids, such as Al _0.4 O _0.6 , which is equivalent to Al ₂ O ₃ . In the atomic fraction formula, the sum of all atoms in the formula is 0.4 + 0.6 = 1, and the atomic fractions of Al and O in the formula are 0.4 and 0.6, respectively. Atomic fraction description is used in many general textbooks to describe, and atomic fraction description is usually used to describe alloys. See, for example: (i) Charles Kittel, "Introduction to Solid State Physics", seventh edition, John Wiley & Sons, Inc., NY, 1996, pp. 611-627; (ii) Smart and Moore, "Solid State Chemistry, An introduction", Chapman & Hall University and Professional Division, London, 1992, pp. 136-151; and (iii) James F. Shackelford, "Introduction to Materials Science for Engineers", sixth edition, Pearson Prentice Hall , New Jersey, 2005, pp. 404-418.

Refer again to the "AlO _x N _y ", "SiO _x N _y ", and "Si _u Al _x O _y N _z "materials in this disclosure. The subscript allows those with ordinary knowledge in the technical field to which this case belongs to refer to these materials as A type of material without specifying a specific subscript value. In general, regarding an alloy, such as alumina, without specifying a specific subscript value, I can call it Al _v O _x . The description of Al _v O _x may represent Al ₂ O ₃ or Al _0.4 O _0.6 . If the sum of v + x is 1 (that is, v + x = 1), then the formula can be described as atomic fraction. Similarly, more complex mixtures can be described, such as Si _u Al _v O _x N _y , where, again, if the sum of u + v + x + y is equal to 1, we can have atomic fraction description examples.

Refer again to the "AlO _x N _y ", "SiO _x N _y ", and "Si _u Al _x O _y N _z "materials in this disclosure, these symbols allow those with ordinary knowledge in the technical field to which this case belongs to easily compare these materials And other materials. In other words, sometimes the atomic fraction formula is easier to compare. For example, an example alloy consisting of (Al ₂ O ₃ ) _0.3 (AlN) _{0.7 is} almost equivalent to Al _0.448 O _0.31 N _0.241 and Al ₃₆₇ O ₂₅₄ N ₁₉₈ . Another example alloy composed of (Al ₂ O ₃ ) _0.4 (AlN) _{0.6 is} almost equivalent to the formula descriptions Al _0.438 O _0.375 N _0.188 and Al ₃₇ O ₃₂ N ₁₆ . The atomic fraction formulas Al _0.448 O _0.31 N _0.241 and Al _0.438 O _0.375 N _{0.188 are} relatively easy to compare with each other. For example, Al in the atomic fraction decreases by 0.01, O in the atomic fraction increases by 0.065, and N in the atomic fraction decreases by 0.053. More detailed calculations and considerations are needed to compare the integer descriptions Al ₃₆₇ O ₂₅₄ N ₁₉₈ and Al ₃₇ O ₃₂ N ₁₆ . Therefore, sometimes it is better to use the atomic fraction formula of solid description. Nevertheless, the use of Al _v O _x N _y is versatile because it traps any alloy containing Al, O, and N atoms.

As understood by those with ordinary knowledge in the technical field to which this disclosure belongs, for any of the foregoing materials (eg, AlN) related to the optical film 120, each subscript "u", "x", "y", and "z" may be Varying between 0 and 1, the sum of the subscripts will be less than or equal to one, and the balance of the composition is the first element in the material (eg, Si or Al). In addition, those with ordinary knowledge in the technical field to which this case belongs can recognize that "Si _u Al _x O _y N _z "can be configured so that "u" equals zero, and the material can be described as "AlO _x N _y ". Furthermore, the aforementioned components for the optical film 120 exclude subscript combinations that can lead to pure element types (eg, pure silicon, pure aluminum metal, oxygen gas, etc.). Finally, those with ordinary knowledge in the technical field to which this case belongs will also realize that the aforementioned components may include other elements that are not clearly labeled (eg, hydrogen), which may result in non-stoichiometric components (eg, SiN _x vs. Si ₃ N ₄ ) . Therefore, depending on the value of the subscript in the aforementioned composition notation, the aforementioned material used for the optical film may represent SiO ₂ -Al ₂ O ₃ -SiN _x -AlN or SiO ₂ -Al ₂ O ₃ -Si ₃ N ₄ -AlN Free space in the phase diagram. Color and color deviation with angle

In some examples, the optical coating can be designed to have a relatively neutral (gray or silver) color and a relatively small color change with the incident angle of light.

Specifically, the hard-coated article can exhibit a single surface reflection color range for all viewing angles from 0 to 60 degrees, which includes having 20 or less, 10 or less, 8 or less, 5 in all viewing angle ranges All a* points and all b* points of the absolute value of or less, 4 or less, 3 or less, or even 2 or less.

Furthermore, for all viewing angles from 0 to 90 degrees, the hard-coated article may have a two-surface transmission color range that includes having 2 or less, 1 or less, 0.5 or less, 0.4 in all viewing angle ranges All a* points and all b* points of absolute values of or less, 0.3 or less, or even 0.2 or less.

In alternative examples, the coating may be designed to have a relatively high color (eg, blue, purple, red, green, gold, orange, and combinations thereof) to maintain a certain color within a certain viewing angle range, or Change the color as the viewing angle changes within the controlled color quadrant.

In the case of high-color coatings, the coating may have an a* value or a b* value higher than 20 for at least one viewing angle or range of viewing angles. In combination, the colors can be constrained to remain substantially within one, two, or three color quadrants on the a*, b* color chart over a viewing angle range from 0 to 60 degrees or from 0 to 90 degrees. The different colors produced by these hard coats may span the entire palette, from red, orange, gold (yellow), green, blue to purple. In some cases, colors may shift across multiple colors with angle. In other cases, the color will be limited to a certain range of a* and b* with the incident angle. In some embodiments, the "high color" coating can still preferably limit its color with a viewing angle. For example, for all viewing angles from 0 to 90 degrees, the "green" coating may have an a* less than 5 or less than 1. For all viewing angles from 0 to 90 degrees, a "blue" or "green" coating may have a b* of less than 5 or less than 1. For all viewing angles from 0 to 90 degrees, the "red" or "orange" or "purple" coating may have an a* greater than -5 or greater than -1. For all viewing angles from 0 to 90 degrees, the "golden" coating may have a b* greater than -5 or greater than -1. These limits can be combined with each other to produce the designed color in high-color coatings. For example, the "blue-green" coating can combine the limits of b* less than 5 and a* less than 5 for all viewing angles. The "red-gold" coating can be combined for all viewing angles b* greater than -5 and a* greater than -5.

Even in the case of describing a specific range of viewing angles, in some embodiments, the ranges of a* and b* described herein may be for different viewing angle ranges, such as 0 to 10 degrees, 0 to 60 degrees, or 0 to 90 degree. Other color combinations and restrictions are also possible.

The above reflectivity and color values are most suitable for certain applications, such as facing the surface of the sunglasses lens away from the user, scratch-resistant mirrors, or protective covers that do not view the display through them, such as electronic devices (smart watches, smart Phones, car displays, etc.) have a high scratch resistance and a specific reflectivity.

The optical interference between the reflected waves from the optical coating 120/air interface and the optical coating 120/substrate 110 interface will cause the spectral reflectance and/or transmittance to fluctuate, thereby producing a distinct color in the product 100. The color in the reflection may be more obvious. Because the spectral reflectance fluctuation shifts with the incident irradiation angle, the angular color shift in reflection occurs with the viewing angle. And because the fluctuation of the spectral transmittance shifts with the incident irradiation angle, the angular color shift in transmission occurs with the viewing angle. Viewing the color and the role deviation with the incident illumination angle usually distracts or dislikes the device user, especially under the bright spectral characteristics, such as fluorescent lamps and some LED lighting. The angular color shift in transmission is also a factor in the angular color shift in reflection, and vice versa. Factors of angular color shift in transmission and/or reflection may also include angular color shift caused by deviation of the viewing angle or angular color from certain white points, which may result from material absorption defined by the specific light source or test system (slightly independent of angle ).

As used herein, "near normal" incidence angle refers to an incidence angle that differs from the normal incidence angle by 10 degrees or less. "Near normal" includes normals. When the transmission or reflection criterion is described as occurring at a "near normal" angle, the criterion is met if the specified transmission or reflection criterion occurs at any near normal angle. In many cases, the optical properties (such as reflectance, transmittance, and color shift) caused by multilayer interference stacks do not change much as a function of the angle of the near normal angle. Therefore, for practical purposes, "near normal" incidence and "normal" incidence are the same. In addition, some measurement techniques do not operate well at precise normal incidence angles, so characteristics at normal incidence angles are usually estimated based on measurements at near normal angles. All occurrences of "normal" in this article should be interpreted as including "near normal".

Fluctuations can be described in terms of amplitude. As used herein, the term "amplitude" includes peak-to-valley changes in reflection or transmission. The term "average amplitude" includes a number of fluctuation cycles in the wavelength range of light or a peak-to-valley change in average reflection or transmission in the wavelength sub-range. As used herein, unless otherwise indicated, "light wavelength range" includes a wavelength range from about 400 nm to about 700 nm (more specifically from about 450 nm to about 650 nm). In some embodiments, the article exhibits an average transmittance or average reflectance of 10% or less, 8% or less, 6% or less, 4% or more in the optical wavelength range Low, 2 percentage points or lower, or 1 percentage point or lower average fluctuation amplitude.

One aspect of the present disclosure relates to articles that even when viewed at different incident illumination angles under a light source, the articles still exhibit the color or colorless nature of reflectance and/or transmittance. As used herein, the term "color shift" (angle or reference point) refers to a* and b* in reflection and/or transmission under the CIE L*, a*, b* colorimetric system Change. This color cast is usually called C* and is not affected by any change in L*. For example, the following equation (1) can be used to determine the angular color shift C*: √((a* ₂ -a* ₁ ) ² +(b* ₂ -b* ₁ ) ² ), where a* ₁ and b * ₁ indicates the a* and b* coordinates of the product viewed at the incident reference illumination angle (which can include normal incidence), a* ₂ and b* ₂ indicates the a* and b* coordinates of the product viewed at the incident illumination angle, provided that the incidence is The incident illumination angle is different from the reference illumination angle, and in some cases differs from the reference illumination angle by about 1 degree or more (eg, about 2 degrees or about 5 degrees). In some cases, under a light source, when viewed from multiple incident illumination angles that deviate from the reference illumination angle, the article exhibits a specific angular color shift in reflection and/or transmission. Light sources can include standard light sources determined by CIE, including A light source (representing tungsten filament lamp), B light source (daylight simulation lighting), C light source (daylight simulation lighting), D series light source (representing natural lighting) and F series light source (representing various Fluorescent lights). Unless otherwise specified, colors and color casts are presented under D65 light source.

The reference illumination angle may include normal incidence (ie, from about 0 degrees to about 10 degrees), or 5 degrees from normal incidence, 10 degrees from normal incidence, 15 degrees from normal incidence, 20 degrees from normal incidence, 25 degrees off normal, 30 degrees off normal, 35 degrees off normal, 40 degrees off normal, 45 degrees off normal, 50 degrees off normal, 55 degrees off or normal Normal incidence is 60 degrees, provided that the difference between the incident illumination angle and the reference illumination angle is about 1 degree or more (for example, about 2 degrees or about 5 degrees). With respect to the reference irradiation angle, the incident irradiation angle may deviate from the reference irradiation angle from about 5 degrees to about 80 degrees, from about 5 degrees to about 70 degrees, from about 5 degrees to about 65 degrees, from about 5 degrees to about 60 degrees, From about 5 degrees to about 55 degrees, from about 5 degrees to about 50 degrees, from about 5 degrees to about 45 degrees, from about 5 degrees to about 40 degrees, from about 5 degrees to about 35 degrees, from about 5 degrees to About 30 degrees, from about 5 degrees to about 25 degrees, from about 5 degrees to about 20 degrees, from about 5 degrees to about 15 degrees, and all ranges and subranges therebetween. The article may exhibit an angular color shift of reflection and/or transmission at all incident illumination angles in the range from about 0 degrees to about 60 degrees or about 0 degrees to about 90 degrees and along all incident illumination angles in the range.

In some embodiments, the angular color cast can be measured at all angles between the reference illumination angle (eg, normal incidence) and the incident illumination angle, which ranges from 0 degrees to about 60 degrees , Or about 0 degrees to about 90 degrees.

In one or more embodiments, the reference point for measuring the color deviation may be the origin (0, 0) (or the color coordinates a*=0, b) in the CIE L*, a*, b* colorimetric system * =0), or the substrate's transmittance or reflection color coordinates. Unless otherwise specified, the reference points are color coordinates a*=0, b*=0. It should be understood that unless otherwise noted, the L* coordinates of the products described herein will not affect the color shift calculated according to the description herein. The reference color shift of the product is defined relative to the substrate. The transmission color coordinate of the product is compared with the transmission color coordinate of the substrate, and the reflective color coordinate of the product is compared with the reflection color coordinate of the substrate.

When the reference point is a color coordinate a*=0, b*=0, the color deviation of the reference point can be calculated by the following formula (2). Reference point color shift = √(( a * _product ) ² +( b * _product ) ² )

When the reference point is the color coordinate of the substrate, the color deviation of the reference point can be calculated by the following formula (4). Reference point color shift = √(( a * _product - a * _substrate ) ² +( b * _product - b * _substrate ) ² )

In some embodiments, when the reference point is any one of the color coordinate and the color coordinate (a*=0, b*=0) of the substrate, the article may exhibit a transmission color (or transmission color coordinate) and a reflection color (Or reflection color coordinates), so that the reference color shift is as specified.

In some embodiments, under D65, A, and F2 light sources, at an incident illumination angle ranging from about 0 degrees to about 60 degrees, the article (at the outer surface and the opposite bare surface) exhibits transmittance Specific a* value. In some embodiments, under D65, A, and F2 light sources, at an incident illumination angle ranging from about 0 degrees to about 60 degrees, the article (at the outer surface and the opposite bare surface) exhibits transmittance Specific b* value.

In certain embodiments, under D65, A, and F2 light sources, the article (only on the outer surface) exhibits a specific a* value of reflectivity at an incident illumination angle ranging from about 0 degrees to about 60 degrees. In certain embodiments, under D65, A, and F2 light sources, at an incident illumination angle ranging from about 0 degrees to about 60 degrees, the article (only on the outer surface) exhibits a specific b* value of reflectivity.

The maximum reflection color deviation value means that the highest color point value measured at any angle in the specified angle range minus the lowest color point value measured in the same range. The value may represent the maximum change in a* value (a* _highest-a * _minimum ), the maximum change in b*value (b* _highest- b* _minimum ), the maximum change in both a*value and b*value, Or the maximum change in magnitude √((a* _highest-a * _lowest ) ² +(b* _highest- b* _lowest ) ² ). Unless otherwise specified, the maximum reflected color shift refers to the maximum change in this magnitude. Visual average reflectance and transmittance

，乘以光源光譜，

，及CIE之色彩匹配函數

，與眼睛的光譜反應有關：

In some embodiments, the article of one or more embodiments, or the outer surface 122 of the article or articles, may exhibit a specific average visible light average reflectance and/or average visible light in the optical wavelength range Apparent average transmittance. These apparent reflectance values can be exhibited at incident illumination angles ranging from about 0° to about 20°, from about 0° to about 40°, or from about 0° to about 60°. Unless otherwise specified, the average apparent visual average reflectance or transmittance is measured at an incident illumination angle ranging from about 0 degrees to about 10 degrees. As used in this paper, by weighting the reflectance versus the wavelength spectrum according to the sensitivity of the human eye, the average reflectance of bright vision simulates the response of the human eye. According to the CIE color space agreement, the average visual reflectance is defined as the brightness of the reflected light or the Y value of the tristimulus. The average bright-view average reflectance is defined by (4) as the spectral reflectance,

, Multiplied by the light source spectrum,

, And CIE's color matching function

, Related to the spectral response of the eye:

Similarly, unless otherwise specified, the average reflectance and transmittance are measured at an incident illumination angle in the range of about 0 degrees to about 10 degrees.

In certain embodiments, the article exhibits a specific one-sided average apparent reflectance, measured only at normal or near normal incidence (eg, 0 to 10 degrees) on the outer surface. Substrate

The substrate 110 may include an inorganic material, and may include an amorphous substrate, a crystalline substrate, or a combination of the foregoing. The substrate 110 may be made of artificial materials and/or natural materials such as quartz and polymers. For example, in some cases, the substrate 110 may be characterized as organic, and may be specifically a polymer. Examples of suitable polymers include, but are not limited to: thermoplastics, including polystyrene (PS) (including styrene copolymers and blends), polycarbonate (PC) (including copolymers and blends), polymer Esters (including copolymers and blends, including polyethylene terephthalate and polyethylene terephthalate copolymers), polyolefins (PO) and cyclic polyolefins (cyclic PO), polyvinyl chloride (PVC), acrylic polymers, including polymethyl methacrylate (PMMA) (including copolymers and blends), thermoplastic urethane (TPU), polyetherimide (PEI), and these polymers Mutual blending. Other exemplary polymers include epoxy, styrenic, phenolic, melamine, and silicone resins.

In some embodiments, the substrate 110 may specifically exclude polymer, plastic and/or metal substrates. The substrate may be characterized as an alkali metal-containing substrate (ie, the substrate includes one or more alkali metals). In one or more embodiments, the substrate exhibits a refractive index ranging from about 1.45 to about 1.55. In a specific embodiment, when ball-on-ring testing is used to measure 5 or more samples, the substrate 110 may exhibit an average strain at one or more surfaces on the opposite major surface Strain-to-failure: 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more , 1.3% or more, 1.4% or more, 1.5% or more, or even 2% or more. More samples can be used within a reasonable range because it is expected that more samples will result in greater statistical consistency. In a specific embodiment, the substrate 110 may exhibit about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.2%, about 2.4%, about 2.6% at the surface on one or more of its opposite major surfaces , About 2.8% or about 3% or more of the average strain-induced failure.

A suitable substrate 110 may exhibit an elastic modulus (or Young's modulus) in the range from about 30 GPa to about 120 GPa. In some cases, the elastic modulus of the substrate may be from about 30 GPa to about 110 GPa, from about 30 GPa to about 100 GPa, from about 30 GPa to about 90 GPa, from about 30 GPa to about 80 GPa, from about 30 GPa to about 70 GPa, from about 40 GPa to about 120 GPa, from about 50 GPa to about 120 GPa, from about 60 GPa to about 120 GPa, from about 70 GPa to about 120 GPa, and all in between Scope and sub-scope.

In one or more embodiments, the amorphous substrate may include strengthened glass or unstrengthened glass. Examples of suitable glasses include soda lime glass, alkali metal aluminosilicate glass, alkali metal-containing borosilicate glass, and alkali metal aluminoborosilicate glass. In some variations, the glass is free of lithium oxide. In one or more alternative embodiments, the substrate 110 may include a crystalline substrate, such as a glass ceramic substrate (which may or may not be strengthened), or may include a single crystal structure, such as sapphire. In one or more specific embodiments, the substrate 110 includes an amorphous base (eg, glass) and a crystalline coating (eg, sapphire layer, polycrystalline alumina layer, and/or spinel (MgAl ₂ O ₄ ) layer) .

The hardness of the substrate 110 of one or more embodiments may be less than the hardness of the product (measured according to the Berkovich indenter hardness test described herein). The hardness of the substrate can be determined by the Berkovich indenter hardness test as described herein.

The substrate 110 may be substantially planar or sheet-shaped, although other embodiments may use curved or other shapes or shapes. The substrate 110 may be substantially light-transmissive, transparent, and free of light scattering. In such an embodiment, the substrate may exhibit about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater in the light wavelength range, An average light transmittance of about 90% or greater, about 91% or greater, or about 92% or greater. In one or more alternative embodiments, the substrate 110 may be opaque or exhibit less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about An average light transmittance of 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0.5%. In some embodiments, the light reflectance and transmittance values may be total reflectance or total transmittance (taking into account the reflectance or transmittance on the two main surfaces of the substrate), or may be observed on one side of the substrate (That is, only on the outer surface 122, regardless of the opposing surface). Unless otherwise specified, the average reflectance or transmittance is measured at an incident illumination angle of 0 degrees (however, such measurements can be made at an incident illumination angle of 45 degrees or 60 degrees). The substrate 110 can selectively display colors, such as white, black, red, blue, green, yellow, orange, and so on.

Additionally or alternatively, due to aesthetic and/or functional reasons, the physical thickness of the substrate 110 may vary along one or more of its dimensions. For example, the edge of the substrate 110 may be thicker than the more central area of the substrate 110. The length, width, and physical thickness of the substrate 110 may also vary according to the application or use of the product 100.

Various different processes can be used to provide the substrate 110. For example, when the substrate 110 includes an amorphous substrate such as glass, various forming methods may include a floating glass process and a downward drawing process, such as fusion drawing and slot drawing.

Once formed, the substrate 110 can be strengthened to strengthen the substrate. As used herein, the term "reinforced substrate" refers to a chemically strengthened substrate, for example, by ion exchange between larger ions and smaller ions on the surface of the substrate. However, other strengthening methods known in the art can also be used to form the strengthened substrate, such as thermal tempering, or the use of mismatched thermal expansion coefficients of the substrate to generate compressive stress and central tension regions.

When the substrate is chemically strengthened by the ion exchange process, the ions on the surface of the substrate will be replaced or exchanged with larger ions with the same valence or oxidation state. The ion exchange process is usually performed by immersing the substrate in a molten salt bath that contains larger ions to exchange with smaller ions in the substrate. Those of ordinary skill in the technical field to which this case belongs will understand the parameters of the ion exchange process (including but not limited to: bath composition, temperature, immersion time, number of times the substrate is immersed in one or more salt baths, use of multiple salt baths, such as annealing, washing And other additional steps), generally depends on the substrate composition and the predetermined compressive stress (CS), the substrate compression stress layer depth (or layer depth) caused by the strengthening operation. For example, by immersing in at least one molten salt bath containing salts, such as nitrates, sulfates and chlorides of larger alkali metal ions, but not limited to this, alkali-containing glass can be used Substrate ion exchange. The temperature of the molten salt bath is usually about 380 ºC to about 450°C, and the immersion time is about 15 minutes to about 40 hours. However, temperatures and immersion times other than those described above can also be used.

In addition, an example of a non-limiting ion exchange process is described in US Patent Application No. 12/500,650, entitled "Glass with Compressive Surface for Consumer Applications", filed on July 10, 2009 by Douglas C. Allan et al. The substrate is immersed in multiple ion exchange baths and there is a washing and/or annealing step between the immersion. This application also claims the priority of US Provisional Patent Application No. 61/079,995 filed on July 11, 2008, of which the glass substrate Strengthened by multiple continuous ion exchange treatments by immersion in salt baths of different concentrations; and awarded to Christopher M, Lee et al. in the United States on November 20, 2012 with the name "Dual Stage Ion Exchange for Chemical Strengthening of Glass" Patent Case No. 8,312,739, which also claims the priority of US Provisional Patent Application No. 61/084,398 filed on July 29, 2008, in which the glass substrate is ion-exchanged in the first bath diluted with effluent ions Then, it is strengthened by immersing in a second bath with a lower ion concentration than the first bath. The entire contents of US Patent Application No. 12/500,650 and US Patent No. 8,312,739 are incorporated herein by reference.

A commercially available instrument such as FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan) can be used, and the compressive stress (including surface CS) is measured by a surface stress meter (FSM). Surface stress measurement is based on the accurate measurement of stress optical coefficient (SOC), which is related to the birefringence of glass. Furthermore, the SOC was measured according to the procedure C (Glass Disc Method) described in the ASTM standard C770-16 named "Standard Test Method for Measurement of Glass Stress-Optical Coefficient". The full text of this document is cited by reference Incorporated in this article. The maximum CT value can be measured using a scattered light polariscope (SCALP) technique known in the technical field to which this case belongs.

As used herein, DOC means the depth to which the stress in the chemically strengthened alkali metal aluminosilicate glass product changes from compression to stretching. Depending on the ion exchange process, DOC can be measured by FSM or scattered light polarimeter (SCALP). If stress is generated in the glass product by exchanging potassium ions into the glass product, FSM is used to measure DOC. If stress is generated by exchanging sodium ions into glass products, DOC is measured using SCALP. If stress is generated in the glass product by exchanging both potassium ions and sodium ions into the glass, the DOC is measured by SCALP, because the exchange depth of sodium is believed to indicate DOC, and the exchange depth of potassium ions indicates compressive stress Changes in magnitude (but not stress changes from compression to tension); the exchange depth of potassium ions in such glass products is measured by FSM.

In some embodiments, the strengthened substrate 110 may have a surface CS of 250 MPa or greater, 300 MPa or greater, for example, 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, or 800 MPa or more. The strengthened substrate may have a DOC of 10 µm or more, 15 µm or more, 20 µm or more (eg, 25 µm, 30 µm, 35 µm, 40 µm, 45 µm, 50 µm or more), and/or 10 MPa Or greater, 20 MPa or greater, 30 MPa or greater, 40 MPa or greater (eg, 42 MPa, 45 MPa, or 50 MPa or greater) but less than 100 MPa (eg, 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa or less) maximum CT. In one or more specific embodiments, the strengthened substrate has one or more of the following: a surface CS greater than 500 MPa, a DOC greater than 15 µm, and a maximum CT greater than 18 MPa.

Examples of glass that can be used for the substrate include alkali metal aluminosilicate glass components or alkali metal aluminoborosilicate glass components, although other glass components can also be considered. Such glass components can be chemically strengthened by the ion exchange process. An example glass composition includes SiO ₂ , B ₂ O ₃ and Na ₂ O, where (SiO ₂ + B ₂ O ₃ ) ≥ 66 mol% and Na ₂ O ≥ 9 mol %. In certain embodiments, the glass composition includes 6 wt% or more alumina. In a further embodiment, the substrate includes a glass component having one or more alkaline earth metal oxides, such that the content of alkaline earth metal oxides is 5% by weight or more. In certain embodiments, suitable glass components further include at least one of K ₂ O, MgO, and CaO. In some embodiments, the glass composition used for the substrate may include: 61 to 75 mol% SiO2; 7 to 15 mol% Al ₂ O ₃ ; 0 to 12 mol% B ₂ O ₃ ; 9 to 21 mole% of Na ₂ O; 0. 4 to mole% of K ₂ O; 0. 7 to mole percent of MgO; and 0-3 mole% of CaO.

Further examples of glass compositions suitable for substrates include: 60 to 70 mol% SiO ₂ ; 6 to 14 mol% Al ₂ O ₃ ; 0 to 15 mol% B ₂ O ₃ ; 0 to 15 mol % Li ₂ O; 0 to 20 mol% Na ₂ O; 0 to 10 mol% K ₂ O; 0 to 8 mol% MgO; 0 to 10 mol% CaO; 0 to 5 mol% % ZrO _{2 in} ears; 0 to 1 mol% SnO ₂ ; 0 to 1 mol% CeO ₂ ; less than 50 ppm As ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; of which 12 mo Ear% £ (Li ₂ O + Na ₂ O + K ₂ O) £20 mole%, and 0 mole% £ (MgO + CaO) £10 mole%.

Further examples of glass compositions suitable for substrates include: 63.5 to 66.5 mol% SiO ₂ ; 8 to 12 mol% Al ₂ O ₃ ; 0 to 3 mol% B ₂ O ₃ ; 0 to 5 mol % Li ₂ O; 8 to 18 mol% Na ₂ O; 0 to 5 mol% K ₂ O; 1 to 7 mol% MgO; 0 to 2.5 mol% CaO; 0 to 3 mol% % ZrO _{2 in} ears; 0.05 to 0.25 mol% SnO ₂ ; 0.05 to 0.5 mol% CeO ₂ ; less than 50 ppm As ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; 14 of which Ear% £ (Li ₂ O + Na ₂ O + K ₂ O) £ 18 mole %, and 2 mole% £ (MgO + CaO) £ 7 mole %.

In some embodiments, the alkali metal aluminosilicate glass composition suitable for the substrate includes alumina, at least one alkali metal, and in some embodiments, greater than 50 mol% SiO ₂ , in other embodiments it is 58 mole% or more of SiO _2, and in other embodiments from 60 mole% or more of SiO _2, wherein the _{(Al 2 O 3 + B 2} O 3) / Σ modifier (i.e., change The ratio of the sum of the quality agents is greater than 1, wherein in the ratio, the components are expressed in mole %, and the modifier is an alkali metal oxide. In specific embodiments, this glass composition comprises: 58 to 72 mol% SiO ₂ ; 9 to 17 mol% Al ₂ O ₃ ; 2 to 12 mol% B ₂ O ₃ ; 8 to 16 mol % Na ₂ O; and 0 to 4 mol% K ₂ O, where the ratio of (Al ₂ O ₃ + B ₂ O ₃ )/modifier (ie, the sum of modifiers) is greater than 1.

In certain embodiments, the substrate may include an alkali metal aluminosilicate glass composition, including: 64 to 68 mol% SiO ₂ ; 12 to 16 mol% Na ₂ O; 8 to 12 mol% Al ₂ O ₃ ; 0 to 3 mol% B ₂ O ₃ ; 2 to 5 mol% K ₂ O; 4 to 6 mol% MgO; and 0 to 5 mol% CaO, of which: 66 mol % SiO ₂ + B ₂ O ₃ + CaO 69 mole %; Na ₂ O + K ₂ O + B ₂ O ₃ + MgO + CaO + SrO> 10 mole %; 5 mole% MgO + CaO + SrO 8 mole Ear %; (Na ₂ O + B ₂ O ₃ ) – Al ₂ O ₃ 2 mole %; 2 mole% Na ₂ O Al ₂ O ₃ 6 mole %; and 4 mole% (Na ₂ O + K ₂ O) – Al ₂ O ₃ 10 mol%.

In some embodiments, the substrate may include an alkali metal aluminosilicate glass composition, including: 2 mol% or more Al ₂ O ₃ and/or ZrO ₂ , or 4 mol% or more Al ₂ O ₃ and/or ZrO ₂ .

When the substrate 110 includes a crystalline substrate, the substrate may include a single crystal, and the single crystal may include Al ₂ O ₃ . Such a single crystal substrate is called sapphire. Other suitable materials that can be used for crystalline substrates include polycrystalline alumina layers and/or spinel (MgAl ₂ O ₄ ).

As the case may be, the crystalline substrate 110 may include a glass-ceramic substrate, which may or may not be strengthened. Examples of suitable glass ceramics may include Li ₂ O-Al ₂ O ₃ -SiO ₂ system (ie, LAS-system) glass ceramics, MgO-Al ₂ O ₃ -SiO ₂ system (ie, MAS-system) glass ceramics, And/or include glass ceramics whose main crystal phases include b-quartz solid solution, b-spodumene ss, cordierite and lithium disilicate. The glass ceramic substrate can be strengthened using the chemical strengthening process described herein. In one or more embodiments, the MAS-system glass-ceramic substrate can be strengthened in Li ₂ SO ₄ molten salt so that 2Li ⁺ can be exchanged with Mg ²⁺ .

The substrate 110 according to one or more embodiments may have a physical thickness ranging from about 100 µm to about 5 mm. The physical thickness of the example substrate 110 ranges from about 100 µm to about 500 µm (eg, 100, 200, 300, 400, or 500 µm). Other example substrates 110 have a physical thickness ranging from about 500 µm to about 1000 µm (eg, 500, 600, 700, 800, 900, or 1000 µm). The substrate 110 may have a physical thickness greater than about 1 mm (eg, about 2, 3, 4, or 5 mm). In one or more specific embodiments, the substrate 110 may have a physical thickness of 2 mm or less or less than 1 mm. The substrate 110 may be subjected to acid polish or other treatments to eliminate or reduce the effects of surface defects. method

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

In one or more embodiments, the method may include the steps of: loading the substrate onto the carrier, and then using the carrier to move the substrate into and out of the different coating chambers under the loading gate condition, so as to move the substrate Keep the vacuum.

Various deposition methods may be used to form the optical coating 120 and/or other layers, such as vacuum deposition techniques, for example, chemical vapor deposition (eg, plasma enhanced chemical vapor deposition (PECVD), low pressure chemical Vapor deposition, atmospheric pressure chemical vapor deposition, and plasma enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (eg, reactive or non-reactive sputtering, metal-mode reactive sputtering, or Laser stripping), thermal or electron beam evaporation and/or atomic layer deposition. Liquid system methods can also be used, such as spraying, dipping, spin coating, or slot coating (for example, using a sol-gel material). When vacuum deposition is used, an inline process may be used to form the optical coating 120 and/or other layers in one deposition run. In some cases, vacuum deposition can be achieved by a linear PECVD source.

In some embodiments, the method may include the step of controlling the thickness of the optical coating 120 and/or other layers such that the thickness varies along about 80% or more of the surface 122 area, or along the substrate area The target thickness difference of each layer at any point does not exceed about 4%. In certain embodiments, the thickness of the optical coating 120 and/or other layers varies by no more than about 4% along the thickness of about 95% or more of the area of the outer surface 122.

In some embodiments, for any of the embodiments described herein, the method of forming an article includes the following steps: obtaining a substrate, the substrate including a first major surface and including an amorphous substrate or a crystalline substrate; On a main surface, the optical coating includes a second main surface and a thickness, the second main surface is opposite to the first main surface, and the thickness is in a direction perpendicular to the second main surface; and at least the thickness along the optical coating In the first gradient part, a refractive index gradient is generated. The refractive index of the optical coating varies along the thickness of the optical coating between the first main surface and the second main surface.

In some embodiments, for any of the embodiments described herein, generating a refractive index gradient includes the step of changing at least one of the composition and porosity of the optical coating along the thickness of the optical coating. The composition and/or porosity can be changed stepwise or continuously by adjusting the deposition parameters and conditions in a stepwise or continuous manner. Examples of specific products

FIG. 35 illustrates glasses 3500 according to some embodiments. The glasses 3500 includes a lens 3510, a frame 3520, a bridge 3530, and a temple 3540. Any suitable spectacle structure can be used. It is not intended to be limited by the specific structure of Figure 35. For example, some glasses have a single continuous lens instead of two lenses that are partially separated by bridging. And, for example, some sunglasses have different frame configurations, including half frame and frameless configurations. In certain embodiments, the scratch resistant coating described herein may be applied to the front surface of the lens 3510, ie, the surface facing away from the wearer. As described herein, the coating may also be applied to the rear surface of the lens 3510.

The glass products disclosed herein can be incorporated into another product, such as a product with a display (or display product) (eg, consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (eg, watches), etc. Etc.), head-up displays (e.g. coated glass designed to reflect certain wavelengths of light from projectors (such as LED or laser projectors) while penetrating other wavelengths), construction products, transportation products ( For example, cars, trains, airplanes, ships, etc.), home appliances, or any product that can benefit from some transparency, scratch resistance, film resistance, or a combination of the foregoing characteristics. Transparency may include visible/optical transparency, or may include microwave/RF transparency (even if the article is opaque in the visible spectrum, such as black glass-ceramic). Exemplary products incorporating any of the glass products disclosed herein are shown in Figures 36 and 37. Specifically, FIGS. 36 and 37 illustrate a consumer electronic device 3600, which includes a housing 3602 having a front surface 3604, a back surface 3606, and a side surface 3608; electronic components (not shown) are at least partially or completely Is located in the housing and includes at least one controller, memory and display 3610, the display 3610 is located at or near the front surface of the housing; and the cover plate 3612, the cover plate 3612 is located at or covers the front surface of the housing so that it covers On the monitor. In some embodiments, the cover plate 3612 may include any glass article disclosed herein. In certain embodiments, at least one of a portion of the housing or the cover plate includes the glass article disclosed herein. Examples

Various embodiments are further clarified by the following examples.

It has been observed through various scratch, indentation, and delamination experiments that the gradient interface can provide improved resistance to mechanical damage, including delamination. It is expected that gradients with a lower slope (slowest composition change) will most resemble bulk materials and therefore have the highest resistance to delamination. However, as explained further herein and illustrated by examples and comparative examples, gradients with very low slopes may not achieve the desired optical interference effects to produce ideal reflectivity and other optical properties with dense coating materials. The examples in this article show that an RI gradient with an appropriate slope can enhance mechanical robustness while still having a refractive index change fast enough to provide the desired optical interference effect. The most desirable embodiment will depend on the application requirements. Some applications may require the highest mechanical properties while targeting high reflectivity and specific colors; other applications may allow lower reflectivity while targeting neutral (silver) colors; and so on.

Comparative Examples 1 to 2 and Molded Examples 1 to 3 used model construction to demonstrate the reflectance and transmittance spectra of articles including the embodiments of optical coatings described herein. In the making of Example 2 and Comparative Examples 1-1 mold through 3, unless otherwise specified, the optical coating comprises AlO _x N _y, SiO, and mixtures thereof layer _2. Substrate molding parameters are based on glass substrates commercially available from Corning® (Corning Glass Code 5318).

The refractive index dispersion curve of the coating material used for modeling is based on measured values. A single film of SiO ₂ and AlO _x N _y was formed by reactive sputtering on the metal mold rotating cylinder on the melt-formed and ion-exchanged 5318 glass. The AlO _x N _y manufactured and used in the molding example has the following nominal composition: about 10 to 16 atomic% oxygen (~12% by weight oxygen), 32 to 40 atomic% nitrogen, and 48 to 54 atomic% aluminum. The refractive index of these single films was measured using a spectroscopic ellipsometer. The results of these measurements are shown in Table 2. In some examples, the linear average of the refractive index of SiO ₂ and AlO _x N _y is used for the intermediate coefficient mixed material. In summary, these refraction coefficients were measured from experimentally manufactured materials, where the molding examples used optical simulated coating designs based on the experimental refraction coefficients listed here. For convenience, the modeling example uses a single refractive index value in its description table, which corresponds to a point selected from the dispersion curve at a wavelength of about 550 nm.

Table 2: Measured refractive index of 5318 glass substrate, SiO ₂ sputtered film and AlO _x N _y sputtered film

In the example, the thickness is a physical thickness, not an optical thickness. The structure of Examples 1 to 3 is similar to the structure of Figure 5, Figure 6, or Figure 7, but with the specific layers, layer composition, and layer thickness provided in the examples. The structure of Example 2 is similar to FIG. 5, in which the refractive index of one gradient part fluctuates throughout the gradient part, rather than monotonously increasing or decreasing. However, the transition between the high refractive index and the low refractive index is not an abrupt interface, but satisfies the gradient part as defined herein.

In an example, the outer surface may also be referred to as the "front" surface, and is the surface opposite the substrate. One-sided reflectance and one-sided reflection color are measured on the front (coated) surface while removing reflection from the back side of the coated article (usually achieved by optically coupling the back surface to the absorbing substrate). The transmittance is measured by the light passing through the front surface toward the substrate. For example, if the example is used on the outward facing surface of the glasses, the transmission through the outer surface or front surface will be seen by the wearer, while the reflection from the outer surface or front surface will be seen by others . A CIE D65 light source and D65 detector were used to simulate the molding example.

Unless otherwise noted, the reflectance and transmittance of the molded examples are plotted at 0 degrees (normal incidence). In practice, the change in optical properties from 0 to 10 degrees is negligible, meaning that normal incidence and near-normal incidence can be considered to be functionally equivalent, as defined by the angle range of 0 to 10 degrees. The average polarization is used for all reflectance, transmittance and color calculations.

In all the examples of the present disclosure, the thickness of the thickest hard layer (2000 nm in Examples 1 to 3) can be changed to any value from 500 nm to 5000 nm without significantly changing the optical properties. Similarly, the thickest hard layer can be composed of multiple sub-layers, for example, a layer <10 nm to form a "superlattice" while maintaining high hardness and similar effective optical properties.

In the drawing showing the structures of Examples and Comparative Examples, the glass substrate is on the left. The thickness axis is centered, where 0 marks the beginning of the thickest hard layer. The gradient part of the coating is modeled as a series of discrete small steps of thickness and coefficient. It should be appreciated that continuous gradients with similar gradient slopes, or gradients with different discontinuous step sizes but similar overall slopes, can be designed to have substantially the same optical properties. Comparative Example 1

Table 3 shows the structure of Comparative Example 1. Comparative Example 1 has a discontinuous layered structure.

Table 3: Comparative Example 1, structure

Table 4 lists the 1-side reflection color, 2-side transmission color, bright-view average reflectance and bright-view average transmittance of Comparative Example 1.

Table 4

Figure 7 depicts the coating design of Comparative Example 1 as a graph of refractive index versus position. Figure 8 depicts the details of the partial coating design of Comparative Example 1 as a graph of refractive index versus position. FIG. 9 shows the reflection spectrum of Comparative Example 1. FIG. 10 shows the transmission spectrum of Comparative Example 1. FIG. 11 is a graph showing the relationship between D65 color and angle reflected by the surface of Comparative Example 1. FIG. Figures 9 and 10 are based on incident light passing from the right side to the left side of Figure 7. Comparative Example 2

Table 5 shows the structure of Comparative Example 2. Comparative Example 2 has a simple gradient, which results in a relatively high reflectivity.

Table 5: Comparative Example 2, structure

Table 6 lists the 1-side reflection color, 2-side transmission color, bright-view average reflectance and bright-view average transmittance of Comparative Example 2.

Table 6

Figure 12 depicts the coating design of Comparative Example 2 as a graph of refractive index versus position. Figure 13 depicts the details of the partial coating design of Comparative Example 2 as a graph of refractive index versus position. FIG. 14 shows the reflection spectrum of Comparative Example 2. FIG. 15 shows the transmission spectrum of Comparative Example 2. FIG. 16 is a graph showing the relationship between D65 color and angle reflected by the surface of Comparative Example 2. FIG. Figures 14 and 15 are based on incident light passing from the right side to the left side of Figure 12. Example 1

Example 1 includes hard-coated, chemically strengthened glass with a multilayer (non-gradient) structure that is on the substrate along with the gradient-containing anti-reflective top of the hard coating layer (located above the thick high hardness layer) High reflectivity is produced between thick high hardness layers. This coating produces a "blue" reflection color under near normal incidence, a maximum visible light reflectance of approximately 70%, and a bright-vision average visible light reflectance of approximately 35%. For all viewing angles between 0 and 90 degrees, the "blue" color can be well controlled and maintained, as shown in Figure 23. For all viewing angles between 0 and 90 degrees, the color of the 1 ^{st -surface} reflection is between -35 ≤ b* ≤ 0 and -12 ≤ a* ≤ 2.

Table 7 lists the structure of Example 1.

Table 7: Example 1, structure

Table 8 lists the 1-side reflection color, 2-side transmission color, bright-view average reflectance and bright-view average transmittance of Example 1.

Table 8

Figure 18 depicts the coating design of Example 1 as a graph of refractive index versus position. Figure 19 depicts the details of the partial coating design of Example 1 as a graph of refractive index versus position. Figure 20 shows the details of the partial coating design of Example 1 as a graph of refractive index versus position. FIG. 21 shows the reflection spectrum of Example 1. Figure 22 shows the transmission spectrum of Example 1. FIG. 23 shows the relationship between D65 color and angle reflected by the surface of Example 1. FIG. Figure 20 is based on incident light passing from the right side to the left side of Figure 17. Example 1 exhibits a multilayer interference stack from the substrate to a thick hard coating layer (the multilayer interference stack has a sharp interface), and a monotonically reduced refractive index from the thick hard coating layer to the external user surface. Example 2

Example 2 includes hard-coated, chemically strengthened glass with a multi-layered gradient-containing structure, which together with the gradient-containing anti-reflective top of the hard coating layer (located above the thick high-hardness layer) on the substrate and thick High reflectivity is produced between the high hardness layers. Similar to Example 1, this coating produces a "blue" reflection color under near normal incidence, a maximum visible light reflectance of approximately 70%, and an average visible light reflectance of approximately 35%. For all viewing angles between 0 and 90 degrees, the "blue" color can be well controlled and maintained, as shown in Figure 29. For all viewing angles between 0 and 90 degrees, the color of the 1 ^{st -surface} reflection is between -35 ≤ b* ≤ 0 and -12 ≤ a* ≤ 2.

Table 9 lists the structure of Example 2.

Table 9: Example 2, structure

Table 10 lists the 1-side reflection color, 2-side transmission color, bright-view average reflectance and bright-view average transmittance of Example 2.

Table 10: Example 2, reflection and transmission colors

Figure 24 depicts the coating design of Example 2 as a graph of refractive index versus position. Figure 25 depicts the details of the partial coating design of Example 2 as a graph of refractive index versus position. Figure 26 depicts the details of the partial coating design of Example 2 as a graph of refractive index versus position. Figure 27 shows the reflection spectrum of Example 2. Figure 28 shows the transmission spectrum of Example 2. FIG. 29 is a graph showing the relationship between D65 color and angle reflected by the surface of Example 2. FIG. Figures 27 and 29 are based on incident light passing from the right side to the left side of Figure 24. Example 2 exhibits a gradient portion from the substrate to the thick hard coating layer, the gradient portion having alternating high and low refractive index, and having a gentle refractive index slope between high and low refractive index ( 0.31 / nm or 0.318 / nm). Example 2 also exhibited a monotonous reduction in the refractive index from the thick hard coating down to the external user surface. Example 3

Example 3 includes a hard-coated, chemically strengthened glass with a gradient structure, which together with a non-graded top portion (located above the thick high hardness layer) that produces a multilayer with high reflectivity on the substrate and the thick Low reflectivity is produced between high hardness layers. This coating also produces a "blue" reflection color under near normal incidence, and has a maximum visible light reflectance of approximately 58%, and an average visible light reflectance of approximately 33%. For all viewing angles between 0 and 90 degrees, the "blue" color can be well controlled and maintained, as shown in Figure 34. For all viewing angles between 0 and 90 degrees, the color of 1 ^{st -surface} reflection is between -41 ≤ b* ≤ 0 and -20 ≤ a* ≤ 0.

Table 11 lists the structure of Example 3.

Table 11: Example 3, structure

Table 12 lists the 1-side reflection color, 2-side transmission color, bright-view average reflectance and bright-view average transmittance of Example 3.

Table 12

Figure 30 depicts the coating design of Example 3 as a graph of refractive index versus position. Figure 31 depicts the details of the partial coating design of Example 3 as a graph of refractive index versus position. Figure 32 shows the reflection spectrum of Example 3. Figure 33 shows the transmission spectrum of Example 3. FIG. 34 is a graph showing the relationship between D65 color and angle reflected by the surface of Example 3. FIG. Figures 32 and 34 are based on incident light passing from the right to the left of Figure 30. Example 3 exhibits a monotonically increasing refractive index from the substrate to the thick hard coating, and a multilayer interference stack with a sharp interface from the thick hard coating down to the external user surface. Example 4

Example 4 includes hard-coated, chemically strengthened glass, where the hard coating is an all-gradient design. Example 6 was actually manufactured and its hardness was evaluated.

Figure 38 shows the composition of the hard coat of Example 4 in terms of the oxygen atom concentration of different elements. Line 3810 shows the elemental carbon content. Line 3820 shows the element nitrogen content. Line 3830 shows the elemental oxygen content. Line 3840 shows the elemental aluminum content. Line 3850 shows the elemental silicon content. Line 3860 shows the elemental potassium content.

FIG. 39 shows the refractive index distribution of the hard coating of Example 4. Figure 39 is generated based on data measurements at a limited number of points across the gradient, which confirms the expected refractive index distribution, which can be used to determine the expected atomic concentration of the element at each location.

The highest absolute value of the slope of the refractive index in Example 4 is 0.0017 / nm. The maximum hardness of the product of Example 4 was measured to be 14.9 GPa. Example 4 demonstrates a full gradient hard coating with high hardness.

It is obvious to those with ordinary knowledge in the technical field to which this case belongs that various modifications or changes can be made without departing from the spirit or scope of the present disclosure.

As used herein, the term "about" means that the amount, size, formulation, parameters, and other quantities and characteristics are not precise and need not be precise, but may be approximate and/or larger or smaller as needed, reflecting Tolerances, conversion factors, rounding, measurement errors, etc., as well as other factors known to those with ordinary knowledge in the technical field to which this case belongs. When the term "about" is used to describe a value or endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to. Regardless of whether the numerical value or end point of the range in the specification describes "about", the numerical value or end point of the range is intended to include two embodiments: one modified by "about" and one not modified by "about". It will be further understood that the endpoint of each range is important with respect to the other endpoint and is independent of the other endpoint.

As used herein, the terms "substantial", "substantially" and variations thereof are intended to note that the described feature is equal to or approximately equal to the value or description. For example, a "substantially planar" surface is intended to mean a flat or nearly flat surface. Also, "substantially" is intended to mean that two values are equal or nearly equal. In certain embodiments, "substantially" may mean values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

The directional terms used herein—for example, up, down, right, left, front, back, top, and bottom—are only made with reference to the drawings that are drawn, and are not meant to imply absolute orientation.

As used herein, the transitional term "comprising", which is synonymous with "including", "containing" or "characterized by", is inclusive or open-ended and does not exclude additional, undocumented elements or method steps. The transitional term "consisting of" excludes any elements, steps, or ingredients not specified in the list after "consisting of". The transitional term "consisting essentially of" limits the scope to the specified materials or steps, as well as those materials or steps that do not substantially affect the basic and novel features described in the scope of the patent application.

As used herein, the terms "the" and "one" mean "at least one" and should not be limited to "only one" unless there is a clear indication to the contrary. Thus, for example, reference to "a component" includes embodiments having two or more such components, unless the context clearly indicates otherwise.

100: product 110: substrate 112: main surface 114: main surface 116: secondary surface 118: secondary surface 120: optical coating 122: primary surface/outer surface 124: primary surface 125: additional layer 126: thickness direction 130: first Gradient part 140: thick high hardness part 150: second gradient part 170: optional layer 180: optional layer 200: product 300: product 400: product 500: product 600: product 610: multilayer interference stack 620: section 622 : Low RI layer 624: High RI layer 3500: Glasses 3510: Lens 3520: Frame 3530: Bridge 3540: Temple 3600: Consumer electronics 3602: Case 3604: Front 3606: Back 3608: Side surface 3610: Display 3612 : Cover

Figure 1 is a side view of an article according to one or more embodiments;

Figure 2 is a side view of an article according to one or more embodiments;

Figure 3 is a side view of an article according to one or more embodiments;

Figure 4 is a side view of an article according to one or more embodiments;

Figure 5 is a side view of an article according to one or more embodiments;

Figure 6 is a side view of an article according to one or more embodiments;

Figure 7 is a side view of an article according to one or more embodiments;

Figure 8 shows the coating design of Comparative Example 1;

Figure 9 shows the coating design of Comparative Example 1;

Figure 10 shows the reflection spectrum of Comparative Example 1;

Figure 11 shows the transmission spectrum of Comparative Example 1;

FIG. 12 is a graph showing the relationship between D65 color and angle reflected by the surface of Comparative Example 1;

Figure 13 shows the coating design of Comparative Example 2;

Figure 14 shows the coating design of Comparative Example 2;

Figure 15 shows the reflection spectrum of Comparative Example 2;

Figure 16 shows the transmission spectrum of Comparative Example 2;

FIG. 17 is a graph showing the relationship between D65 color and angle reflected by the surface of Comparative Example 2;

Figure 18 shows the coating design of Example 1;

Figure 19 shows the coating design of Example 1;

Figure 20 shows the coating design of Example 1;

Figure 21 shows the reflection spectrum of Example 1;

Figure 22 shows the transmission spectrum of Example 1;

Figure 23 shows the relationship between the D65 color and angle reflected by the surface of Example 1;

Figure 24 shows the coating design of Example 2;

Figure 25 shows the coating design of Example 2;

Figure 26 shows the coating design of Example 2;

Figure 27 shows the reflection spectrum of Example 2;

Figure 28 shows the transmission spectrum of Example 2;

Figure 29 shows the relationship between the D65 color and angle reflected by the surface of Example 2;

Figure 30 shows the coating design of Example 3;

Figure 31 shows the coating design of Example 3;

Figure 32 shows the reflection spectrum of Example 3;

Figure 33 shows the transmission spectrum of Example 3;

Figure 34 shows the relationship between D65 color and angle reflected by the surface of Example 3;

Figure 35 shows the relationship between D65 color and angle reflected by the surface of Example 4;

Figure 36 shows an article (eyeglass lens) according to one or more embodiments;

Figure 37 shows a product (cover for a smart phone) according to one or more embodiments;

Figure 38 shows the composition of the hard coat of Example 4.

FIG. 39 shows the refractive index distribution of the hard coating of Example 4.

Domestic storage information (please note in order of storage institution, date, number) No

Overseas hosting information (please note in order of hosting country, institution, date, number) No

100: product

110: substrate

112: Main surface

114: Main surface

116: Subsurface

118: Subsurface

120: Optical coating

122: main surface/outer surface

124: Main surface

126: thickness direction

170: optional layer

180: optional layer

Claims (18)

An article includes: a substrate including a first main surface; and an optical coating disposed above the first main surface, the optical coating including: a second main surface, relative to the first main surface, A thickness in a direction perpendicular to the second main surface and a first gradient portion, wherein: a refractive index of the optical coating is along a distance between the first main surface and the second main surface The thickness of the optical coating varies; the difference between the maximum refractive index of the first gradient portion and the minimum refractive index of the first gradient portion is 0.1 or more; at each location along the thickness of the first gradient portion , The absolute value of the slope of the refractive index of the first gradient part is 0.1 / nm or less; where the product exhibits: measured at the second main surface, averaged over one of the wavelength range 400 nm to 700 nm The single surface reflectivity is 15% to 98%; one of the maximum hardness in the range from about 10 GPa to about 30 GPa, in which an indentation is formed by pressing into the second main surface with a Berkovich indenter, so that The maximum hardness is measured on the second main surface, and the indentation includes an indentation depth of about 100 nm or greater from the surface of the second main surface; where within a range of a change in refractive index of 0.04, along the Thickness measurement slope. The article according to claim 1, wherein: at each location along the thickness of the first gradient portion, the absolute value of the slope of the refractive index of the optical coating is 0.001/nm or more. The article of claim 1, wherein the optical coating further comprises a high hardness portion, wherein: the thickness of the high hardness portion is 200 nm or more: the average refractive index of the high hardness portion is 1.6 or more Large; and the maximum hardness of the high hardness portion is 10 GPa or higher, in which the maximum hardness is measured by pressing a thick high hardness portion with a Berkovich indenter to form an indentation, the indentation including about 100 nm Or a greater depth of indentation. The article according to claim 3, wherein the difference between the maximum refractive index of the high hardness portion and the minimum refractive index of the high hardness portion is 0.05 for 95% or more of the thickness of the high hardness portion Or smaller. The article according to claim 3, wherein in the direction of the thickness from the second main surface toward the first main surface, the optical coating sequentially includes: the first gradient portion; and the high hardness portion, In contact with the first gradient portion; wherein, where the high hardness portion contacts the first gradient portion, the difference between the refractive index of the high hardness portion and the maximum refractive index of the first gradient portion is 0.05 or less . The article according to claim 3, wherein the optical coating further includes a second gradient portion disposed between the high hardness portion and the substrate, wherein the second gradient portion and the high hardness portion Contact, and wherein: the difference between the maximum refractive index of the second gradient portion and the minimum refractive index of the second gradient portion is 0.05 or greater; along each location of the thickness of the second gradient portion, the optical The absolute value of the slope of the refractive index of the coating is 0.1/nm or less. The article of claim 3, wherein: the refractive index of the first gradient portion increases monotonously along the thickness in a direction away from the second main surface; the optical coating further includes a multilayer interference stack, The multi-layer interference stack includes discontinuous layers that are disposed between the high-hardness portion and the substrate. The article of claim 3, wherein: the refractive index of the first gradient portion increases monotonously along the thickness in a direction away from the second main surface; the optical coating further includes a second gradient portion, The second gradient portion fluctuates across the thickness of the gradient portion as a function of the distance from the substrate. The article according to any one of claims 1 to 8, wherein the absolute value of the slope of the refractive index of the optical coating is 0.1/nm or less at each of the optical coatings. The product according to any one of claims 1 to 8, wherein at least one of the following is satisfied: When measured on the second main surface, the product exhibits a single view in all viewing angles from 0 to 60 degrees Side reflection color range, the single side reflection color range contains all a* points with a value of 5 or less; and when measured on the second main surface, the product exhibits all viewing angles from 0 to 60 degrees A single-sided reflection color range is included. The single-side reflection color range includes all b* points with a value of 5 or less. The article according to any one of claims 1 to 8, wherein the article exhibits a single-sided reflection color range for all viewing angles from 0 to 10 degrees when measured on the second main surface, the The one-sided reflection color range includes at least one a* point or b* point having a value of 20 or more. The article of any one of claims 1 to 8, wherein the optical coating includes one having a thickness ranging from about 0.5 µm to about 3 µm. The article according to any one of claims 3 to 8, wherein the cumulative thickness of any portion of the optical coating between the high-hardness portion and the second main surface including the RI of 1.6 or less is 200 nm or less. The article of any one of claims 1 to 8, wherein the optical coating includes a composition gradient including at least two of Si, Al, N, and O. The article according to any one of claims 1 to 8, wherein the article is an anti-scratch mirror. An eyeglass comprising a lens, wherein the lens comprises the article according to any one of claims 1 to 8. A consumer electronic product includes: a housing having a front surface, a rear surface, and a plurality of side surfaces; a plurality of electronic components, at least partially disposed in the housing, the electronic components including at least a controller, A memory and a display, the display is located at or near the front surface of the housing; and a cover plate is provided above the display, wherein at least one of a part of the housing or the cover plate includes items as requested The product according to any one of 1 to 8. A method for forming an article includes the following steps: obtaining a substrate including a first main surface and including an amorphous substrate or a crystalline substrate; providing an optical coating on the first main surface, the optical coating The layer includes a second main surface and a thickness, the second main surface is opposite to the first main surface, and the thickness is in a direction perpendicular to the second main surface, along at least the thickness of the optical coating A first gradient portion produces a refractive index gradient, wherein: a refractive index of the optical coating changes along a thickness of the optical coating between the first main surface and the second main surface; the The difference between the maximum refractive index of the first gradient portion and the minimum refractive index of the first gradient portion is 0.1 or more; at each location along the thickness of the first gradient portion, the refractive index of the first gradient portion The absolute value of the slope of is 0.1/nm or less; where the article exhibits: Measured at the second major surface, the average single surface reflectivity is within a range of 400nm to 700nm from 15% to 98% ; And one of the maximum hardness in the range from about 10 GPa to about 30 GPa, in which a maximum pressure is measured on the second main surface by pressing a Berkovich indenter into the second main surface to form an indentation The indentation includes an indentation depth of about 100 nm or greater from the surface of the second main surface; wherein the slope is measured along the thickness within a range of 0.04 refractive index change.

Images