Anti-glare surface treatment method and articles thereof

Description of related application

This application is based on its contents and is inclusive of all, prioritized under US Code 35, Article 119, filed on November 29, 2010, US Provisional Patent Application No. 61/417674. It claims the benefits of rights.

Description of simultaneous pending application This application is entitled "Anti-Glare Surface Treatment Method and Articles Thereof", US Provisional Patent Application No. 61/329936 of the same applicant filed on August 30, 2010, and "Anti-Glare Surface Treatment Method". and Articles There of , related to US Provisional Patent Application No. 61/372655 of the same applicant filed on August 11, 2010.

The present disclosure broadly relates to methods of manufacturing and using antiglare surfaces and articles thereof.

<p> The present disclosure provides a method of manufacturing an antiglare surface, an article manufactured by that method, and a display system comprising an article having an antiglare surface. In embodiments, the manufacturing method involves depositing sacrificial deformable particles on at least one surface of an article, treating the surface on which the deformable particles are placed, i.e., the granulated surface. , At least a step of adhering particles to the surface, and a step of bringing the resulting granulated surface into contact with an etching solution to form an antiglare rough surface.</p>

<figref num="1">Explanatory drawing of the method of manufacturing an antiglare layer on a glass surface</figref><figref num="2">Illustrative microscopic image of wax particles slot die coated on the surface of Gorilla® glass</figref><figref num="3">An exemplary microscopic image of the surface of the "Gorilla" glass in Figure 2, which was then heat treated at 75 ° C for 30 seconds.</figref><figref num="4">4A and 4B are two different magnification microscopic images of the exemplary etched surface, respectively, after the glass sample was slot die coated with a polymer particle formulation and then heat treated at 106 ° C for 30 seconds.</figref><figref num="5A">High magnification surface analysis image of surface roughness of etched pieces after coating and heat treatment at 106 ° C for 30 seconds and etching time for 30 seconds</figref><figref num="5B">Low magnification surface analysis image of surface roughness of etched pieces after coating and heat treatment at 106 ° C for 30 seconds and etching time for 30 seconds</figref><figref num="6A">Illustrative microscopic image of particles slot die coated on the surface of "Gorilla" glass before heat treatment at 80 ° C for 40 seconds.</figref><figref num="6B">Illustrative microscopic image of slot die-coated particles on the surface of "Gorilla" glass after heat treatment at 80 ° C for 40 seconds</figref><figref num="7A">Illustrative microscopic image of particles slot die coated on the surface of "Gorilla" glass before heat treatment at 105 ° C for 30 seconds.</figref><figref num="7B">Illustrative microscopic image of slot die-coated particles on the surface of "Gorilla" glass after heat treatment at 105 ° C for 30 seconds.</figref><figref num="8A">Histogram showing an example of particle size distribution for an exemplary particle suspension formulation measured by laser light scattering</figref><figref num="8B">Histogram showing an example of particle size distribution for an exemplary particle suspension formulation measured by laser light scattering</figref>

In embodiments, the disclosed articles and disclosed methods of manufacture and use provide one or more advantageous features or embodiments, including, for example, those discussed below. The features or aspects listed in any of the claims are generally applicable to all aspects of the invention. Any one or more enumerated features or embodiments in any one claim may be combined with or out of order with any other enumerated features or embodiments in any other claim. It doesn't matter.

Definition "Anti-glare" or similar term refers to a changing physical transformation of light that comes into contact with a treated surface of an article of the present disclosure, such as a display, or a change that reflects from the surface of an article to diffuse reflection rather than specular reflection. Refers to the nature of light. In embodiments, the surface treatment can be performed by mechanical, chemical, electrical, and similar etching methods, or a combination thereof. Anti-glare does not reduce the amount of light reflected from the surface, it only changes the characteristics of the reflected light. The image reflected on the antiglare surface has no clear boundaries. In contrast to anti-glare surfaces, anti-reflective surfaces are generally thin film coatings that reduce the reflection of light from the surface by the use of refractive index fluctuations, in some cases by offsetting interference.

The term "contact" or similar term refers to a close physical touch that can cause a physical change, a chemical change, or both in at least one touched entity. In the present disclosure, various microparticle deposition or contact techniques, such as spray coating, immersion coating, slot coating, and similar techniques, are granulated when contacted as illustrated herein and illustrated. Can provide a surface. In addition or instead, various chemical treatments of the granulated surface, such as spraying, immersion, immersion, and similar techniques, as illustrated and illustrated here, etch one or more types. An etched surface can be provided when contacted with the liquid composition.

"Reflective image sharpness", "image sharpness", "DOI" or similar terms are entitled "Standard Test Methods for Instrumental Measurements of Distinctness-of-Image Gloss of Coating Surfaces", ASTM Method D5767 (ASTM) It is defined by Method A of 5767). According to ASTM 5767 Method A, the reflectance coefficient measurements of glass are made on at least one rough surface of the glass article at an emmetropic angle and at an angle slightly offset from the emmetropic angle. The values obtained from these measurements are combined to provide the DOI value. Specifically, the DOI is Eq. (1):<maths num="1"><img file="JP2013545708A_D0001.tif" /></maths>

In the equation, Rs is the relative amplitude of the forward reflectance and Ros is the relative amplitude of the reflectance deviated from the positive direction. As described herein, Ros is calculated by averaging the reflectance over an angular range of 0.2 ° to 0.4 ° away from the positive direction, unless otherwise stated. Rs can be calculated by averaging the reflectance over an angular range of ± 0.05 ° centered in the positive direction. Both Rs and Ros are light distribution measuring instruments (Novo-gloss IQ, Rhopoint) calibrated to certified black glass standards, as specified in ASTM techniques D523 and D5767. Measured using Instruments). This Novo-gloss device uses a detector array whose conformal angle is centered on the highest value of the detector array. DOIs were also evaluated using the single-sided (black absorber bonded to the back of the glass) and double-sided (reflections generated from both sides of the glass without binding anything to the glass). Single-sided measurements can determine gloss, reflectance, and DOI for one side of a glass article (eg, one rough surface), while double-sided measurements can determine gloss, reflectance, and DOI for the entire glass article. DOI can be determined. The Ros / Rs ratio can be calculated from the mean values obtained for Rs and Ros as described above. 20 ° DOI or DOI 20 ° refers to a DOI measurement in which light is incident on a sample 20 ° off perpendicular to the glass surface, as described in ASTM D5767. Measurements of either DOI or general gloss using the double-sided method can best be done in a dark room or enclosure so that measurements of these properties are zero in the absence of a sample.

For the antiglare surface, it is generally desirable that the DOI is relatively low and the reflectance ratio (Ros / Rs) of Eq. (1) is relatively high. This results in blurred or unclear reflection image vision. In embodiments, at least one rough surface of the glass article is Ros greater than about 0.1, greater than about 0.4, and greater than about 0.8 when measured at an angle of 20 ° from the positive direction using single-sided measurements. Has / Rs. Using the double-sided method, the Ros / Rs of a glass article at an angle of 20 ° from the positive direction is greater than about 0.05. In embodiments, Ros / Rs measured by the double-sided method for glass articles is greater than about 0.2 and greater than about 0.4. General gloss, as measured by ASTM D523, is insufficient to distinguish a surface with a strong specular component (clear specular image) from a surface with a weak specular component (blurred specular image). This may be due to a small angle scattering effect that cannot be measured using a general gloss meter designed according to ASTM D523.

The terms "transmitted haze", "haze" or similar refer to specific surface light scattering properties related to surface roughness. Haze measurements are described in more detail below.

The terms "roughness", "surface roughness (Ra)" or similar terms are flat or irregular, such as average root mean square (RMS) roughness or the RMS roughness described below, below the microscopic level. Refers to a surface condition.

The terms "gloss", "gloss level" or similar terms refer to, for example, the luster, vividness, or brilliance of a surface, and more specifically, the standards according to ASTM Method D523, all of which are cited herein (eg,) Refers to a specular reflectance measurement calibrated to a certified black glass standard). General gloss measurements are typically made at incident light angles of 20 °, 60 °, and 85 °, with the most commonly used gloss measurements being made at 60 °. However, due to the wide reception angle of this measurement, general gloss is often indistinguishable between surfaces with high reflection image sharpness (DOI) values and surfaces with low DOI values. The antiglare surface of a glass article has a gloss up to 90 SGU (standard gloss unit) measured according to ASTM standard D523 (ie, the amount of light specularly reflected from the sample against the standard at a particular angle). In one embodiment, it has a gloss in the range of about 60 SGU to about 80 SGU. See also the definition of DOI below.

The terms "adhesive", "adhesive", "anneal", "anneal" or similar terms are deformed individually or collectively and then firmly attached to the surface of the glass being treated. Accumulated particles, including particle-to-surface attraction or binding (adhesion), particle-to-particle attraction or bonding (aggregation), and similar interactions when binding, sticking, and exhibiting similar binding conditions. Refers to the state or action of.

The terms "deformable", "deformable", "deformable" or similar are deposited when attached to a glass surface by, for example, thermal, mechanical, radiant, or similar means. Refers to the state or action of the particles.

The term "ALF" or "average specific maximum feature size" or similar term refers to a measure of the variation in surface features in the x and y directions, i.e., in the plane of the substrate, as further discussed below.

The terms "sparkle", "sparkle of display" or similar terms refer to the relationship between the size of a feature on at least one rough glass surface and the pixel pitch of interest, especially the smallest pixel pitch. .. The "sparkle" of a display is generally evaluated by human visual inspection of the material placed adjacent to the pixelated display. Its relationship to ALF and display "sparkles" has been found to be a valid metric for different materials with different surface morphologies, including glass and particle coated polymeric materials of various compositions. There is a strong correlation between the average specific maximum feature size (ALF) and the visual order of the sparkle intensity of the display across a number of different sample materials and surface morphologies. In embodiments, the glass article may be a glass panel that forms part of the display system. The display system may include a pixelated image display panel arranged adjacent to the glass panel. The minimum pixel pitch of the display panel can be larger than ALF.

The terms "uniformity", "uniformity" or similar refer to the surface quality of an etched sample. Surface uniformity is generally assessed by human visual inspection at various angles. For example, a glass article sample is held at approximately eye level and then slowly rotated from 0 degrees to 90 degrees under standard white fluorescent lighting conditions. If pinholes, cracks, unevenness, roughness, or other similar defects cannot be detected by the observer, the surface quality is considered "uniform", otherwise the sample is considered non-uniform. Be done. A "good" or "OK" rating means that the uniformity is acceptable or satisfactory, with the former being subjectively better than the latter.

The term "contains" or similar means inclusive but not limited, i.e., inclusive and not exclusive.

In the embodiment, "becomes substantial" means, for example, A method of producing a glass article, as defined herein, by depositing particles on the surface of the glass article, adhering the particles to the surface of the article, and bringing the granulated surface into contact with an etching solution. A glass article having an antiglare surface with haze, image sharpness, surface roughness, and uniform properties, as defined herein, or Display systems with glassware, as defined here, Can be referred to.

This method of manufacture, article, display system, composition, formulation, or any device of the present disclosure, in addition to the components or steps listed in the claims, may be a particular reactant, a particular additive or ingredient, The basic properties of the compositions, articles, devices, or methods of manufacture and use of the present disclosure, such as specific agents, specific surface modifiers or conditions, or selected similar structures, materials, or process variables. It may include other components or processes that do not substantially affect the new properties. Examples of items that may substantially affect the basic properties of the components or processes of the present disclosure or that may give undesired features to the present disclosure include intermediate values and ranges herein. Surfaces with undesired high glare or high gloss properties that exceed defined and defined values, such as haze, image sharpness, surface roughness, uniformity, or a combination thereof.

As used here, a singular noun means at least one, or one or more, unless otherwise stated.

The abbreviations familiar to those skilled in the art may be used (eg, "h" or "hr" for hours, "g" or "gm" for grams, "mL" for milliliters, "rt" for room temperature, nanometers. Abbreviations such as "nm" for meters).

The specific and preferred values disclosed for components, ingredients, additives, and similar embodiments, and their ranges are for illustration purposes only; they are other defined or defined ranges. It does not exclude other values in. The compositions, devices, and methods of the present disclosure may include any value described herein or any combination of values described herein, specific values, more specific values, and preferred values.

Chemically tempered glass is used in many handheld and touch-sensitive devices as display windows and cover plates where resistance to mechanical damage can be important to the appearance and function of the product. During chemical strengthening, the larger alkaline ions in the molten salt bath are exchanged for smaller mobile alkaline ions located within some distance from the glass surface. The ion exchange process compresses the surface of the glass, making it more resistant to mechanical damage commonly exposed during use.

In particular, it is often desirable for manufacturers of products designed for outdoor use where glare can be amplified by sunlight to reduce specular reflection (a significant cause of glare) from many display surfaces. One way to reduce the gloss and the intensity of specular quantification is to roughen the glass surface or coat it with a textured film. The roughness or texture dimensions should be large enough to scatter visible light, resulting in a slightly blurred or matte surface, but too large to significantly affect the transparency of the glass. is not it. If it is not important to maintain the properties of the glass substrate (eg, scratch resistance), textured or particle-containing polymeric films can be used. While these films may be cheap and easy to apply, they have the ease of wear that can reduce the display capabilities of the device. Another drawback of using films or coatings is that they can interfere with the operation of certain touchsense devices or reduce their performance. Another technique for roughening the glass surface is chemical etching. U.S. Pat. Nos. 4921626, 6807824, and 5989450, as well as WO 2002/053508, describe glass etching compositions and methods of etching glass with those compositions. Has been done. The wet etching method is a method of producing an antiglare surface on glass while maintaining the inherent mechanical surface properties. During this process, the glass surface is exposed to chemicals that degrade the surface to accurate roughness dimensions due to visible light scattering. When multiple microstructural regions with different solubilities are present, as in soda lime silicate glass, rough surfaces are formed by placing the glass in a mineral acid solution (generally containing fluoride ions). can do. Such selective leaching or etching includes alkaline earth aluminosilicates and mixed alkalis.

One of the consequences of roughening the glass surface is the formation of a perceived "sparkle" with a granular appearance. Sparkle is manifested by the appearance of bright and dark or tinted spots on a nearly pixel-level size scale. The presence of sparkle reduces the viewability of the pixelated display, especially under high ambient light conditions.

In embodiments, the present disclosure is a method of manufacturing an article having an antiglare surface. The process of depositing deformable particles on at least one surface of an article, The process of deforming the deformable particles deposited on the surface and attaching them to the surface, and A process of forming an antiglare surface by bringing a surface having deformed and adhered particles into contact with an etching solution. To provide a method of having.

In embodiments, the present disclosure is a method of manufacturing an article having an antiglare surface. The process of depositing particles on at least one surface of an article, The process of deforming the particles deposited on the surface and attaching them to the surface, and A process of contacting a surface with adhered particles with an etching solution to form an antiglare surface, To provide a method of having.

In embodiments, the present disclosure is a method of manufacturing an article having an antiglare surface. The process of depositing particles on a portion of at least one glass surface of an article, The process of heating the particle surface to attach the particles deposited on the glass surface, and A process of forming an antiglare surface by bringing the glass surface having adhered particles into contact with an etching solution. To provide a method of having.

In embodiments, the present disclosure is a method of manufacturing an article having an antiglare surface. The process of depositing deformable particles on a portion of at least one glass surface of an article, The process of deforming the deformable particles deposited on the surface and attaching them to the glass surface, and A process of forming an antiglare surface by bringing the glass surface having adhered particles into contact with an etching solution. To provide a method of having.

In embodiments, the present disclosure is a method of manufacturing an article having an antiglare surface. The process of depositing polymer particles on a portion of at least one glass surface of an article, The process of heating the surface of the polymer particles to attach the polymer particles deposited on the glass surface, and A process of forming an antiglare surface by bringing the glass surface having adhered particles into contact with an etching solution. To provide a method of having.

In embodiments, the glass surface is, for example, soda lime silicate glass, alkaline earth aluminosilicate glass, alkaline aluminosilicate glass, alkaline borosilicate glass, boroaluminosilicate glass, or at least a combination thereof. The deformable particles can be, for example, at least one polymer, wax, or a combination thereof, and the etchant can be HF, H.₂SO₄, Or at least one acid selected from a combination thereof. Examples of polymer particles include polymers, copolymers, polymer nanoparticles, crosslinked polymer particles, UV curable polymer particles, core-shell polymers with core polymers having a Tg lower than the Tg of shell polymers, waxes, or combinations thereof. Be done.

In the embodiment, the deformation of the deposited deformable particles can be performed by heating, for example. The heating may be carried out by any suitable means such as heat means, radiant means, pressure means, and similar methods, or a combination thereof. Examples of such heating means include heat ray guns, hot gas knives, convection ovens, heating lamps, radiant radiators, press plates, heated irons, and similar means, or combinations thereof.

In embodiments, the step of depositing deformable particles on at least a portion of at least one glass surface of an article is, for example, a suspension of at least one glass surface with wax particles, polymer particles, or a combination thereof. It can be done by contacting with. The step of contacting at least one glass surface with a suspension of wax particles, polymer particles, or a combination thereof can be performed, for example, by a slot coater. In embodiments, the deposition process can be carried out, for example, without binders, fluidity modifiers, or combinations thereof.

In embodiments, the deposited deformable particles can be, for example, monolayers of particles, regular monolayers of particles, multilayers of particles, regular multilayers of particles, and combinations thereof.

In embodiments, contact with the etchant can be made, for example, by exposing the glass surface with the deposited deformable particles to the etchant for about 1 second to about 30 minutes.

In embodiments, the deposited particles are D of about 1 to about 30 micrometers, including, for example, median and median range.₅₀Can have a diameter.

In embodiments, the deposited particles can be, for example, polymeric particles containing thermoplastics, waxes, or combinations thereof. In embodiments, the deposited particles are, for example, from about 25 ° C to about 95 ° C, from about 25 ° C to about 85 ° C, from about 30 ° C to about 80 ° C, including intermediate values and ranges. It has a glass transition temperature (Tg) of about 35 ° C to about 50 ° C, and a similar glass transition temperature.

In embodiments, the step of depositing polymer particles, wax particles, or a mixture of polymer particles and wax particles on the surface of an article can be performed by a slot die coater and similar coating devices and methods.

In embodiments, the particles deposited on the surface have a wet thickness of about 1 to about 200 micrometers, such as about 2 to about 100 micrometers, including, for example, median and intermediate ranges, and, for example, median and It can be single-layer to multi-layer with a dry thickness of about 0.1 to about 50 micrometers, including an intermediate range, such as about 1 to about 25 micrometers.

In embodiments, the method may further comprise the step of treating the resulting rough surface with a low surface energy coating, eg, a fluorinated compound, to reduce wettability and facilitate cleaning.

In embodiments, the method may further include, after etching, a step of cleaning the resulting antiglare surface, a step of chemically strengthening the antiglare surface, or a combination thereof.

In embodiments, the method may further include contacting at least another surface of the article with an etching resistant protective layer that can be removed, if desired, prior to etching.

In embodiments, the present disclosure also provides glass articles prepared by any of the processes described above, including combinations or sequences thereof.

In embodiments, the present disclosure is About 0.1 to about 30 haze, Image sharpness of about 25 to about 85 (DOI 20 °), Surface roughness (Ra) of about 50 to about 500 nm, and Mountain-valley difference profile with average roughness of about 0.1 to about 10 micrometers, Has at least one anti-glare surface, Provide a glass article with.

In embodiments, the glass article can have, for example, an antiglare surface with a distribution of topographic features having an average diameter of about 1 to about 100 micrometers. The preferred diameter of the topographical features can be from about 0.1 to about 20 micrometers, including, for example, median values and ranges.

In embodiments, the glass article can be, for example, a protective cover glass plate for a display device.

In embodiments, the present disclosure is, for example, About 0.1 to about 30 haze, Image sharpness of about 25 to about 85 (DOI 20 °), Surface roughness (Ra) of about 50 to about 500 nm, and Mountain-valley difference profile with average roughness of about 0.1 to about 10 micrometers, A glass panel with at least one antiglare rough surface prepared by any of the methods described above, and Pixelized image display panel adjacent to the glass panel, To provide a display system including.

In embodiments, preferred haze can be, for example, less than about 10, including, for example, intermediate values and ranges, more preferred haze can be, for example, about 6 to about 9, and even more preferred haze can be, for example, for example. It can be about 5 to about 6 or less.

In embodiments, the present disclosure provides a coating and wet etching process for forming nano-scale to micro-scale texture surfaces on glass surfaces such as silicate glass. In embodiments, the process coats the glass surface, for example, with low molecular weight polymer particles, wax particles, or a combination thereof, and then contains, for example, intermediate values and ranges, from about 30 to about 140 °. C, about 35 to about 135 ° C, about 40 to about 130 ° C, about 45 to about 100 ° C, about 50 to about 90 ° C, about 55 to about 85 ° C, about 60 to about 80 ° C, And at relatively low temperatures of similar temperature, the heat treatment is included for a time sufficient to promote the deformation and adhesion of the particles on the glass surface. The granulated surface is then etched, for example, in HF, or a multi-component acid solution. The etching solution preferentially etches around the deformed particles on the glass surface to form an AG rough surface layer on the treated glass article.

A known etching process for producing an antiglare layer on a glass surface can include at least three baths. For example, the first bath may contain ABF to grow ammonium fluoride (ABF) crystals on the glass surface. The second bath is H to remove its crystals₂SO₄Can be contained. The third bath is H to smooth the glass surface₂SO₄It can be a mixture of / HF. A typical treatment time from the beginning to the end of the three-bath process can be, for example, about 60 to about 80 minutes.

Corning, Inc. has developed an alternative process, including the use of particle suspensions, as disclosed in US Provisional Patent Application No. 61/329936 of the same applicant. This particle suspension can be used to form a differential etching mask when applied to the glass surface and then etched. This process is significantly faster, but more complex and more expensive than the process disclosed herein. This disclosure process can have significant benefits compared to other processes, including, for example, the following features:

This process is an antiglare glass with significantly improved appearance properties, including very low sparkles, such as about 4 to about 6, compared to, for example, about 7 to about 12 sparkles that can be achieved by conventional processes. Provide the board in a reproducible manner.

The haze properties of the glass articles treated according to the present disclosure can be adjusted from low to very high. Low haze may be desirable for applications that require high display contrast, while high haze reduces the appearance of "black holes" in off-state displays or for optics with scattering, such as edge lighting. It can be useful for aesthetic reasons such as. Consumer or end-user preferences, as well as their end-use and mode of use, motivate the general preference for low-haze vs. high-haze (and the antinomy of performance).

The disclosed process allows the surface roughness of one or both sides of a glass plate to be adjusted over a range of roughness values from low to very high. Low roughness is commonly used to create small angle scattering and result in low DOI with low haze and corresponding high display contrast. However, the rough surface is high for some applications, such as certain touch-sensitive display devices, where the rough surface can provide the desired "sliding feel" for the user's contact points such as fingers, knuckles, toes, or nose. Roughness may be desirable. High roughness curing can also be useful in non-display applications such as mouse pad surfaces. For these touch applications, it may also be desirable to post-treat the rough surface with a low surface energy coating such as fluorosilane. This can reduce surface friction, improve the "sliding feel" effect, and make the surface less likely to get wet with oil and water, facilitating cleaning.

Widely adjustable, using a short etching time, eg about 30 seconds, with very little glass thickness loss compared to traditional antiglare processes, eg less than about 5 micrometers glass thickness loss. The haze value and roughness value could be achieved.

The disclosure process has a lower acid concentration or higher to achieve higher haze and roughness values compared to the process described in US Provisional Patent Application No. 61/372655, which is simultaneously pending by the same applicant. A short etching time can be used.

The ability to adjust haze, DOI, roughness, or a combination thereof by particle annealing temperature is the new flexibility to use the same acid composition for multiple haze levels, or to achieve a given haze level. It provides new flexibility to reduce the acid concentration used. The ability to control the glass surface profile by deformation of the particles before etching can be independent of the coating method (wet or dry).

The slot die coating process used to apply particles to glass deposits very thin layers of particles on the surface, such as one or two layers, or in some cases less than a single layer. This improves the ability of the acid to penetrate the space in the mask, which makes etching more efficient, consumes less acid, and consumes less particles.

In US Provisional Patent Application No. 61/329936, co-pending by the same applicant, the antiglare surface suspends particles in a liquid vehicle containing other components such as fluidity modifiers, modifiers, binders and the like. It was made turbid, then sprayed onto the glass surface, and then dried and etched. Due to the combination of particle binders, fluidity modifiers, and other components in the liquid, complexity may be added and the strength of the acid may be impaired, eg, reacting with one or more of the other components. May weaken the acid. The present disclosure can be done without these additives, which can reduce process complexity and reduce process costs.

In embodiments, the present disclosure provides a wet etching method for producing an antiglare surface on glass while maintaining inherent mechanical surface properties. During this process, the granulated glass surface is exposed to chemicals that can degrade the surface and change the surface roughness dimensions that are responsible for the scattering of visible light. When a large amount of mobile alkaline ions are present in the glass, as in soda lime silicate glass, the rough surface is formed, for example, by contacting the glass surface with an acid etching solution such as a solution containing fluoride ions. Can be formed.

In embodiments, at least one surface of the article can be, for example, glass, composite, ceramic, plastic or resin-based materials, and similar materials, or a combination thereof. In embodiments, the deposited deformable particles can be polymeric particles, on top of which or instead, for example, any suitable low melting point material: glass, composite, ceramic, plastic or resin-based material, metal, It may include salts, clays, polymers, copolymers, nanoparticles, crosslinked polymer particles, UV curable particles, wax particles, and similar materials, or combinations thereof. In embodiments, the etchant may contain at least one acid suitable for etching the surface underneath the deposited particles.

In embodiments, the glass surface can be selected from, for example, at least one of aluminosilicate glass, aluminoborosilicate glass, soda-lime glass, borosilicate glass, silica glass, and similar glass, or a combination thereof. Etching liquid is HF, H₂SO₄, Or a combination thereof, may contain at least one acid.

The step of bringing at least one surface into contact with the particles on or instead can be carried out with a concentrated particle suspension or an intermediate concentration particle suspension. Contact between the particles and the surface can be done by any suitable method, such as slot die coating, screen printing, roll knife coating (gap coating), rod coating, spray coating, curtain coating, and similar application methods, or them. It is preferable to use the combination of. The deposited particles are, for example, about 0.1 to about 30 micrometers, about 1 to about 30 micrometers, and about 1 to about 25 micrometers D, including intermediate values and ranges.₅₀Can have a diameter. In embodiments, the particle size range can be, for example, from about 0.1 to about 50 micrometers, from about 1 to about 30 micrometers, and from about 2 to about 20 micrometers, including intermediate values and intermediate ranges. In embodiments, the particle size properties are monomodal, bimodal, trimodal, including, for example, monodisperse, oligodisperse, polydisperse, and similar particle size and particle properties, or combinations thereof. , And can be similar peaks.

In embodiments, contact of the granulated surface with the etchant is, for example, on a surface with deposited particles, the etchant, eg, from about 10 seconds to about 10 minutes, from about 20 seconds to about 1 minute, and similar. It can be done by exposure for about 1 second to about 30 minutes, including intermediate values and ranges, such as exposure or interval.

In embodiments, the preparation method, as required, includes, for example, cleaning the resulting etched antiglare surface, chemically strengthening the antiglare surface, functional coating or film (eg, photosensitive or film). Polarized films) or protective surface coatings or films, and the steps of applying similar coatings or films, or combinations thereof, may further be included.

In embodiments, one side of the glass can be protected from the etchant if single-sided acid etching or similar modifications are desired on the glass plate. Protection can be provided, for example, by applying an insoluble non-porous coating such as acrylic wax, or an adhesive layer, such as a laminate film with acrylic, silicone, and similar adhesives, or a combination thereof. Examples of the coating application method include brush coating, roll coating, spray coating, laminating, and similar methods. The insoluble non-porous protective coating exposed to the acid etching solution withstands the etching process and can be easily removed after etching. What is the process of removing the protective film from the surface of the article, such as contact with the solution of the protective film, the process of heating the film to liquefy and drain it, and similar methods and materials, or a combination thereof. You can use the appropriate method. Therefore, the preparation method optionally provides an etching resistant protective layer capable of removing at least another surface of the article, eg, a second surface such as the back surface of a glass plate, if necessary, prior to etching. The step of contacting may be further included.

In embodiments, the disclosure is prepared by any of the preparation processes disclosed herein, such as glass articles prepared by the particle deposition step, particle deformation step, particle surface adhesion step, and etching step described above. Providing goods. In embodiments, the preparation process can be carried out sequentially, simultaneously, continuously, semi-continuously, in batches, and in similar permutations, or in combination thereof.

In embodiments, the surface of at least one of the articles can be glass, the deposited particles can be wax, and the etchant can be at least one acid.

In embodiments, the present disclosure is a glass article. For example, about 0.1 to about 30 hazes, such as about 0.1 to about 25, about 0.1 to about 20, about 0.1 to about 10, and about 1 to about 10, and about 0.1 to about 5, including intermediate values and ranges. , And low haze, such as about 1 to about 5, For example, image sharpness (DOI 20 °) of about 25 to about 85, about 40 to about 80, about 45 to about 75, and about 50 to about 70, including median and range. For example, surface roughness (Ra) of about 50 to about 500 nm, and about 80 to about 300 nm, including intermediate values and ranges, and Mountain-valley difference profile with average roughness of about 0.1 to about 10 micrometers, including median and range. Has at least one anti-glare surface, Provide a glass article with.

In embodiments, the glass articles with antiglare surfaces of the present disclosure include intermediate values and ranges, from about 0.1 to about 100 micrometers, from about 0.1 to about 50 micrometers, from about 0.1 to about 30 micrometers, and. It may include a distribution of topographical features with a similar range of average diameters.

In embodiments, the present disclosure is, for example, Haze from about 0.1 to less than about 30, including median and range Image sharpness (DOI 20 °), about 40 to about 80, including median and range Surface roughness (Ra) of about 100 to about 300 nm, including intermediate values and ranges, and Mountain-valley difference profile with average roughness of about 0.1 to about 10 micrometers, including median and range. A glass panel with at least one anti-glare rough surface, and Pixelized image display panel adjacent to the glass panel, To provide a display system including.

In embodiments, the present disclosure provides a wet etching process for forming uniform nano-scale to micro-scale texture surfaces on most silicate glasses without significantly affecting the chemical strengthening capacity of the glass. To do. This process deposits deformable particles, such as polymer particles, glass particles, or composite particles, or otherwise coats them on the glass surface, followed by deformation or surface adhesion of the particles, HF, Alternatively, each step of acid etching of the granulated surface is included, such as in a multi-component acid solution. In embodiments, the HF solution can be preferentially etched around particles attached or annealed on the glass surface, and then optionally from the etched surface, depending on conditions and duration. The attached or annealed particles may then be corroded and the surface roughness may be reduced.

In embodiments, the desired reduced luster or glare can be, for example, the following parameters: viscosity of particulate suspension, level or concentration of particles in the suspension, concentration of acid etchant, particles deposited on the surface. It can be obtained by adjusting at least one or more of the amount of particles used, the particle size distribution (PDS) of the particles used, and the exposure interval or duration during which the particle-bearing surface of the glass sample is in contact with the acid etchant. In embodiments, the masked surface can be etched, the mask can be removed from the masked surface, and the masked etched surface can be etched one or more times, eg, the mask is removed. It is possible to give at least some smoothness to the etched surface.

In embodiments, antiglare glass articles are provided. The glass article is ion exchangeable and may have at least one rough surface. This rough surface has a reflected image sharpness (DOI) (DOI at 20 °) of less than 90 when measured at an incident angle of 20 °. A pixelated display system including this antiglare glass article is also provided. The glass article can be, for example, a flat plate or panel having two main surfaces joined together by at least one edge, while the glass article is formed into another shape, for example, a three-dimensional shape. There is no problem. At least one of the surfaces is, for example, protrusions, protrusions, recesses, pits, closed or open cell structures, particles, islands, land, grooves, crevices, crevices, and similar contours or features, or combinations thereof. A rough surface containing phase or morphological features such as.

In embodiments, the present disclosure provides aluminosilicate glass articles. The aluminosilicate glass article is, for example, at least 2 mol% Al.₂O₃Can include, can be ion exchangeable, and can have at least one rough surface. The aluminosilicate glass article may have at least one rough surface containing multiple topographical features. These topographical features can have an average unique maximum feature size (ALF) of about 1 micrometer to about 50 micrometers.

In embodiments, the present disclosure provides a display system. The display system may include, for example, at least one glass panel and a pixelated image display panel adjacent to the glass panel. The image display panel may have the smallest original pixel pitch dimension. The average unique maximum feature size (ALF) of a glass panel can be less than the minimum original pixel pitch dimension of the display panel. The pixelated image display panel can be, for example, one of an LCD display, an OLED display, or a similar display device. The display system may also include a touch sense element or surface. The glass may be any of the above-mentioned glasses, for example, an aluminosilicate ion exchange glass having at least one rough surface containing a plurality of features having ALF, and the image display panel is the smallest originally. Has a pixel pitch of. The minimum original pixel pitch can be, for example, greater than the ALF of the rough surface of the glass panel.

ALF is measured in-plane (ie, parallel to the rough surface) of the rough surface of the glass and is therefore independent of roughness. ALF is a measure of the variation in features in the x and y directions, i.e., in the rough plane of the glass. Choosing the largest unique feature is a useful distinction from other methods of determining the more global average feature size. The greatest feature is the most visible to the human eye and is therefore most important in determining the appearance of the glass article. In embodiments, the phase or morphological features of at least one rough surface include intermediate values and ranges, from about 1 micrometer to about 50 micrometers, from about 5 micrometers to about 40 micrometers, about 10 micrometers. It has an average distinctive maximum feature (ALF) size from about 30 micrometers, and from about 14 micrometers to about 28 micrometers. The average specific maximum feature size is the average cross-sectional length dimension of the largest 20 repeating features in the field of view on the rough surface. A standard calibrated light microscope can typically be used to measure feature size. The field of view is proportional to feature size and typically has an area of approximately 30 (ALF) x 30 (ALF). For example, if the ALF is about 10 micrometers, the field of view from which the 20 maximum features are selected is about 300 micrometers x 300 micrometers. Small changes in field size do not significantly affect ALF. The standard deviation of the 20 maximum features used to determine the ALF should generally be less than about 40% of the mean, i.e. the main outliers are that these are "unique" features. It is unthinkable and should be ignored.

Examples of antiglare surface terrain include features such as protrusions or protrusions, recesses, and similar features with a maximum dimension of less than about 400 nm. In embodiments, these topographical features may be separated from or spaced apart from each other at an average distance of about 10 nm to about 200 nm. The resulting antiglare surface can have average roughness as measured by mountain valley difference (PV) measurements on the surface. In embodiments, the antiglare surface can have RMS roughness of about 800 nm, about 500 nm, and about 100 nm.

The features used to calculate the ALF are "Characteristic", that is, at least 20 similar features may be located in a proportional field of view. Different morphologies or surface structures may be characterized using ALF. For example, one surface structure appears to be a repeating structure of closed cells, another appears to be small pits separated by a large flat area, and a third structure appears to be intermittent large smoothing. It may look like a region of small particles interrupted by the region. In each case, the ALF is determined by measuring up to 20 repeating surface regions that are substantially optically smooth. In the case of iterative closed cell surface structures, the feature to be measured is the largest of the cells in the closed cell matrix. For surface structures containing small pits separated by a large flat area, the maximum flat area between the pits should be measured. Intermittent large smooth areas should be measured for surfaces containing areas of small particles interrupted by intermittent large smooth areas. Therefore, virtually all surfaces with varying morphologies can be characterized using ALF.

In embodiments, at least one rough surface of the glass article can have an average RMS roughness of about 10 nm to about 800 nm, about 40 nm to about 500 nm, and about 40 nm to about 300 nm. In embodiments, the mean RMS roughness can be greater than about 10 nm and less than about 10% of ALF, greater than about 10 nm and less than about 5% of ALF, and greater than about 10 nm and less than about 3% of ALF.

The low DOI and high Ros / Rs specifications constrain the unique feature size and ALF. It has been found that for a given roughness level, a larger feature size results in lower DOI and higher Ros / Rs. Therefore, in embodiments, it is desirable to form an antiglare surface with an intermediate distinctive feature size that is neither too small nor too large in order to balance the sparkle and DOI targets of the display. Also, if the transmitted haze is scattered at a very high angle, which can give the article roughened under ambient lighting a milky white appearance, it is desirable to minimize the reflected or transmitted haze.

The terms "transmitted haze", "haze", or similar terms refer to the proportion of transmitted light scattered outside the cone at an angle of ± 4.0 ° according to ASTM D1003. For optically smooth surfaces, transmission haze is generally close to zero. Transparent haze (haze) of a glass plate with roughened both sides_Double-sided) Is the transmission haze (haze) of a glass plate having an equivalent surface in which only one side is roughened according to the equation (2)._{One side}) Is associated with:<maths num="2"><img file="JP2013545708A_D0002.tif" /></maths>

Haze values are usually reported as haze percentages. Haze from equation (2)_Double-sidedThe value of must be multiplied by 100. In embodiments, the disclosed glass articles can have a transmission haze of less than about 50%, even less than about 30%.

A multi-step surface treatment process has been used to form the rough surface of the glass. In US Provisional Patent Application No. 61/165154, a simultaneous pending application of Carlson's same applicant, filed March 31, 2009, entitled "Glass Having Anti-Glare Surface and Method of Making". An example of a multi-step etching process is disclosed, in which the glass surface is treated with a first etching solution to form crystals on the surface, then the area of the surface adjacent to each crystal to the desired roughness. Etching is then performed to remove crystals from the glass surface to reduce the surface roughness of the glass article, giving the surface the desired haze and luster.

In embodiments, particle suspensions, etchings of various performance-enhancing additives, including, for example, surfactants, co-solvents, diluents, lubricants, gelling agents, and similar additives, or combinations thereof. It may be contained in the liquid or both.

The step of contacting the granulated surface with the etchant is from 2 to 10% by weight of hydrofluoric acid and hydrochloride, sulfuric acid, nitric acid, phosphoric acid, and similar acids, or combinations thereof. It may include, for example, selective partial or complete dip coating, spraying, dipping, and similar treatments for acidic etching solutions containing 30% by mass of mineral acid. The glass surface can be etched in solution for a period of about 1 second to about 10 minutes, including intermediate values and ranges, and generally the longer the time, the greater the reduction in surface roughness. The disclosed concentrations and etching times represent good examples. Although not very efficient, it is permissible to use concentrations and etching times outside the disclosed range to obtain a rough surface of the glass article. Other etching concentrations include, for example, intermediate values and intermediate ranges, 3M HF / 3.6M H.₂SO₄, 5.5M HF / 6.5M H₂SO₄, 6M HF / 7M H₂SO₄, And similar etching concentrations and compositions.

In chemical strengthening, smaller mobile alkaline ions near the glass surface are exchanged for larger alkali metal ions. This ion exchange process puts the surface of the glass under compression, making it more resistant to mechanical damage. In embodiments, the outer surface of the glass article may be ion-exchanged as needed, in which smaller metal ions are replaced or exchanged by larger metal ions having the same valence as the smaller ions. .. For example, sodium ions in a glass can be replaced with larger potassium ions by immersing the glass in a molten salt bath containing potassium ions. Substitution of smaller ions with larger ions creates compressive stresses in the layer. In embodiments, large ions near the outer surface of the glass can be replaced with smaller ions, for example, by heating the glass to a temperature above the strain point of the glass. When cooled to a temperature lower than the strain point, compressive stress is generated in the outer layer of the glass. If necessary, the chemical strengthening of the glass may be performed after the roughening treatment, and the strength or ion exchange behavior of the glass article is hardly adversely affected.

In embodiments, the present disclosure is a method of producing an antiglare surface, for example, a step of "granulating" (ie, arranging) the surface with particles, such as by a suspension or a soot gun, with fine particles on the surface. A step of deforming or adhering, a step of etching the adhered granulated surface with a suitable etching solution, a step of ionizing the etched surface, and, if necessary, yet another process of reducing unwanted surface scratches (ie,). , Scratch reduction). Alternatively, or in addition, the surface may be ion-exchanged, granulated with particles, adhered to the surface, etched with an etching solution, and optionally scratch-reduced.

With reference to the figure, FIG. 1 shows each step in the process of forming an antiglare layer on the surface of "GORILLA" glass. Wax particles or similar deformable particles with an average particle size of about 0.1 to about 20 micrometers are suspended in a suitable liquid such as isopropyl alcohol and the resulting suspension is deposited on a glass substrate ( It can be made 100), for example slot coated, and the solvent removed to leave a residual layer of weakly adhered wax particles (105) on the glass substrate (110). The sample can then be dipped, or dipped, in an acid etching solution (120) bath. HF / H₂SO₄The etchant attacks the area around the wax particles and gradually submerges under the area covered by the individual particles. During or after the rinsing step (120), wax particles can be released from the substrate surface to form a texture surface (130) with antiglare properties on the glass substrate. FIG. 1 shows the general process of how to form an antiglare layer on the surface of "Gorilla" glass, for example using the slot die method. First, the particles are suspended in a liquid such as isopropanol or a similar liquid, and then the suspension is slot die coated on a glass substrate. The solvent can be removed by any suitable means, such as evaporation, vacuum, hot air, and similar means to leave a thin layer of particles on the glass substrate. Removing the solvent by hot air or similar means can be small, medium or large and sufficient and efficient to attach the deformable particles to the glass surface. Then sample HF / H₂SO₄It can be immersed in an etching solution bath. This acid attacks the area around the particle and gradually submerges under some or all areas of the particle. During rinsing, some or substantially all particles are separated from the glass surface, leaving an etched surface to provide an anti-glare layer or anti-glare surface on the article.

FIG. 2 shows an exemplary microscopic image of wax particles slot die coated on the surface of "Gorilla" glass. Numerous experiments have shown that wax particles deposit uniformly on the glass surface, providing small openings, voids, or crevices between the particles.

FIG. 3 shows an exemplary microscopic image of the surface of the Gorilla glass of FIG. 2 that was subsequently heat treated at 75 ° C for 60 seconds. The particles deformed, fused to each other, and were well attached to the glass surface. A significant number of microopenings appear as dim areas.

Figures 4A and 4B show two different magnifications of the exemplary etched surface, respectively, after the glass sample was slot die coated with a wax particle formulation and then heat treated (annealed) at 106 ° C for 30 seconds. The microscopic image of is shown. Figure 4A shows a scale of 200 micrometers and Figure 4B shows a scale of 100 micrometers. The etching solution used was 5.5M HF / 6.5M H.₂SO₄The sample was etched for 30 seconds. The measured optical properties of the resulting surface are: haze = 39 and DOI = 44, sparkle = 5.1.

Figures 5A and 5B show high (Figure 5A) and low magnification (Figure 5B) for the surface roughness of the etched pieces after coating and heat treatment at 106 ° C for 30 seconds and then etching time for 30 seconds, respectively. ) Surface analysis image is shown. The same area was captured by two different optical objectives (20x and 10x). Ra = 82nm was captured with 20x and 2x zoom, and Ra = 245nm was captured with 10x and 1x zoom. The etched surface is a 30 second "6/7" acid solution (ie 6M HF / 7M H).₂SO₄(Mole ratio of acid).

Figures 6A and 6B show exemplary microscopic images of slot die-coated particles on the surface of "Gorilla" glass, before and after heat treatment at 75 ° C for 30 seconds, respectively. The position of the captured image is in FIGS. 6A and 6B to show the surface 30 seconds before (top of Figure 6A) and after (bottom of Figure 6B) of the wax particle surface with small openings by heat treatment at 75 ° C. It was in the same position.

Figures 7A and 7B show exemplary microscopic images of slot die-coated particles on the surface of "Gorilla" glass, before and after heat treatment at 85 ° C for 30 seconds, respectively. The positions of the captured images are the same in Figures 7A and 7B to show the appearance and condition of the surface 30 seconds before (top of Figure 7A) and after (bottom of Figure 7B) of the particle surface by heating at 115 ° C. It was a position.

FIG. 8A shows a histogram showing an example of particle size distribution for an exemplary particle suspension formulation measured by laser light scattering. FIG. 8B shows a histogram showing another example of particle size distribution for an exemplary monomodal particle suspension formulation consisting of DEUREX MM 8015 wax particles. "% Chan" refers to the relative percentage of the average particle size channel or bin, eg, particle size distribution within 6.0 ± 0.5 micrometers. This polymer particle distribution profile is substantially between about 2 and 20 micrometers and has bimodal features centered on a particle size of about 8 to 10 micrometers. Other suitable particle sizes can be from 0.5 micrometers to about 20 micrometers, including, for example, median values and ranges. Using a particle size greater than about 20 micrometers can result in an etched surface with increased sparkle.

The disclosed etching method includes intermediate values and ranges, for example, from about 2 seconds to about 4 minutes, to form an antiglare layer on the glass surface, from about 1 second to about 10 minutes, about 1 It can be carried out quickly for about 5 minutes from 1 second. The conventional multi-bath method can take about 60 minutes or more. In the disclosed etching method, one chemical etching solution bath (eg, HF and H) replaces the three or more baths used in the conventional process.₂SO₄) Is used.

In embodiments, the disclosed method is about 1 to about 50 micrometers (ie, of the substrate) of the substrate being etched, including, for example, intermediate values and ranges, to form the desired antiglare layer. In the surface or in the z direction), about 1 to about 30 micrometers of substrate, about 1 to about 20 micrometers of substrate, about 1 to about 10 micrometers of substrate, can be removed by etching. In contrast, conventional etching processes can typically remove about 100 to about 200 micrometers of glass surface. Using the disclosed method, the glass can have a maximum warp of less than about 250 micrometers, as relatively little glass is lost from the glass substrate. A conventional glass etching process can produce, for example, a glass substrate having a warp of about 300 micrometers or more.

Samples prepared by the disclosed process exhibit similar optical properties (eg, haze, gloss, and image sharpness (DOI)) when compared to samples etched by conventional processes, but according to the invention. The methods and samples have the advantage of significantly reducing process time and costs. The disclosure process is easily extended to large parts such as glass plates of 1 square meter or more, whereas the conventional immersion process is not so easily extended to large units.

By choosing the right design, the disclosure process does not require back protection to produce single-sided samples. Single-sided samples can be prepared using, for example, single-sided immersion, spraying, screen printing, or rotary coating methods. The traditional process of multi-bath requires a back protection film, which can increase manufacturing costs.

In embodiments, the glass article may comprise one of soda lime silicate glass, alkaline earth aluminosilicate glass, alkaline aluminosilicate glass, alkaline borosilicate glass, and combinations thereof, from the substantial. Can be, or can consist of. In embodiments, the glass article is, for example, 60-72 mol% SiO.₂, 9-16 mol% Al₂O₃, 5-12 mol% B₂O₃, 8-16 mol% Na₂O, and 0-4 mol% K₂The following ratios, which have a composition of O and the alkali metal modifier is an alkali metal oxide:<img file="JP2013545708A_D0003.tif" />

Can be an alkaline aluminosilicate glass. In the embodiment, the alkaline aluminosilicate glass substrate is, for example, 61 to 75 mol% SiO.₂, 7 ~ 15 mol% Al₂O₃, 0-12 mol% B₂O₃, 9-21 mol% Na₂O, 0-4 mol% K₂It can be O, 0-7 mol% MgO, and 0-3 mol% CaO. In the embodiment, the alkaline aluminosilicate glass substrate is, for example, 60 to 70 mol% SiO.₂, 6-14 mol% Al₂O₃, 0 ~ 15 mol% B₂O₃, 0-15 mol% Li₂O, 0-20 mol% Na₂O, 0-10 mol% K₂O, 0-8 mol% MgO, 0-10 mol% CaO, 0-5 mol% ZrO₂, 0 ~ 1 mol% SnO₂, 0 ~ 1 mol% CeO₂, As less than 50ppm₂O₃, And Sb less than 50ppm₂O₃Can be, where 12 mol% Li₂O + Na₂O + K₂O 20 mol% and 0 mol% MgO + CaO 10 mol%. In an embodiment, the alkaline aluminosilicate glass substrate is, for example, 64 to 68 mol% SiO.₂, 12-16 mol% Na₂O, 8-12 mol% Al₂O₃, 0-3 mol% B₂O₃, 2-5 mol% K₂O, 4-6 mol% MgO, and 0-5 mol% CaO, where 66 mol% SiO₂+ B₂O₃+ CaO 69 mol%, Na₂O + K₂O + B₂O₃+ MgO + CaO + SrO&gt; 10 mol%, 5 mol% MgO + CaO + SrO 8 mol%, (Na₂O + B₂O₃)-Al₂O₃2 mol%, 2 mol% Na₂O-Al₂O₃ 6 mol%, and 4 mol% or more (Na₂O + K₂O) -Al₂O₃10 mol%. In the embodiment, the alkaline aluminosilicate glass is, for example, 50 to 80% by mass of SiO.₂, 2 ~ 20% by mass Al₂O₃, 0 ~ 15% by mass B₂O₃, 1 ~ 20% by mass Na₂O, 0-10% by mass Li₂O, 0 ~ 10% by mass K₂O and 0-5% by weight (MgO + CaO + SrO + BaO), 0-3% by weight (SrO + BaO) and 0-5% by weight (ZrO)₂+ TiO₂), Where 0 (Li₂O + K₂O) / Na₂O 0.5.

In embodiments, the alkaline aluminosilicate glass may be substantially free of, for example, lithium. In embodiments, the alkaline aluminosilicate glass may be substantially free of, for example, at least one of arsenic, antimony, barium, or a combination thereof. If necessary, Na on the glass₂SO₄, NaCl, NaF, NaBr, K₂SO₄, KCl, KF, KBr, SnO₂, And similar substances, or at least one fining agent such as a combination thereof, may be blended in batches of 0 to 2 mol%.

In embodiments, the selected glass is, for example, down-drawable, i.e., moldable by methods known in the art, such as slot-draw or fusion-draw methods. In these cases, the glass may have a liquidus viscosity of at least 130 kilopores. An example of an alkaline aluminosilicate glass has priority over US Provisional Patent Application No. 60/930808 filed May 22, 2007, filed July 31, 2007, "Down-Drawable". , US Patent Application No. 11/888213 of the same applicant as this application to Ellison et al. entitled "Chemically Strengthened Glass for Cover Plate"; priority from US Provisional Patent Application No. 61/004677 filed on November 29, 2007. US Patent Application No. 12/227573 to Dejneka et al., Titled "Glasses Having Improved Toughness and Scratch Resistance," filed on November 25, 2008; filed on February 26, 2008. U.S. Patent Application No. 12/392577 to Dejneka et al., Filing February 25, 2009, claiming priority from U.S. Provisional Patent Application No. 61/067130; "Ion-Exchanged," filed on February 26, 2009, claiming priority in U.S. Provisional Patent Application No. 61/067732 filed on February 29, 2008. U.S. Patent Application No. 12/393241 to Dejneka et al., entitled "Fast Cooled Glasses"; to U.S. Provisional Patent Application No. 61/087324, entitled "Chemically Tempered Cover Glass," filed August 8, 2008. US Patent Application No. 12/537393, filed on August 7, 2009, with priority, to Barefoot et al., entitled "Strengthened Glass Articles and Methods of Making"; filed on August 21, 2009. , US Provisional Patent Application No. 61/235767 to Barefoot et al., entitled "Crack and Scratch Resistant Glass and Enclosures Made There from"; and "Zircon Compatible Glasses for Down Draw," filed August 21, 2009. It is described in US Provisional Patent Application No. 61/235762 to Dejneka et al.

The glass surfaces and plates described in the examples below can be any suitable particle-coated and etchable glass substrate or similar substrate, eg, glass compositions 1 to 11 listed in Table 1, or The combination may be included.<tables num="1"><img file="JP2013545708A_D0004.tif" /></tables>

<p> The examples further illustrate the method and how the articles of the present disclosure are produced.</p><p><u style="single">Example 1</u> Preparation of particle suspension This example is one exemplary method for practicing the methods of the invention. Each step of how the glass is coated, heat treated and then etched is described below. Specimens of 2318 glass (6 "x 6" (about 15 cm x about 15 cm)) were washed in a Crest Line with about 4% cleaning agent in deionized (DI) water. The washed glass plate was then placed on a flat surface, 33.33% by weight DEUREX ME 1519 wax particles were weighed in the container and 66.64% by weight 2-propanol was added. DEUREX ME 1519 wax particles are commercially available from DEUREX Micro-Technologies (www.deurex.com), located in Germany. Resodyn Acoustic with this container at a power level of 60% Treated with Mixer for 5 minutes. The resulting particle size distribution measured by laser light scattering is shown in Figure 8A. The concentrated suspension may be used directly without further modification, or may be stored, for example, for about a week if it is shaken continuously before use.</p><p><u style="single">Example 2</u> Granulation Surface Preparation-Coating or Depositing Particle Suspensions This example is an exemplary technique of coating or depositing a wax particle suspension on a glass surface. The particle suspension of Example 1 was manually coated on a glass plate using a 1 mil (25 micrometer) drawdown bar.</p><p> Volatile liquids or solvents were evaporated in air or by accelerated drying methods such as vacuum, gentle heating, or a combination thereof. The residual surface layer of the wax particles partially protects the underlying surface or support of the glass substrate, so not all of the substrate is etched during acid etching. Preparation of the particulate suspension comprises, for example, a two-step process involving the step of preparing a concentrated suspension stock solution, followed by adding (diluting with) a volatile liquid that can be easily evaporated after coating prior to surface coating. ), The concentration of the concentrate can be reduced. In embodiments, the diluted suspension is stable over a period of, for example, days to weeks and can be resuspended by rolling or shaking.</p><p> The following is an exemplary manual covering technique.</p><p> A small amount (1 mL) of particle suspension was poured onto the glass sample. A 25 micrometer gap drawdown bar was used to sweep the poured particle suspension from one end to the other of the glass sample. A thin film with a wet thickness of 25 micrometers remained on the glass.</p><p> The glass was placed on a hot plate set, eg, 75 ° C., for 40 seconds, with the coating side up.</p><p> After heat treatment, the sample is then subjected to a specific concentration, eg 5.5M HF / 6.5M H, for a specific time, eg 30 seconds.₂SO₄It was immersed in an etching solution bath containing an acid solution having. The resulting etched sample was then removed from the acid bath and rinsed. If the mask of wax particles remains, rinsing with an organic solvent may be used if necessary. For example, acetone or similar solvents are particularly useful for removing various types of polymer particles. This piece was dried before measuring the haze, sparkle, and DOI of the etched sample.</p><p> Various methods can be selected for applying the particles. For example, the particle suspension may be spray coated, curtain coated, screen printed, dip coated, rotary coated, roller coated, rod coated, rolled, and similar methods, or a combination thereof. Many of the examples in the present disclosure were prepared using the slot die coating method. This method has a number of manufacturing and productivity advantages. The advantage of the slot die coating technique is that the coating thickness can be precisely controlled. After coating and heat treatment, a very thin layer of particles (nearly only one or two layers, in some cases less than a complete single layer) remained on the surface. This type of coating improves the ability of acid to penetrate or penetrate the space in the particle coating mask, resulting in, for example, more efficient etching, less acid concentration, and less particle consumption. Yet another process improvement includes optimizing the interaction between the particles and the glass surface, for example by adjusting the properties of the glass or particles, the concentration of the particles, the surface charge properties, or a combination thereof. Be done. In embodiments, the preferred wet coating method is to apply only approximately one to two layers, or even less than a single layer, to the glass surface. Table 2 shows examples of various temperature setting points while maintaining the same heat treatment time. The same acid etching solution concentration was used.<tables num="2"><img file="JP2013545708A_D0005.tif" /></tables></p><p> As the treatment temperature increases, more particles fuse with each other and adhere strongly to the glass surface, thus allowing the acid to etch the glass more. This was clearly shown in Table 2 when the haze level increased and the DOI decreased. When heat-treated at a low temperature, the particles did not fuse with each other and adhered poorly to the glass. The particles could be quickly removed by acid or easily washed off the surface. This resulted in a high DOI value and a low haze value.</p><p> HF / H₂SO₄Targets from high haze to very high haze were achieved with good DOI, even with very short etching times in solution. Sparkle was very low and the anti-glare appearance characteristics were judged to be excellent by a large number of observers. This clearly showed that the polyethylene wax particle formulation was used as a masking layer to obtain excellent optical performance.</p><p> Table 3 shows additional examples using polyethylene wax particles to form an antiglare layer on "Gorilla" glass. The samples were heat treated at various temperatures and etched for a shorter period of time. The results in Table 3 show that when shorter etching times were used, the DOI increased while maintaining similar haze and sparkle. This indicates flexibility and a small loss of glass thickness.<tables num="3"><img file="JP2013545708A_D0006.tif" /></tables></p><p> Table 4 shows additional examples using low molecular weight polyethylene wax particles to form an antiglare layer on "Gorilla" glass. Samples were heated at various temperatures and etched at lower acid concentrations. With lower acid concentrations, sparkle remained excellent, with high haze still achieving very high haze. For example, by adjusting the particle heating temperature, heating time, particle concentration, etching temperature, coating thickness, etching time, or a combination thereof, it is predicted that similar results can be achieved using lower acid concentrations. Will be done.<tables num="4"><img file="JP2013545708A_D0007.tif" /></tables></p><p> The particles used were based on low molecular weight polyethylene particles with a relatively low Tg. A wide variety of alternative polymer particles with annealing temperatures approximately proportional to the Tg of the polymer particles may be selected. Examples of other polymer particle materials include, for example, polystyrene, polyester, polyolefin, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, silicone, polyethylene, melamine, (meth) acrylate, polyethylene terephthalate. The particles can be homopolymers, copolymers, or mixtures thereof. The beads may be modified by surface treatment such as cross-linking, temperature or radiation sensitive shells, and similar modifications, or combinations thereof. The particles may be crosslinked or uncrosslinked, and spherical or flat fine particle morphological factors made of plastic may be used. Other suitable alternative materials include, for example, waxes or polymers with wax-like properties and are effective in achieving the features and embodiments of the present disclosure. The wax category may be, for example, plant-based, mineral-based, or animal-based, including petroleum-derived waxes and synthetic waxes. Some exemplary waxes include elcamides, stearamides, oleamides, montans, polyethylene oxide, copolymers containing combinations thereof, and particles with a core of one polymer and a shell of a different polymer, as well as other similar materials. Can be mentioned. Other polymer particle types can be selected based on a variety of considerations, including cost, ease of removal, or robustness in acid solutions.</p><p> The size of the polymer particles need not be limited. For antiglare surfaces for display applications, a generally desirable particle size range can be from about 1 micrometer to about 50 micrometers, including, for example, intermediate values and intermediate ranges. Below this range, anti-glare scattering may be reduced due to the sub-wavelength effect, and above this range, unacceptable display "sparkles" may begin to appear in some pixelated displays. However, it is believed that the disclosed process can still be applied using particle sizes outside this range. For example, the slot die coating method can be used to create several layers of particles and heat the particle mask prior to etching to control the final glass roughness. Particles larger than 50 micrometers can be useful in non-display applications such as mouse pads or other touch input devices, anti-glare surfaces for non-pixelated displays, and similar applications. Polymer particles less than about 1 micrometer can be useful for making nanostructured surfaces, such as gradient index antireflection coatings or hydrophobic or oleophobic structural surfaces. Other non-display applications that can benefit from the methods of disclosure are on glass, including light traps or photovoltaic panels with improved light absorption, and aesthetic panels or covers for consumer electronics and architectural applications. Is to make a light scattering surface of.</p><p><u style="single">Example 3</u> Preparation of granulated surface DEUREX MM 8015 was slot die coated according to the conditions listed in Table 5. In the table, S-Gap (μm) is the starting slot pouring dimension expressed in micrometers and C-Gap (μm) is the covering gap slot dimension expressed in micrometers, Horix Del and Vert Del is the time delay and Liq Trig (mm) is the dimension when the slot die pump is stopped at the end of the coating operation. Table 6 shows the etching conditions and results.<tables num="5"><img file="JP2013545708A_D0008.tif" /></tables><tables num="6"><img file="JP2013545708A_D0009.tif" /></tables></p><p><u style="single">Example 4</u> Preparation of mixed granulated surface If desired, the DEUREX MM 8015 material or similar material may be mixed with other particulate materials or other performance additives, such as a mixture of wax particles and polymer particles. The particle suspension was coated with the same slot die settings as described above. DUEREX particle suspensions were prepared as described above. Polymer particle suspensions, such as PMMA or similar polymers or copolymers of methyl methacrylate and ethylene glycol dimethacrylate, were prepared according to the formulations listed in Table 7. Alternatively, for example, one or more of viscosity modifiers, binders, or dispersants may be omitted from the formulation.<tables num="7"><img file="JP2013545708A_D0010.tif" /></tables></p><p> Mixing with other polymer particle sizes, particle compositions, and two or more particle sizes of the same or different compositions to produce a finished substrate with the desired roughness, haze level, and DOI properties in the finished article. , Or the glass substrate may include additional or yet another compounding operation.</p><p> A mixed suspension is prepared by combining a 90% by weight DEUREX wax suspension with a 10% by weight polymer particle suspension and the mixed suspension is placed on a roller for about 1 hour to make it uniform. The mixture was provided. The mixture was then slot die coated with the same settings as described above. The particle-coated sample was then heated at 75 ° C. for 45 seconds, followed by chemical etching. Table 8 lists the etching conditions used and the properties of the resulting antiglare glass. This example shows that the addition of crosslinked polymer particles to the DEUREX material can provide good optical properties to the resulting anti-glare "Gorilla" glass.<tables num="8"><img file="JP2013545708A_D0011.tif" /></tables></p>

105 wax particles 110 glass substrate 130 texture surface