# US 8,771,532 B2 · Glass having anti-glare surface and method of making > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,771,532 B2 - Document ID: US8771532B2 - Status: Granted - Kind: B2 - Application number: 12/730,502 - Filed: 2010-03-24 - Published: 2010-09-30 - Granted: 2014-07-08 - Earliest claimed: 2009-03-31 - Assignees: Corning Incorporated - Applicants: Krista L Carlson; Shandon D Hart; Kelvin Nguyen; Robert Sabia; Daniel A Sternquist; Lu Zhang - Inventors: Krista L Carlson; Shandon D Hart; Kelvin Nguyen; Robert Sabia; Daniel A Sternquist; Lu Zhang - Web page: https://patentgrep.com/patent/US8771532B2 ## CPC - C03C 15/00: Surface treatment of glass, not in the form of fibres or filaments, by etching (etching or surface-brightening compositions, in general C09K13/00) - C03C 23/00: Other surface treatment of glass not in the form of fibres or filaments - C09G 1/00: Polishing compositions (French polish C09F11/00; detergents C11D) - C03C 2217/77: Coatings having a rough surface - C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS - C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES ## Abstract A glass article having an anti-glare surface. The anti-glare surface has a distinctness-of-reflected image of less than 95, and a haze of less than or equal to 50%. In one embodiment, the glass article further includes a smudge-resistant surface disposed on the anti-glare surface. Methods of making the glass article and anti-glare surface are also described. ## Claims ### Claim 1 A method of making a glass article having an anti-glare surface, the method comprising the steps of: a. providing a glass article; b. growing crystals on a surface of the glass article; c. etching glass from the surface surrounding the crystals with a first etching solution to form a roughened texture on the surface; d. removing the crystals from the surface by applying a second aqueous etching solution to the surface, wherein the second aqueous etching solution comprises a mineral acid and is free of HF, to form the anti-glare surface; and e. etching the surface after removing the crystals to obtain at least one of a selected surface roughness, a selected surface haze, and a selected distinctness-of-reflected image, wherein the step of etching the surface after removing the crystals comprises applying an aqueous etching solution comprising a mineral base and a chelating agent to the surface. ### Claim 2 The method according to claim wherein the surface haze is less than or equal to 50%. ### Claim 3 (depends on 1) The method according to claim 1, wherein the surface roughness is less than or equal to 800 nm. ### Claim 4 (depends on 1) The method according to claim 1, wherein the distinctness-of-reflected-image is less than 95. ### Claim 5 (depends on 1) The method according to claim 1, wherein the step of growing crystals on the surface includes etching the surface with an aqueous etching solution comprising an inorganic fluoride salt and a wetting agent. ### Claim 6 (depends on 5) The method according to claim 5, wherein the inorganic fluoride salt is one of ammonium fluoride, ammonium bifluoride, sodium fluoride, sodium bifluoride, potassium fluoride, potassium bifluoride, and combinations thereof. ### Claim 7 (depends on 5) The method according to claim 5, wherein the wetting agent is one of a glycol, a glycerol, an alcohol, a surfactant, and combinations thereof. ### Claim 8 (depends on 5) The method according to claim 5, further wherein the aqueous etching solution further comprises at least one of a mineral acid and hydrofluoric acid. ### Claim 9 (depends on 8) The method according to claim 8, wherein the mineral acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. ### Claim 10 (depends on 1) The method according to claim 1, wherein the mineral acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. ### Claim 11 (depends on 1) The method according to claim 1, wherein the step of removing the crystals from the surface comprises rinsing the surface with water. ### Claim 12 (depends on 1) The method according to claim 1, wherein the glass article comprises one of a soda lime silicate glass, an alkaline earth aluminosilicate glass, an alkali aluminosilicate glass, an alkali borosilicate glass, and combinations thereof. ### Claim 13 (depends on 12) The method according to claim 12, wherein the step of providing a glass article comprises providing a glass article comprising an alkali aluminosilicate glass, and wherein the alkali aluminosilicate glass is chemically strengthened by ion exchange. ### Claim 14 (depends on 12) The method according to claim 12, wherein the glass article comprises an alkali aluminosilicate glass, and wherein the alkali aluminosilicate glass comprises: 60-70 mol % SiO2; 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; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; wherein 12 mol %≦Li2O+Na2O+K2O≦20 mol % and 0 mol %≦MgO+CaO≦10 mol %. ### Claim 15 (depends on 12) The method according to claim 12, wherein the glass article comprises an alkali aluminosilicate glass, and wherein the alkali aluminosilicate glass comprises: 61-75 mol % SiO2; 7-15 mol % Al2O3; 0-12 mol % B2O3; 9-21 mol % Na2O; 0-4 mol % K2O; 0-7 mol % MgO; and 0-3 mol % CaO. ### Claim 16 (depends on 12) The method according to claim 12, wherein the glass article comprises an alkali aluminosilicate glass, and wherein the alkali aluminosilicate glass comprises: 60-72 mol % SiO2; 9-16 mol % Al2O3; 5-12 mol % B2O3; 8-16 mol % Na2O; and 0-4 mol % K2O, wherein the ratio A ⁢ ⁢ l 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) + B 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) ∑ ⁢ alkali ⁢ ⁢ metal ⁢ ⁢ modifiers ⁢ ⁢ ( mol ⁢ ⁢ % ) > 1. ### Claim 17 (depends on 1) The method according to claim 1, further comprising the step of applying an amphiphobic fluorine-based layer on at least a portion of the anti-glare surface. ### Claim 18 (depends on 1) The method according to claim 1, wherein the step of providing the glass article further comprises masking a second surface of the glass. ### Claim 19 (depends on 1) The method according to claim 1, further comprising the step of strengthening the substrate having the anti-glare surface by ion exchange. ### Claim 20 A method of making an anti-glare surface, the method comprising the steps of: a. providing a glass substrate; b. forming crystals on a surface of the substrate; c. etching glass from the surface surrounding the crystals with a first etching solution, d. removing the crystals from the surface to form the anti-glare surface by applying a second aqueous etching solution to the surface, wherein the second aqueous etching solution comprises a mineral acid and is free of HF, wherein the anti-glare surface has a haze less than or equal to 50% and a distinctness-of-reflected image of less than 95; and e. etching the surface after removing the crystals to obtain at least one of a selected surface roughness, a selected surface haze, and a selected distinctness-of-reflected image, wherein the step of etching the surface after removing the crystals comprises applying an aqueous etching solution comprising a mineral base and a chelating agent to the surface. ### Claim 21 (depends on 20) The method according to claim 20, wherein the steps of forming crystals on the surface and etching glass from the surface surrounding the crystals comprises applying an aqueous etching solution to the surface, wherein the aqueous etching solution comprises an inorganic fluoride salt and a wetting agent. ### Claim 22 (depends on 21) The method according to claim 21, wherein the inorganic fluoride salt is one of ammonium fluoride, ammonium bifluoride, sodium fluoride, sodium bifluoride, potassium fluoride, potassium bifluoride, and combinations thereof. ### Claim 23 (depends on 21) The method according to claim 21, wherein the wetting agent is one of a glycol, a glycerol, an alcohol, a surfactant, and combinations thereof. ### Claim 24 (depends on 21) The method according to claim 21, further wherein the aqueous etching solution further comprises at least one of a mineral acid and hydrofluoric acid. ### Claim 25 (depends on 24) The method according to claim 24, wherein the mineral acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. ### Claim 26 (depends on 20) The method according to claim 20, wherein the mineral acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. ### Claim 27 (depends on 20) The method according to claim 20, wherein the step of removing the crystals from the surface to form the anti-glare surface further comprises applying a third aqueous etching solution to the surface, wherein the third aqueous etching solution comprises HF and, optionally, a mineral acid. ### Claim 28 (depends on 27) The method according to claim 27, wherein the mineral acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. ### Claim 29 (depends on 27) The method according to claim 27, wherein the third aqueous etching solution comprises a mineral base and a chelating agent. ### Claim 30 (depends on 20) The method according to claim 20, further comprising the step of applying an amphiphobic fluorine-based layer on at least a portion of the etched surface. ### Claim 31 (depends on 20) The method according to claim 20, wherein the step of providing the glass article further comprises masking a second surface of the glass.