Method of making heat treated and ion-beam etched/milled coated article using diamond-like carbon (dlc) protective film.
Abstract
There is provided a method of making a heat treated (HT) coated ar¬ ticle to be used in shower door applications, window applications, or any other suitable applications where transparent coated articles are desired. For example, certain embodiments of this invention relate to a method of making a coated article, the method comprising: provid¬ ing a glass substrate including first and second major surfaces, the first major surface being exposed to a tin bath during fabrication of the glass substrate and the second major surface being opposite the first major surface and being acid etched; ion beam treating the first major surface of the substrate so as to remove a surface portion of the substrate, the surface portion comprising one or more of tin, tin oxide and/or surface contaminants; disposing a zirconium-inclusive layer on the first major surface following said ion beam treating; and disposing a layer comprising diamond-like carbon (DLC), directly or in¬ directly, on the zirconium-inclusive layer; wherein the glass substrate with the zirconium-inclusive layer and the layer comprising DLC is heat treatable at a temperature sufficient for thermal tempering, heat strengthening, and/or heat bending so as to cause burn off of the lay¬ er comprising DLC but without also causing significant burn off of the zirconium-inclusive layer.

Term
5.7 yearsleft in the term
Expires 21 June 2032.
- Priority
- Filed
- Granted
- Today
- Expires
15 claims: 13 independent, 2 dependent
- 1CLAIMS REIVINDICACIONES A method of making a coated article, characterized in that the method comprises:providing a glass substrate that includes a first surface Un método para hacer un artículo revestido, caracterizado porque el método comprende: proporcionar un substrato de vidrio que incluye una primera superficie 5 main and a second main surface, the first main surface is exposed to a tin bath during the manufacture of the glass substrate and the second main surface is opposite to the first main surface and is etched with acid;deal with ion beam 5 principal y una segunda superficie principal, la primera superficie principal se expone a un baño de estaño durante la fabricación del substrato de vidrio y la segunda superficie principal es opuesta a la primera superficie principal y es atacada con ácido;tratar con haz de iones 10 the first major surface of the substrate in order to remove a portion of the surface of the substrate, the portion of the surface comprises one or more of tin, tin oxide and / or surface contaminants;lay an inclusive layer of zirconium on the first surface 10 la primera superficie principal del substrato con el fin de retirar una porción de la superficie del substrato, la porción de la superficie comprende uno o más de estaño, óxido de estaño y/o contaminantes superficiales;disponer una capa inclusiva de zirconio sobre la primera superficie 15 principal después del tratamiento con haz de iones;disponer una capa que comprende carbón tipo diamante (DLC), directa o indirectamente, sobre la capa inclusiva de zirconio;y tratar térmicamente el substrato de vidrio con la capa inclusiva de zirconio y la capa que comprende DLC fifteen main after ion beam treatment;arranging a layer comprising diamond-like carbon (DLC), directly or indirectly, over the inclusive zirconium layer;and heat treating the glass substrate with the inclusive zirconium layer and the layer comprising DLC 20 sobre el mismo a una temperatura suficiente para la templadura térmica, fortalecimiento térmico y/o doblamiento térmico con el fin de causar la calcinación de la capa que comprende DLC pero sin causar también una calcinación significativa de la capa inclusiva de zirconio. twenty thereon at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause calcination of the layer comprising DLC but without also causing significant calcination of the zirconium inclusive layer. 25 25
- 2The method in accordance with 2. El método de conformidad con la IMPí? IMPí? INSTITUTO MiXICANO de la propiedad MEXICAN INSTITUTE of the property INDUSTWAL claim 1, characterized in that the zirconium inclusive layer comprises zirconium nitride before heat treatment. INDUSTWAL reivindicación 1, caracterizado porque la capa inclusiva de zirconio comprende nitruro de zirconio antes del tratamiento térmico.
- 3The method according to any of the preceding claims, characterized in that the zirconium inclusive layer comprises zirconium oxide after heat treatment. 3. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa inclusiva de zirconio comprende óxido de zirconio después del tratamiento térmico.
- 4El método de conformidad, con cualquiera de las reivindicaciones anteriores, caracterizado porque comprende además aplicar una lámina protectora temporal en forma líquida o sólida sobre la capa que comprende DLC. Four. The method according to any of the preceding claims, characterized in that it further comprises applying a temporary protective sheet in liquid or solid form on the layer comprising DLC.
- 5The method according to any of the preceding claims, characterized in that it comprises heat treating the glass substrate with the inclusive zirconium layer and the layer comprising DLC thereon. 5. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque comprende tratar térmicamente el substrato de vidrio con la capa inclusiva de zirconio y la capa que comprende DLC sobre el mismo.
- 7The method according to any of the preceding claims, characterized in that it further comprises removing a temporary protective sheet before heat treatment. 7. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque comprende además retirar una lámina protectora temporal antes del tratamiento térmico.
- 8The method according to any of the previous claims, characterized in that by the 8. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque por la ΙΜΡΙ ΙΜΡΙ INSTITUTO MEXICANO Cl LA PROPIEDAD INDUSTRIAL lo menos parte de la capa inclusiva de zircoriio se expone con el fin de que sea la capa exterior del artículo revestido como resultado del tratamiento térmico. INSTITUTO MEXICANO Cl THE INDUSTRIAL PROPERTY at least part of the inclusive layer of zircorium is exposed in order to be the outer layer of the coated article as a result of heat treatment.
- 9The method according to any of the preceding claims, characterized in that the ion beam treatment is carried out using Ar. 9. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el tratamiento con haz de iones se realiza utilizando Ar.
- 10The method according to any of the preceding claims, characterized in that the ion beam treatment is carried out using N2. 10. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el tratamiento con haz de iones se realiza utilizando N2. A method of making a heat treated coated article, the method is characterized in that it comprises:have a glass substrate including a first main surface and a second main surface, the first main surface has been exposed to a tin bath during the manufacture of the glass substrate and has been ion beam treated in order to remove a portion of the surface thereof comprising tin, tin oxide and / or surface contaminants, the second main surface is opposite to the first main surface and has been attacked with acid, away from the substrate, the first main surface supports an inclusive zirconium layer and a layer comprising diamond-like carbon (DLC);and heat treating the glass substrate with the inclusive zirconium layer and the layer comprising DLC thereon, with Un método para hacer un artículo revestido tratado térmicamente, el método está caracterizado porque comprende: tener un substrato de vidrio que incluye una primera superficie principal y una segunda superficie principal, la primera superficie principal ha sido expuesta a un baño de estaño durante la fabricación del substrato de vidrio y ha sido tratada con haz de iones con el fin de retirar una porción de la superficie del mismo que comprende estaño, óxido de estaño y/o contaminantes superficiales, la segunda superficie principal es opuesta a la primera superficie principal y ha sido atacada con ácido, la primera superficie principal soporta, alejándose del substrato, una capa inclusiva de zirconio y una capa que comprende carbón tipo diamante (DLC);y tratar térmicamente el substrato de vidrio con la capa inclusiva de zirconio y la capa que comprende DLC sobre el mismo, con IMPI IMPI INSTITUTO MEXICANO Dt LA PROPIEDAD INDUSTRIAL el fin de retirar la capa que comprende DLC y causar que ~ rΊ 1' «JLJrr..- . _ r _i i iu por lo menos una porción de la capa inclusiva de zirconio sea expuesta como la capa exterior del artículo revestido tratado térmicamente. INSTITUTO MEXICANO Dt LA PROPIEDAD INDUSTRIAL in order to remove the layer containing DLC and cause ~ r ~ 1 '«JLJrr ..-. _ r _i i iu at least a portion of the zirconium inclusive layer is exposed as the outer layer of the heat treated coated article.
- 1213. The method according to any of claims 11-12, characterized in that it comprises removing a temporary protective sheet that is applied on top of the inclusive zirconium layer and the layer comprising 13. El método de conformidad con cualquiera de las reivindicaciones 11-12, caracterizado porque comprende retirar una lámina protectora temporal que se aplica encima de la capa inclusiva de zirconio y la capa que comprende DLC as a result of heat treatment. DLC como resultado del tratamiento térmico.
- 1314. The method according to any of the preceding claims, characterized in that the zirconium inclusive layer consists essentially of zirconium nitride before heat treatment and consists essentially of zirconium oxide after heat treatment. 14. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa inclusiva de zirconio consiste esencialmente de nitruro de zirconio antes del tratamiento térmico y consiste esencialmente de óxido de zirconio después del tratamiento térmico.
- 1415. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque la capa que comprende DLC es de 1-10 nm de espesor antes del tratamiento térmico. fifteen. The method according to any of the preceding claims, characterized in that the layer comprising DLC is 1-10 nm thick before heat treatment.
- 1516. The method according to any of the preceding claims, character | .zj 16. El método de conformidad con cualquiera de las reivindicaciones anteriores, caracter|.zj INSTITUTO MEXICANO DE LA tROPitOAO capa inclusiva de zirconio es de 15-150 nm de espéíStírr arrees y después del tratamiento térmico. INSTITUTO MEXICANO DE LA tROPitOAO zirconium inclusive layer is 15-150 nm from espéíStírr arrees and after heat treatment. ΙΜΡΙ ΙΜΡΙ INSTITUTO MEXICANO DE LA PROPIEDAD MEXICAN INSTITUTE OF PROPERTY INEVSTUAL INEVSTUAL
Independent claims13
343 paragraphs in 36 sections, as filed
(54) Title: METHOD FOR MAKING A COATED ITEM THERMALLY TREATED AND ATTACKED / GROUNDED WITH ION BEAM USING A DIAMOND TYPE CARBON PROTECTIVE FILM (DLC).
(54) Title: METHOD OF MAKING HEAT TREATED AND ION-BEAM ETCHED / MILLED COATED ARTICLE USING DIAMONDLIKE CARBON (DLC) PROTECTIVE FILM.
(57) Summary
A method is provided for making a heat treated (HT) coated article for use in shower door applications, window applications or any other suitable application where clear coated articles are desired. For example, certain embodiments of this invention relate to a method of making a coated article, the method comprising: providing a glass substrate that includes a first major surface and a second major surface, the first major surface being exposed to a bath of tin during the manufacture of the glass substrate and the second main surface is opposite to the first main surface and is etched with acid; ion beam treating the first major surface of the substrate in order to remove a surface portion of the substrate, the surface portion comprising one or more tin, tin oxide and / or surface contaminants; lay an inclusive zirconium layer on the first main surface after ion beam treatment; and arranging a layer comprising diamond-like carbon (DLC), directly or indirectly, on the inclusive zirconium layer; wherein the glass substrate with the inclusive zirconium layer and the layer comprising DLC can be heat treated at a temperature sufficient for thermal tempering, heat hardening and / or heat bending in order to cause burn of the layer comprising DLC but without also causing significant burnout of the zirconium inclusive layer.
(57) Abstract
There is provided a method of making a heat treated (HT) coated arÁ-i ticle to be used in shower door applications, window applications, or any other suitable applications where transparent coated articles are desired. For example, certain embodiments of this invention relate to a method of making a coated article, the method comprising: providÁ-i ing a glass substrate including first and second major surfaces, the first major surface being exposed to a tin bath during fabrication of the glass substrate and the second major surface being opposite the first major surface and being acid etched; ion beam treating the first major surface of the substrate so as to remove a surface portion of the substrate, the surface portion comprising one or more of tin, tin oxide and / or surface contaminants; disposing a zirconium-inclusive layer on the first major surface following said ion beam treating; and disposing a layer comprising diamond-like carbon (DLC), directly or inÁ-i directly, on the zirconium-inclusive layer; where the glass substrate with the zirconium-inclusive layer and the layer comprising DLC is heat treatable at a temperature sufficient for thermal tempering, heat strengthening, and / or heat bending so as to cause burn off of the layÁ-i er comprising DLC but without also causing significant burn off of the zirconium-inclusive layer.
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PATENT TITLE NO. 338872
- '.. • Μι? · '·.
_I KNOW_
StCWTXRU Ot tOWOMÍt
Institute
Mexican Property
Industrial
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Headlines):
Home:
Denomination:
Classification:
Inventor (s):
GUARDIAN INDUSTRIES CORP.
2300 Harmon Road, Auburn Hills, Michigan, 48326-1714, USA
METHOD FOR MAKING A COATED ITEM HEAT TREATED AND ATTACKED / GROUNDED WITH ION BEAM USING A DIAMOND TYPE CARBON PROTECTIVE FILM (DLC).
lnt.CI.8: C03B27 / 012; C03C15 / 02; C03C17 / 34
4IANGP gaa * ** .RUOOLPH HUG
REQUEST
HUGO PETRMÍCHL,
ITUD
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MX / a / 2013/015030
Country:
US figencla: Twenty years
Expiration Date: June 21, 2032
Intemai filing date of June 2012
PRIORITY
Date:
June 2011
- · '*' .T .j.
Number:
13/174,310
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Xa reference patent is granted coi á '° d
In accordance with the Counted from the rights.
de f de presij damerteeplps articles 1, 2 fraction V, 6 * fraction lll, and 59 of the Industrial Property Law.
This patent has a validity of twenty articles that are not eligible, and will be subject to the payment of the fee to maintain the validity of the
Itation law
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Who subscribes to the present title I do with Fundí Industrial Property (Official Gazette of the Federation 01/26/2004, 06/16/2005, 2001/2006, subsection a), subsection iii) 4 * and 12 ° fra, amended on 07/01/2002, 07/16/2004, 07/08/2004 and 09/07/2007); 30 of the Organic Statute of the Instituf
07k 1 ° 3 ° and 5 by articles 6 fractions lll and 7 * bis 2 of the law of, amended on 02/08/1994, 10/25/1998, 12/26/1997, 1W5 / 1999, I / 201C ¿-Í017012 and 09/04/2012); Articles 1, 3 Sacción V kWBututo Mexicano de la Propiedad Industrial (DOF 1 <12/1999, I<sup>to</sup> 3<sup>to</sup> 4<sup>to</sup> 5<sup>to</sup> fraction V Man i, subsection iii), 16 fraction I and III and Mexican of Industrial Property (OOF 12/27/1999, amended on 10/10/2002, 2W7 / 2004,
IMHiil «WWW WiWMftMiW MMWiiC / 05 / 2009,06 / 01/2 'Ions Ill of the Rule'
Directors
Departmental and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).
Issue Date: May 4, 2016
DIVISIONAL ASSISTANT DIRECTOR OF PATENT FUND EXAMINATION, AREAS
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338812.
«I
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/1··?
MEXICAN INSTITUTE
METHOD FOR MAKING AN ARTICLE COVERED '^ feÁ ^ AfaO'-í
THERMALLY AND ATTACKED / GROUND WITH HA7. nB TONKS
USING A CARBON PROTECTIVE FILM
DIAMOND TYPE (DLC)
FIELD OF THE INVENTION
Certain embodiments of this invention relate to a method of making a heat treated (HT) coated article that is used in shower door applications, window applications, table top applications, or any other application. adequate. For example, certain embodiments of this invention relate to a method of making a coated article that includes a step of heat treating a glass substrate coated with at least one layer comprising diamond-type carbon (DLC). English) and an overlying protective film on it. In certain exemplary embodiments, the protective film can be of or can include both (a) an oxygen barrier or blocking layer and (b) a release layer. After and / or during the heat treatment (eg, heat tempering or the like) the protective film can be completely or partially removed. Other embodiments of this invention relate to the coated article before HT or
<img file="MX338872B_D0008.tif" />
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL to coated article after HT.
BACKGROUND AND SUMMARY OF EXEMPLARY MODALITIES OF THE
INVENTION
Coated items such as clear shower doors and IG window units are frequently heat treated (HT), such as being heat tempered, for safety and / or strengthening purposes. For example, coated glass substrates for use in shower and / or window door units are frequently heat treated at high temperature (s) (eg, at least about 580 ° C). , more typically about 600-650 ° C) for quenching purposes.
Diamond-type carbon (DLC) is sometimes known for its scratch resistance properties. For example, different types of DLC are discussed in the following United States Patent Nos. 6,3 03,226,6,303,225; 6,261,693; 6,338,901; 6,312,808; 6,280,834;
6,284,377; 6,335,086; 5,858,477; 5,635,245; 5,888,593;
5,135,808; 5,900,342; and 5,470,661, all of which are hereby incorporated herein by reference.
Sometimes it would be desirable to provide a window unit or other glass item with a protective coating that includes DLC with the intended
<img file="MX338872B_D0009.tif" />
scratches and the like. Unfortunately, DLC tends to oxidize and calcine at temperatures of about 380-400 ° C, since heat treatment is typically conducted in an oxygen-inclusive atmosphere. In this way, it will be appreciated that DLC as a protective outer coating cannot resist heat treatments (HT) at the extremely high temperatures described above which are frequently required in the manufacture of vehicle windows, IG window units, tops of glass tables and / or the like.
Accordingly, those skilled in the field will appreciate that there is a need in the field for a method of providing heat treated (HT) coated articles with a protective coating (one or more layers) comprising DLC. There is also a need for corresponding coated articles, both heat treated and pre-HT.
Certain exemplary embodiments of this invention relate to a method of making a heat treated (HT) coated article that is used in shower door applications, window applications, table top applications, or any other suitable application. For example, certain modalities of this
<img file="MX338872B_D0010.tif" />
invention refer to a method for<sup>1 </sup>Coated including a step consisting of heat treating a glass substrate coated with at least one layer comprising diamond-like carbon (DLC) and an overlying protective film thereon. In certain exemplary embodiments, the protective film may be of or may include both (a) an oxygen barrier or blocking layer and (b) a release layer. After and / or during the heat treatment 10 (eg, heat tempering or the like) the protective film can be completely or partially removed.
Other embodiments of this invention relate to the coated article before HT or the coated article after
HT.
An exemplary advantage of using different and different oxygen-blocking and release layers in the protective film is that each layer of the protective film can be optimized for its intended function. Consequently, the optimized performance of the protective film can be improved and can be made thinner if desired.
In certain exemplary embodiments of this invention, there is provided a method of making a heat treated coated article, the method comprising:
providing a glass substrate; form at least
<img file="MX338872B_D0011.tif" />
<img file="MX338872B_D0012.tif" />
. MEXICAN INSTITUTE a layer that includes diamond-like coal (glass substrate; form a peí í a _ ρτ-nt-piVm-a on
<td colspan="3">the glass substrate on top of per</td><td rowspan="2">least It includes</td><td colspan="3">the layer that</td>
<td>comprises DLC,</td><td>the</td><td>protective film</td><td>a</td><td>cap</td><td>of</td>
<td>5 detachment</td><td>and</td><td>a barrier layer of</td><td>oxygen,</td><td>the</td><td>cap</td><td>of</td>
<td>detachment</td><td>and</td><td>the barrier layer</td><td colspan="2">oxygen</td><td>are</td><td>of</td>
<td colspan="2">different material</td><td colspan="2">and / or different stoichiometry</td><td>in</td><td colspan="2">relationship</td>
mutual heat treating the glass substrate with the layer comprising DLC and the protective film thereon so that during heat treatment the protective film prevents significant calcination of the layer comprising DLC, wherein the heat treatment comprises heating the substrate of glass at sufficient temperature (s) for thermal tempering, thermal strengthening and / or thermal bending; and exposing the protective film to a release liquid and removing at least part of the protective film during and / or after heat treatment.
In certain exemplary embodiments of this invention, a method of making a heat treated coated article is provided, the method comprising: heat treating a coated glass substrate, the coated glass substrate comprising, prior to heat treatment, a glass substrate, a layer comprising diamond-like carbon (DLC) on the glass substrate; and
ΙΜ
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MEXICAN INSTITUTE
OF (A panpitmn .'A *
FROM INDUSTRIAL PROPERTY a protective film on the glass substrate on top of at least the layer comprising DLC, wherein the protective film includes a release layer and an oxygen barrier layer and the release layer and the oxygen barrier layer they are of different material and / or different stoichiometry in relation to each other; during the heat treatment of the glass substrate coated with the layer comprising DLC and the protective film thereon, the protective film prevents significant calcination of the layer comprising DLC and wherein the heat treatment comprises heating the glass substrate to temperature (s) sufficient for thermal tempering, thermal strengthening and / or thermal bending; and exposing the protective film to a release liquid and removing at least part of the protective film during and / or after heat treatment.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprising: providing a glass substrate including a first major surface and a second major surface, the first major surface being exposed to a tin bath during the manufacture of the glass substrate and the second main surface is opposite to the first main surface and is attacked with acid; deal with beam. ionssiAjg ^ pffir Maerafr main surface of the substrate in order to remove a portion of the surface of the substrate, the portion of the surface comprises tin, tin oxide and / or surface contaminants; lay an inclusive zirconium layer on the first main surface after ion beam treatment; and arranging a layer comprising diamond-like carbon (DLC), directly or indirectly, over the inclusive zirconium layer. The glass substrate with the zirconium inclusive layer and the layer comprising DLC can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending to cause calcination of the layer comprising DLC but without also causing significant calcination of the inclusive zirconium layer.
In certain exemplary embodiments of this invention, a method is provided for making a heat treated coated article, the method comprising: providing a glass substrate including a first major surface and a second major surface, wherein the first major surface has been exposed to a tin bath during the manufacture of the glass substrate and has been ion beam treated in order to remove a portion of the surface thereof that
<img file="MX338872B_D0014.tif" />
It comprises tin, tin oxide, and / or cfisn ^^ naite: superficial, where the second main surface is opposite to the first main surface and has been attacked with acid, and where the first main surface supports, in order moving away from substrate, an inclusive zirconium layer and a layer comprising diamond-like carbon (DLC); and heat treating the glass substrate with the zirconium inclusive layer and the DLC comprising layer thereon, in order to remove the DLC comprising layer and cause at least a portion of the zirconium inclusive layer to be exposed as an outer layer of the heat-treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, where the first main surface is a tin side of the substrate and is corroded with ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof, the second main surface is attacked with acid. The first main surface supports at least temporarily, in order away from the substrate: a layer comprising
<img file="MX338872B_D0015.tif" />
zirconium nitride and a diamond comp layer (DLC). The glass substrate thermally in order to (a) cause the removal of the layer comprising DLC and (b) converting the layer comprising zirconium nitride to a layer comprising zirconium oxide. The first main surface corroded with ion beam or finely milled causes the fogging to be lower after treatment than it would otherwise be if the first main surface was not corroded with ion beam or finely milled.
In certain exemplary embodiments of this invention, a heat treated coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, wherein the first main surface is a tin side of the substrate and is corroded with ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof and where the second main surface is attacked with acid. The first major surface supports, in order away from the substrate, a layer comprising zirconium nitride and a layer comprising diamond-like carbon (DLC). The first main surface corroded with ion beam or finely milled causes the fogging to be lower iwrasj »· * .te jo. je Vf / * · * ”'INSTiTUTO MEXICANO ^^ saSsSf * after the treatment that the one that would be from ote¿a * i>« iaí * “if the first main surface was not ag» —ee-g-ape-í · ion beam or finely milled.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprising: providing a glass substrate that includes a first major surface and a second major surface, the first major surface being exposed to a tin bath during the manufacturing of the glass substrate and the second main surface is opposite to the first main surface and is etched with acid; ion beam treating the first major surface of the substrate in order to remove a portion of the substrate surface, the portion of
<td>the surface comprises tin,</td><td>oxide</td><td>of</td><td>tin</td><td>me</td>
<td colspan="2">surface contaminants; provide</td><td>a</td><td>cap</td><td>than</td>
<td>comprises diamond type coal</td><td>(DLC)</td><td>on</td><td colspan="2">the first</td>
<td>main surface after</td><td colspan="2">treatment</td><td>with beam</td><td>of</td>
ions; and arranging a protective film on the glass substrate on top of at least the layer comprising DLC, the protective layer including at least release and oxygen barrier layers, release and oxygen barrier layers are of different materials and / or have different stoichiometries compared to each other. The glass substrate with the layer comprising DLC and the protective film s
<img file="MX338872B_D0016.tif" />
MEXICAN INSTITUTE
DE LA FLOPILDAD, V ** », can be heat treated at a temperature '<sup>00</sup> SuÉiciehtéT for thermal tempering, thermal strengthening and / or thermal bending in order to cause removal of the protective film without causing significant calcination of the layer comprising DLC.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprising: provide a glass substrate that includes a first main surface and a second main surface, the first main surface has been exposed to a tin bath during the manufacture of the glass substrate and has been ion beam treated in order to remove a portion of the surface thereof comprising tin, tin oxide and / or surface contaminants, the second main surface is opposite to the first main surface and has been acid etched with a mild or intense acid mordant, the first main surface supports, in order away from the substrate, a layer comprising diamond-like carbon (DLC), a layer release and an oxygen barrier layer; and heat treating the glass substrate with the layer comprising DLC, the release layer and the oxygen barrier layer thereon, in order to remove the release and oxygen barrier layers and
OF THE PROPERTY> », C<sup>r</sup>YES '^<sup>ísn</sup>S3 * INDUSTRIAL minus a portion of the layer comprising DLC is exposed as an outer layer of the heat treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first main surface and a second main surface, the first main surface is a tin side of the substrate and is ion beam corroded or finely milled in order to remove tin, tin oxide and / or surface contaminants of a portion of the surface thereof, the second main surface is attacked with acid. The first major surface supports at least temporarily, in order away from the substrate: a layer comprising diamond-like carbon (DLC); an inclusive release layer of zinc; and a layer comprising aluminum nitride. The glass substrate can be heat treated in order to remove the inclusive zinc stripping layer and the layer containing aluminum nitride, leaving the layer comprising DLC as an outer layer. The first main surface corroded with ion beam or finely milled causes the fogging to be lower after treatment than it would otherwise be if the first main surface were not CorjOjíM * Moa
MEXICAN INSTITUTE OF. the property ion or finely milled. industrial f
In certain modalities eg émpidos-35-é'St'S. ' Invention, a heat treated coated article is provided, comprising a glass substrate having a first main surface and a second main surface, the first main surface being a tin side of the substrate and being corroded with ion beam or finely milled in order to remove tin, tin oxide and / or surface contaminants from a portion of the surface thereof, the second main surface is acid-etched with a mild or intense acid mordant. The first main surface supports a layer comprising diamond-type carbon (DLC). The first main surface corroded with ion beam or finely milled causes fogging to be lower after treatment than would otherwise be if the first main surface was not corroded with ion beam or finely milled.
In certain exemplary embodiments of this invention, a method of making a coated article is provided, the method comprising: providing a glass substrate that includes a first major surface and a second major surface, the first major surface being acid etched with a mordant mild acid
<img file="MX338872B_D0017.tif" />
<img file="MX338872B_D0018.tif" />
and the second main surface is opues main surface; lay a diamond-like carbon layer (DLC) over the primary primer-suptilf ldiT; and arranging a protective film on the glass substrate on top of at least the layer comprising DLC, the protective film includes at least release and oxygen barrier layers, release and oxygen barrier layers are different materials and / or they have different stoichiometries compared to each other. The glass substrate with the layer comprising DLC and the protective film thereon can be heat treated at a temperature sufficient for thermal tempering, thermal strengthening and / or thermal bending in order to cause removal of the protective film without causing significant calcination of the layer comprising DLC.
In certain exemplary embodiments of this invention, a method of making a heat treated coated article is provided, the method comprises: providing a glass substrate that includes a first major surface and a second major surface, the first major surface has been acid etched With a mild acid mordant, the second main surface is opposite the first main surface. The first main surface supports, in order away from
IMPL · substrate: a layer comprising carbon <sup>, NS</sup>BSpo | «; í | ^ (DLC) on the first main surface and a protective film which layers include at least release and oxygen barrier, release and oxygen barrier layers are of different materials and / or have different stoichiometries in comparison with each other. The glass substrate with the layer comprising DLC and the protective film thereon is heat treated in order to remove the release and oxygen barrier layers and cause at least a portion of the layer comprising DLC to be exposed as an outer layer of the heat-treated coated article.
In certain exemplary embodiments of this invention, a heat treatable coated article is provided, comprising: a glass substrate having a first major surface and a second major surface, the first major surface being etched with two passes of an acidic mordant soft. The first major surface supports at least temporarily, in order away from the substrate: a layer comprising silicon; a layer comprising diamond-like carbon (DLC); an inclusive release layer of zinc; and a layer comprising aluminum nitride. The glass substrate can be heat treated in order to ΐΓΜΈΤυ-τρ MF.X-.CMiO to cause removal of the layer of
INDUSTRIAL --— - inclusive of zinc and the layer comprising aluminum nitride, leaving the layer comprising DLC as an outer layer. The coated article has a higher scratch resistance than it would otherwise have if the first major surface were attacked with a strong acid bite.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention.
FIGURE 2 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 3 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 4 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention.
FIGURE 5 is a transverse view<sub>£</sub>
Τ -Λ <-ÉTBJ MEXICAN INSTITUTE.
OF THE V'anrciSIrfSS „PROPERTY. - INDUSTRIAL ^ »a. t ** JZ-M of a coated article, before and after heat treatment, according to another exemplary embodiment of this invention.
FIGURE 6 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 7 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 8 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 9 is a schematic cross-sectional view of a coated article having a silky smooth appearance, before and after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 10 is a schematic view of an ion beam that is used for reconditioning a substrate that has a silky smooth appearance, in accordance with an exemplary embodiment of this invention.
FIGURE 11 is a schematic cross-sectional view
<img file="MX338872B_D0019.tif" />
of a coated article having a silky * INDUSTRIAL and low fog after heat treatment, in accordance with another exemplary embodiment of this invention.
FIGURE 12 is a schematic cross-sectional view of another coated article having a silky smooth appearance and low post-heat fogging in accordance with another exemplary embodiment of this invention.
FIGURE 13 compares coated articles that have been corroded with ion beam according to certain exemplary modalities (left side) with coated articles that have not been corroded with ion beam (right side).
FIGURE 14 is a schematic cross-sectional view of a coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention.
FIGURE 15 is a schematic cross-sectional view of a heat treatable coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention.
THE MODALITIES
<img file="MX338872B_D0020.tif" />
CE LA EROUEDAD INDUST RIAL refers more particularly to in which the numbers of
DETAILED DESCRIPTION OF
INVENTION
Now the similar referenced associated drawings are made indicating similar parts by all the various views.
Certain exemplary embodiments of this invention relate to methods of making coated articles that can use heat treatment (HT), wherein the coated article includes a coating (one or more layers) that includes diamond-type carbon (DLC). In certain cases, HT may involve heating a supporting glass substrate, with DLC thereon, at a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C (which is very higher than the calcination temperature of the DLC). In particular, certain exemplary embodiments of this invention relate to a technique for allowing DLC to resist this HT without significantly calcining during it. In certain embodiments, a protective sacrificial film is formed on the glass substrate on top of the DLC in order to reduce the likelihood of DLC calcination during HT. In this way, most (if not all) of the DLC remains on the glass substrate and is not calcined during HT. After HT, the sacrificial protective film (which can in5 ¿u * rMdan.a?
FROM INDUSTRIAL PROPERTY layers) may or may not be removed in different embodiments of this invention.
In certain exemplary embodiments, the sacrificial protective film may be of or may include both (a) an oxygen barrier or blocking layer and (b) a release layer. An exemplary advantage of using different and different oxygen-blocking and release layers in film 17 is that each layer (17a and 17b) can be optimized for its intended function. Accordingly, the optimized performance of the sacrificial film 17 can be improved and made thinner if desired. In certain exemplary modalities, after HT the DLC inclusive layer protects against abrasion and corrosion and against mineral adhesion in hard water (eg, has good hard water washability).
Figure 1 is a schematic cross-sectional view of a coated article, before and after heat treatment, in accordance with an exemplary embodiment of this invention. Typically, the coated article on the left side of Figure 1 exists during a manufacturing step before heat treatment (HT), but may also exist after HT in certain cases. The coated article shown in Figure 1 includes the glass substrate 1, the DLC inclusive layer 11 and the
<img file="MX338872B_D0021.tif" />
one or more layers. In certain exemplary embodiments, the protective film 17 includes a first layer 17a and a second layer 17b which may be of the same or different materials.
Glass substrate 1 is typically of or includes soda-lime-silica glass, although in certain cases
<td>other types of glass can be used. The inclusive layer of DLC 11</td><td>can be</td><td>of</td>
<td>approximately 5 to 1,000 angstroms (Á)</td><td>of thickness</td><td>in</td>
<td>certain exemplary modalities of this</td><td>invention,</td><td>plus</td>
<td>preferably 10-300 Á thick</td><td>and a lot</td><td>plus</td>
<td>preferably 20 to 65 Á thick,</td><td>possibly</td><td>of</td>
approximately 25-50 Á thick, with an exemplary thickness of approximately 30 angstroms. In certain exemplary embodiments of this invention, a DLC layer 11 can have an average hardness of at least about 10 GPa, more preferably at least about 20 GPa, and much more preferably about 20-90 GPa. This hardness renders the layer (s) 11 resistant to scratches, certain solvents and / or the like. In certain exemplary embodiments, layer 11 may be of or may include a special type of DLC known as highly tetrahedral amorphous carbon (t-aC) and in certain embodiments it may be hydrogenated (t-aC: H). In ¿1
MEXICAN INSTITUTE OF EA PROPERTY,. INDUSTRIAL —- may include 1 to 5 -'20T H and much This type of t-aC from certain hydrogenated modalities, any other suitable type of DLC 30% hydrogen, more preferably more preferably 10-20% H .
DLC includes more carbon-carbon (C - - C) sp bonds<sup>3 </sup>which carbon-carbon (C - - C) sp bonds<sup>2</sup>. In certain exemplary embodiments, at least about 30% to 50% of the carbon-carbon bonds in DLC layer 11 can be carbon-carbon (C - - C) sp<sup>3</sup>, more preferably at least about 60% of the carbon-carbon bonds in layer 11 can be carbon-carbon bonds (C - - C) sp<sup>3</sup> and much more preferably at least about 70% of the carbon-carbon bonds in layer 11 can be carbon-carbon bonds (C - - C) sp<sup>3</sup>. In certain exemplary embodiments of this invention, the DLC can have an average density of at least about 2.4 gm / cm.<sup>3</sup>, more preferably at least about 2.7 gm / cm<sup>3</sup>. Exemplary linear ion beam sources 20 that can be used to deposit the DLC inclusive layer 11 on substrate 1 include any of those in any of US Patent Nos. NOS. 6,261,693, 6,002,208, 6,335,086 OR
6,303,225 (all incorporated herein by reference). When an ion beam source is used to deposit layer (s) 11, the
OF THE PROPERTY ' ' '
INDUSTRIAL hydrocarbon premium (eg C<sub>2</sub>H<sub>2</sub>), HMDSO or any
<td>other</td><td>gas</td><td>suitable,</td><td>I know</td><td>they can)</td><td>use in</td><td>the</td><td colspan="2">source of</td>
<td>you do</td><td>of</td><td>ions with</td><td>the</td><td>purpose</td><td>to cause</td><td>than</td><td>the</td><td>source</td>
<td>5 issue</td><td>a</td><td colspan="2">ion beam</td><td>to him</td><td>substrate</td><td colspan="2">1 for</td><td>to form</td>
the layer (s) 11. It should be noted that the hardness and / or density of the layer (s) 11 can be adjusted by varying the ion energy of the deposition apparatus.
The DLC layer 11 allows the coated article 10 to be more scratch resistant than in the event that the DLC layer 11 was not provided. It should be noted that while the layer 11 is on the glass substrate 1 in In certain embodiments of this invention, an additional layer (s) may or may not be under layer 11 between substrate 1 and layer 11 in certain exemplary embodiments of this invention. Thus, the phrase "on the substrate" as used herein is not limited to being in direct contact with the substrate as yet another layer (s) can be provided therebetween.
For example and without limitation, layer 11 of or including DLC may be any of the DLC inclusive layers of any of the United States Patents.
Nos. 6,592,993; 6,592,992; 6,531,182; 6,461,731; 6,447,891;
6,303,226; 6,303,225; 6,261,693; 6,338,901; 6,312,808;
MEXICAN INSTITUTE
OF THE PROPERTY
INDUSTRIAL
<img file="MX338872B_D0022.tif" />
6,280,834; 6,284,377; 6,335,086; 5,858,477; 5,635,245;
5,888,593; 5,135,808; 5,900,342; or 5,470,661 (all of these patents are hereby incorporated herein by reference), or alternatively may be any other suitable type of DLC inclusive layer. The DLC 11 inclusive layer may be hydrophobic (high contact angle), hydrophilic (low contact angle), or none at all, in different embodiments of this invention. The DLC layer 11 may or may not include about 5-30% Si, more preferably about 5-25% Si, and possibly about 10-20% Si in certain exemplary embodiments of this invention. Hydrogen can also be provided in the DLC in certain cases.
Sacrificial protective film 17 is provided for the purpose of protecting DLC layer 11 during HT. In the event that film 17 was not provided, the DLC layer 11 would significantly oxidize during HT and calcine, consequently rendering the final product defenseless against scratches. However, the presence of the protective sacrificial film 17 prevents or reduces the amount of oxygen that can be reached by the DLC layer 11 during HT from the surrounding atmosphere, thereby preventing DLC from oxidizing significantly during HT. As a result, after HT, the inclusive layer of DLC 11
F i,,. . . . ,. INSTITUTE Μξ / ICANO remains on the glass substrate 1 ccm! -A (sTií: rr iiTJCst Wat to provide scratch resistance and / or the like. In certain exemplary embodiments, the protective film 17 includes both an oxygen barrier or blocking layer 17a as a release layer 17b.
The use of zinc and / or zinc oxide in sacrificial protective film 17 has surprisingly been found to be especially beneficial with respect to the reduction and / or prevention of oxygen diffusion in DLC during HT. In the exemplary embodiment of Figure 1 of this invention, the protective film 17 includes a first zinc inclusive layer 17a and a second zinc oxide inclusive layer 17b. The first zinc inclusive layer 17a may be metallic, substantially metallic or substoichiometric zinc oxide in different exemplary embodiments of this invention; while the second zinc oxide inclusive layer 17b may be of or may include zinc oxide in certain exemplary embodiments of this invention. In certain exemplary embodiments, layer 17a is more metallic than layer 17b. In other words, layer 17b contains more oxygen than layer 17a. In this way, layer 17a can function as a release layer while layer 17b can function as an oxygen barrier or blocking layer. An oxygen barrier or blocking layer means that
IMPI layer prevents quantities signif icat'iv ^^. ^^ /;<sub>D</sub>'okSg-e ^ r', ^
INDUSTRIAL '' • «to'SS 'reach DLC during HT.
In certain exemplary embodiments of this invention, layer 17a can be of or include ZnO<sub>and</sub> and layer 17b can be of or include ZnO<sub>x</sub>, where x> y (ie layer 17b contains more oxygen than layer 17a). Furthermore, in certain exemplary embodiments of this invention,
<td colspan="2">and it is approximately</td><td> 0</td><td>to 0.9, more</td><td>preferably</td><td>of</td>
<td>approximately</td><td>0.1 to 0.</td><td> 9,</td><td>even more</td><td>preferably</td><td>of</td>
<td>10 approximately</td><td> 0.1</td><td>to</td><td>0.8, and</td><td>possibly</td><td>of</td>
<td>approximately</td><td>0.1 to</td><td> 0.7</td><td>While</td><td colspan="2">so much, in certain</td>
exemplary embodiments of this invention, x is greater than y,
<td colspan="3">and x is approximately 0.3 to 1.0,</td><td>plus</td><td>preferably</td><td>of</td>
<td>approximately</td><td>0.3 to</td><td>0.99, even</td><td>plus</td><td>preferably</td><td>of</td>
<td>approximately</td><td> 0.5</td><td>to 0.95</td><td>and</td><td>possibly</td><td>of</td>
<td>approximately</td><td>0.6 a</td><td colspan="4">0.90. In this way, it will be appreciated</td>
<td>that in certain</td><td>cases</td><td>exemplary,</td><td>both</td><td>layers 17a and</td><td>17b</td>
they can be of or include zinc oxide, and both layers 17a and 17b can be substocheometric.
Advantageously, it has been found that the use of the zinc oxide layer 17a which is more metallic than the zinc oxide layer 17b surprisingly allows for more efficient and easier removal of the protective film 17 during and / or after heat treatment (HT). In other words, layer 17a is a release layer. The different compositions: .- / elegies';
FROM THE PROPERTY / iD »INDUSTRIAL zinc oxide inclusive 17a and 17b are used to cause different stresses in layers 17a and 17b, stresses which are manipulated in order to allow film 17 to be more easily removed during and / or after HT. In particular, the more metallic zinc oxide based layer 17a can be considered as a release layer to allow the film 17 to be easily removed from the DLC or the substrate during and / or after the HT due to its reduced or no content. oxygen, while the less metallic (and more oxidized) zinc oxide based layer 17b can be considered as an oxygen barrier or blocking layer that reduces or prevents DLC from calcining and / or oxidizing during HT. It should also be noted that any absorption layer can be considered an oxygen barrier layer in certain exemplary cases. In certain exemplary cases, the more oxidic layer 17b can be considered a blocking / protective layer, to protect the less oxidic, softer absorption / barrier layer 17a during heat treatment and otherwise. Zinc oxide is an extremely advantageous material for film 17 because it can be easily removed (eg, using water and / or vinegar) during and / or after HT in a non-toxic manner.
IMPí
MEXICAN INSTITUTE OF PROPERTY
According to the aforementioned níéfííé<sup>TO</sup>,<sup>L</sup> u? * both layers 17a and 17b when they are from or TñClUysri<sup>1</sup> 2 Int and / σ zinc oxide can be substoichiometric. This is advantageous for the purposes of oxygen absorption during HT. If the full film 17 zinc oxide is highly oxidized (i.e. it is completely stoichiometric) before HT, then oxygen can diffuse through the zinc oxide. However, the substoichiometric character of layer (s) 17a and / or 17b allows zinc in the same (s) to absorb oxygen during HT, so that at least layer 17a (and possibly layer 17b) is not calcined during HT. It should be noted that the zinc oxide based top layer 17b may or may not be calcined (completely or partially) during HT in different exemplary embodiments of this invention. It should be noted that another exemplary advantage of substoichiometric zinc oxide (compared to fully stoichiometric zinc oxide) is that it can be deposited (eg, via ion spray or the like) more quickly. One or both layers 17a, 17b can be deposited by means of the ion spray in a substoichiometric form, in any suitable way; for example, by varying the flow of gaseous oxygen in the ion spray chamber (s). For example, as a non-limiting example, layer 17a can
IMPI
INSTITUTO MEXICANO can be deposited by means of the powder: say ^ £ gíOg¿E using 10 ml / kW (with respect to the content of f1njr> oxygen gas), while layer 17b can be deposited by means of ion spray using 12 ml / kW (with the rest of the gas being Ar or similar) in exemplary cases.
It should be noted that one or both of the zinc oxide layers 17a and 17b can be doped with other materials such as Al, N, Zr, Ni, Fe, Cr, Ti, Mg, mixtures thereof or the like, in certain exemplary embodiments of this invention.
In certain exemplary embodiments of this invention, release layer 17a (eg, zinc or substoichiometric zinc oxide) can be deposited (eg, via ion spray) so that it is approximately 50-20,000 Á thick, more preferably approximately 50-3,000 Á thick, even more preferably approximately 100-1,000 Á thick, with an exemplary thickness being approximately 100-300 Á. In certain embodiments, the zinc oxide inclusive layer 17b can be deposited (eg, via ion spray) to be approximately 200-10,000 Á thick, more preferably approximately 500-5,000 Á thick. thickness, more preferably approximately 1,000-3,000 Á of
<img file="MX338872B_D0023.tif" />
<img file="MX338872B_D0024.tif" />
thickness, being a thickness ¿approximately 2,000 Á. The more metallic layer 17a may be thicker than the less metallic layer 17b in certain exemplary embodiments of this invention; Layer 17a can be at least twice as thick as Layer 17b in certain exemplary cases before HT. A preferred thickness of total sacrificial film 17 in certain exemplary embodiments is less than about 10,000 Á, more preferably less than about 3,000 Á, and much more preferably less than about 1,000
TO.
Figure 2 illustrates another exemplary embodiment of this invention. The embodiment of Figure 2 is the same as the embodiment of Figure 1 set forth above, except that in the embodiment of Figure 2 a barrier layer 6 is provided between the glass substrate 1 and the inclusive DLC layer 11. The layer Barrier 6 may be of a dielectric material in certain exemplary embodiments of this invention. Optional barrier layer 6 is to prevent or reduce oxygen and / or sodium (Na) migrating from glass 1 into DLC layer 11 during HT. In this regard, this optional barrier layer 6 can improve the overall optical characteristics of the coated article after HT. Barrier layer 6 can be of or can include silicon oxide, silicon nitride, silicon oxynitride and / or the like, but also s
<img file="MX338872B_D0025.tif" />
MEXICAN INSTITUTE .. OF THE INDUSTRIAL FROFIEDA.OV
<img file="MX338872B_D0026.tif" />
other barrier materials. The barrier cap (s) 6 are formed on the glass substrate 1 by means of the ion spray or by any means. another suitable technique. Barrier layer 6 can be from about 10 to 1,000A thick in certain exemplary embodiments, more preferably 50 to 500A thick and much more preferably 50 to 200A thick. It should be noted that a barrier layer (s) 6 can also be provided in other exemplary embodiments of this invention, for example in any of Figures 4-7 if desired between the DLC layer 11 and the glass substrate
1.
Figure 3 illustrates another exemplary embodiment of this invention. The mode of Figure 3 is the same as the mode of Figure 1 (or even the mode of Figure 2 if barrier layer 6 is used, which may be the case in the mode of Figure 3), except that Instead of two discrete layers 17a and 17b, the protective film 17 is made of one layer that has oxidation graduation (continuously or not continuously) throughout its thickness. In the embodiment of Figure 3, film 17 is provided such that film 17 includes more oxygen at a location further away from DLC layer 11 than at another location in the film closer to DLC layer 11. It should be noted that .la
<img file="MX338872B_D0027.tif" />
INDUSTRIAL the modalities of Figures 1-2 can also be considered to have oxidation graduation because the global film 17 is more oxidized in the layer 17b furthest from the DLC layer 11 than in the layer 17a closest to the layer of DLC 11. However, in the embodiment of Figure 3, it is also possible that the continuous or substantially continuous oxidation graduation occurs for all or substantially all of film 17 in certain exemplary cases.
An exemplary process for the manufacture of a coated article will now be described, with reference to Figures 1-3. Initially, the glass substrate 1 is provided and at least one barrier layer 6 (eg, silicon oxide, silicon nitride, silicon oxynitride, or the like) can optionally be sprayed onto a surface thereof. Optionally, a multi-layer solar control coating (which is not shown) can be deposited (eg, via ion spray) on the surface of the glass substrate 1 that is opposite the barrier layer 6. Therefore At least one layer 11 of or including DLC is deposited (eg, via ion beam deposition) on the glass substrate 1, on top of at least the optional barrier layer 6 therein. UNCLEAN if it is present. Then ProteX ^ riEp ^ feA ^ s ^^^ X protective 17, for example including layers 17a and 17b, is deposited on the substrate 1 on top of the inclusive layer of DLC 11. The protective film 17 can be deposited via the ion spray, CVD, ion beam deposition or any other suitable technique. Optionally, a thin protective layer comprising DLC, silicon nitride, aluminum nitride, or silicon-aluminum nitride (not shown), can be provided on top of the sacrificial film 17 before HT, for durability and / or hydrogen barrier.
As shown in Figures 1-2, the glass substrate 1 with the films 6 (optional), 11 and 17 thereon is then heat treated (HT) for the purposes of thermal tempering, thermal bending, thermal strengthening and / or Similar. At least part of this HT can be conducted, for example, in an atmosphere that includes oxygen as is known in the field at a temperature (s) of 550 to 800 ° C, more preferably 580 to 800 ° C (i.e. temperature (s) higher than the calcination temperature of the DLC). HT can last for at least one minute, more preferably 1-10 minutes, in certain non-limiting exemplary embodiments of this invention. During HT, the presence of the protective film 17 protects the layer
<img file="MX338872B_D0028.tif" />
JL JL ».Η j5L inclusive uv όθ DLC 11 ό, θΐ HT θ prevent qus' Islin
INDUSTRIAL and / or calcine significantly due to significant oxidation during HT. While in some cases some of layer 11 may calcine during HT, most if not the entire DLC inclusive layer 11 remains on substrate 1 even after HT due to the presence of protective film 17 .
A significant advantage that is associated with the use of zinc and / or zinc oxide in film 17 is its ease of removal after HT. Protective layers such as silicon nitride are sometimes undesirable since they require complex corrosion in order to remove them after HT. Furthermore, it has been discovered that when the film 17 is made of zinc and / or zinc oxide, soluble in vinegar and / or water (possibly only water without vinegar being required in certain preferred embodiments), the application of vinegar and / or water allows portions of film 17 remaining after HT to be easily removed in a non-toxic manner. Again, in certain exemplary modalities, it is possible to remove zinc oxide only with water (no need for vinegar) in certain cases, which is advantageous from a cost and processing point of view. In certain exemplary cases, rubbing with these liquids can be especially beneficial in
Ρ ί
F Ju -δ- J5L 4 το MEXICANO V ;:
film removal 17 after: deT<sup>YOU</sup>DÍ ¥ Sfroch ^ · coated article is still hot from it (for example, when film 17 is approximately 80-200 ° C, more preferably approximately 100-180 ° C; although removal of film 17 may also take place at room temperature in certain exemplary modalities).
After the film 17 has been removed, the remaining coated article is shown on the right hand side of Figures 1-2 and includes an outer layer comprising scratch resistant DLC. The aforementioned processes are advantageous in that they provide a technique for allowing a coated article including a protective DLC inclusive layer 11 to be heat treated without the DLC layer 11 calcining during this HT. In other words, it becomes possible to provide an inclusive layer of protective DLC 11 on a heat-treated (eg, heat-tempered) product in a commercially acceptable manner.
Figure 4 is a cross-sectional view of an exemplary embodiment of this invention that is similar to Figures 1-2, except that the release layer 17a and the oxygen blocking layer 17b need not be zinc oxide. A barrier layer 6 (discussed above) may or may not be provided between the glass and the DLC in the embodiment of Figure 4 (although not <aüL ·, INDUSTRIAL ^ «, - *** figure).
Oxygen barrier or blocking layer 17b may be of or may include a material selected from the group consisting of: zinc oxide, silicon carbide, aluminum nitride, boron oxide, aluminum oxide, aluminum oxynitride, silicon nitride , silicon oxide, silicon oxynitride and mixtures thereof. The preferred materials for the oxygen barrier or blocking layer 17b are aluminum nitride and silicon carbide in certain exemplary embodiments. In certain exemplary embodiments, layer 17b is designed to be approximately as hard and / or durable as glass.
Release layer 17a can be of any suitable material that easily dissolves or reacts with water, vinegar or bleach. Release layer 17a preferably has a melting point (or dissociation temperature) greater than 580 or 600 ° C in certain exemplary embodiments. Release layer 17a can be of or can include boron oxides, suboxides, nitrides and / or subnitrides, titanium boron, magnesium, zinc and mixtures thereof. Preferred materials for release layer 17a in certain exemplary embodiments are zinc, magnesium, and / or titanium boride suboxides. It should be noted that
<img file="MX338872B_D0029.tif" />
the term oxide as used broadly enough to include sub-oxides.
In certain exemplary embodiments, release layer 17a is more dissolvable than layer 17b in water, vinegar, bleach, and / or the like. On the other hand, in certain exemplary embodiments, the oxygen barrier layer 17b is more of an oxygen barrier and / or is harder than the release layer 17a. Exemplary coatings can produce high quality DLC after HT and after peeling, with good scratch resistance and good hard water washability. Release layer 17a and / or oxygen barrier layer 17b can be deposited by way of ion spray, or any other suitable technique, in different exemplary embodiments of this invention.
Figure 5 shows an exemplary embodiment where the release layer 17a is of or includes a magnesium superoxide (MgO<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes silicon carbide. Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases in this embodiment, to reduce sodium migration during or due to HT. After heat treatment or HT (for example tempering), the product is exposed to a slightly reactive liquid (for example,
<img file="MX338872B_D0030.tif" />
water, vinegar, diluted ammonia and / or · bfraoiTqu ^^ qg)
INDUSTRIAL liquid penetrates through the release layer 17a via small holes or grain boundaries in the overlying layer (s) and causes the release layer to disappear from the DLC ll layer. In this way, the release layer 17a and the oxygen barrier layer 17b are removed after HT. Hot water is a release liquid particularly good for
<td colspan="4">use with the materials shown in the</td>
<td>Figure</td><td> 5.</td><td>Exemplary thicknesses</td><td>are as follows</td>
<td>way</td><td>in</td><td>this exemplary modality:</td><td>barrier layer 6</td>
<td>nitride</td><td>of</td><td>silicon or oxynitride</td><td>silicon formed by</td>
ion spray medium approximately 125 or 150 Á thick; DLC layer 11 approximately 50A thick; MgOx 17a layer approximately 190 Á thick and SiC 17b layer approximately 280 Á thick.
Figure 6 shows an exemplary embodiment where the release layer 17a is of or includes a zinc superoxide (ZnO<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (A1N). Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases in this embodiment, to reduce sodium migration during or due to HT. After treatment \ - ΛΑ Mexican thermal institute or HT (for example, tempering), e ^<sup>THE</sup>'$ »C ^ cfc? E £ ^ exposes to a slightly reactive liquid wo .....- (fMMsr e example;
water, vinegar, dilute ammonia and / or bleach) and the liquid penetrates through to the release layer 17a via small holes or grain boundaries in the overlying layer (s) and causes the layer peel off from DLC layer 11. In this way, peel off layer 17a and oxygen barrier layer 17b are removed after HT. Vinegar is a particularly good release liquid for use with the materials shown in the
Figure 6. Exemplary thicknesses are as follows in this exemplary embodiment: barrier layer 6 of silicon nitride approximately 150A thick; DLC layer 11 approximately 50A thick; ZnOx 17a layer approximately 500 Á thick and AlN 17b layer approximately 200 Á thick.
Figure 7 shows an exemplary embodiment where the release layer 17a is of or includes a Mg superoxide (MgO<sub>x</sub>) and the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (AlN). Optionally, a barrier layer 6 can be provided between the DLC layer 11 and the glass substrate 1 in certain cases in this embodiment, to reduce sodium migration during or due to HT. After heat treatment or HT (for
....... i .. · - ..: —'-— ¿i—
ΡI. MEXICAN INSTITUTE V £ r **<sup>:</sup>liW '*'<sub>i</sub>for example, tempering), the product is exposed slightly reactive (eg, water, vinegar, ammonia or diluted and / or bleach) and the liquid penetrates through to the release layer. 17a via small holes or grain boundaries in the overlying layer (s) and causes the release layer to disappear from the DLC layer 11. In this way, the release layer 17a and the layer Oxygen barrier 17b are removed after HT. Hot water is a particularly good release liquid for use with the materials shown in the Figure 7 embodiment. Exemplary thicknesses are as follows in this exemplary embodiment: DLC layer 11 approximately 50A thick; MgOx 17a layer approximately 230 Á thick and A1N 17b layer approximately 200 Á thick.
Figure 8 is also applicable to any of the modalities outlined above. Figure 8 shows an exemplary embodiment where the release layer 17a is of or includes a zinc superoxide (ZnO<sub>x</sub>), the oxygen barrier or blocking layer 17b is of or includes aluminum nitride (A1N) and an outer covering protective layer 17c of or including silicon nitride and / or silicon oxynitride is provided. Optionally, a barrier layer 6 (for example, of or that •, ... ,, .. 1.,.. INSTITUTO, MEXICANO, £ ¿«* = ^ £ 5« *.
includes silicon nitride, siliciODy oxide ^ g »> ^ jj.na silicon) can be provided between the DLC layer 11 and the glass substrate 1 in certain cases of this modality, to reduce sodium migration during or due to to HT. After heat treatment or HT (eg, tempering), the product is exposed to a slightly reactive liquid (eg, water, vinegar, dilute ammonia and / or bleach) and the liquid penetrates through to the release layer 17a by small hole path or grain boundaries in the overlying layer (s) and causes the release layer to disappear from the DLC layer 11. In this way, the release layer 17a, the oxygen barrier layer 17b and the protective layer 17c are removed after HT. Vinegar is a particularly good release liquid for use with the materials shown in the Figure 8 embodiment, although other liquids such as water can also or instead be used for removal of the sacrificial film 17. Brushing (eg, via rotary brushes such as nylon brushes or the like) can be used to remove film 17 when wetted with water or the like in certain exemplary cases. The exemplary thicknesses are as follows in this exemplary embodiment: Silicon nitride barrier layer 6 of / Τ 'Τ7 *
Saw
MEXICAN INSTITUTE $. , «DE LA PROPERTY, V ** 5at3cUÍW approximately 100-300 A thick (p © apsTRiAe] i approximately 200 A thick); layer do — BLC ll · da. approximately 30-60 Á thick (eg, approximately 30-50 Á thick); ZnOx layer 17a approximately 500-2,000 Á thick, oxygen-blocking AlN layer 17b approximately 100-300 Á thick (for example, approximately 200 Á thick) and protective silicon nitride inclusive layer 17c approximately 0 -500 Á thick (for example, approximately 200-300 Á thick). The silicon nitride-based protective layer 17c is advantageous in that it provides improved mechanical durability of the sacrificial film 17 and prevents or reduces damage to the film-coated article during transportation and handling (for example, if the Film 17 is scratched, may not adequately protect DLC from calcination during HT).
In accordance with certain exemplary embodiments of this invention, the articles coated herein lose no more than about 15% of their transmission in the visible spectrum due to HT, more preferably no more than about 10%. On the other hand, the monolithic coated articles herein preferably have a transmission in the visible spectrum after HT of at least about 50%, more
MEXICAN INSTITUTE preferably at least approximateiflefi ^^ jf
As indicated above, the substrate 1 may be a soda-lime-silica glass. This and other glasses can be made using a waterline, for example with a tin bath. As is known, a substrate of or including floated virium can have two main surfaces. A first main surface of the substrate can be in contact with the tin bath during the flotation process and the (second) opposite main surface can be exposed to the environment. Thus, in certain exemplary embodiments, a substrate can have two main surfaces, often called a tin side and an air side, for example, because the first main surface contacts the tin bath while the surface Opposite main is exposed to the environment or air.
In certain exemplary embodiments, one or both of the tin side and the air side of a substrate may be coated, for example, using the coatings described herein. Additionally, the coatings described in this document can be deposited on one or both main surfaces of the substrate, in different exemplary modalities.
Decorative glass is known. This glass can be based on soda-lime-silica glass and can be, for ttíML'u. Γ & ίϋο'-λΐ - * -.
example, SatinDeco glass or SatinB glass ^ ^ c ^^ je
OF THE PROPERTY
INDUSTRIAL ** -
<img file="MX338872B_D0031.tif" />
commercially available from Guardian Industries Corp.
This type of glass has a silky smooth appearance, is easy to clean, and is resistant to body oils that penetrate the glass (making it also resistant to smudges and fingerprints). Provides privacy while still allowing light to shine through. Visible and performance properties can be obtained, for example, by acid etching the glass, thereby creating a microtextured structure. It should be noted that for SatinDeco glass<sup>1</sup>® 6mm thick commercially available, for example, the transmission in the visible spectrum is at least 80% from both sides, more preferably it is at least 85% from both sides and in some cases it is 90.5% or higher for incident light on a satin surface and 88.5% or higher for incident light on an unsaturated surface. Acid attack treatment can be performed on one or both sides of the glass, which can be inked or can be neutral in color. Glass with this kind of silky smooth appearance can be used in a variety of applications including in kitchens, bathrooms, offices and other settings; to create partitions, stairs, doors, murals and shower cabins; to achieve desired effects for windows, floors' -Í &
MEXICAN INSTITUTE
DE LA FSOFItDA.D,,, wp INDUSTRIAL SatinDeco and SatinDeco glass
<img file="MX338872B_D0032.tif" />
and walls; etc.
Elegance<sup>MR</sup> Commercially available may have the following roughness values:
<td></td><td>Ra</td><td>Rz</td><td>Rq</td><td>RSm</td>
<td>Satin deco<sup>MR</sup></td><td> 1.92</td><td> 11.11</td><td> 2.02</td><td> 61</td>
<td>SatinDeco Elegance<sup>MR</sup></td><td> 0.74</td><td> 9.53</td><td> 1.87</td><td> 141</td>
It must be taken into account that Satin glass "<sup>1</sup>* commercially available from Walkerhas is similar to Guardian's SatinDeco Elegance ™ * product, while Velor glasses ”<sup>1</sup>* and Opaque "<sup>1</sup>* commercially available from Walkerhas are similar to the SatinDeco product ”<sup>1</sup>* from Guardian and that the exemplary embodiments of this invention can be used with these and other acid etched substrates or otherwise providing the same or similar silky smooth appearance.
It will be appreciated that when a silky smooth appearance is desired, it may also be desirable to use the DLC inclusive protective coatings described herein. In these cases, the air side of the glass can be acid etched to create the desired silky appearance. The DLC inclusive protective coating, on the other hand, can be applied to the opposite main surface or the tin side of the
<img file="MX338872B_D0033.tif" />
<img file="MX338872B_D0034.tif" />
INDUSTRIAL> «fc a coated article having a silky smooth appearance, before and after heat treatment, according to another exemplary embodiment of this invention.
The type of acid attack can be an intense acid attack or a mild acid attack. SatinDeco glass<sup>MR</sup> can be produced using a single pass of an intense acid mordant, while SatinDeco Elegance glass<sup>MR</sup> It can be produced using two passes of mild acid mordant. Choosing an intense or mild acid mordant can result in different surface textures than the corroded surface of the glass. For example, an intense acid mordant will tend to produce steep peaks and valleys, while a mild acid mordant will tend to produce slightly sloping peaks and valleys that will tend to be shallower than those produced via the intense acid mordant. This will also sometimes result in a difference in the fogging that occurs, such that intense acidic mordants will tend to produce glass that has greater fogging than a glass substrate treated with a mild acidic mordant.
As shown in Figure 9, the glass substrate 1 has an acid etched first major surface which helps to provide a smooth appearance.
<img file="MX338872B_D0035.tif" />
Silky coated item. The spikes
INDUSTRIAL deep valleys shown in Figure 9 are similar to those produced using a pass with intense acid mordant (although other exemplary modalities may have pronounced peaks and valleys that occur via other mordants, and although still other exemplary modalities may have slightly peaks more undulating with shallower valleys than those that can be produced with two passes of mild acid mordant or via some other suitable means). The second main surface Ib supports the protective coating. For example, prior to heat treatment, the second main surface Ib supports one or more dielectric materials 6, a layer comprising DLC 11, and a protective film 17 (including one or more release layers 17a and one or more barrier layers of oxygen 17b). After heat treatment and film removal, the second main surface Ib supports one or more of the dielectric materials 6 and the layer comprising DLC 11.
In certain exemplary embodiments, the first major surface la is the air side of the float glass substrate l, while the second major surface Ib is the tin side of the float glass substrate 1. Naturally, this can be reversed in
<img file="MX338872B_D0036.tif" />
I different embodiments of the invention.
INDUSTRIAL notes that the acid-etched surface also does not support the protective coating. This is because the protective film may interfere with at least some of the advantageous properties conferred by acid attack and / or may not provide a good surface for subsequent deposition of the layer comprising DLC. To obtain a good balance of the protective scratch resistance of the DLC along with the smooth, silky, desired appearance and anti-fingerprint and easy-to-clean properties of acid attack, it may be desirable to provide the DLC on the opposite surface of the acid attacked surface. Typically, the acid etched surface is the air side of the substrate (eg, for ease of manufacture). In this way, as indicated above, the layer comprising DLC 11 can be provided on the tin side of the float substrate, while the acid etching can be performed on the air side of the float glass substrate.
The inventors of the present application have discovered, however, that the arrangement of the protective coating (including the layer comprising DLC) on the tin side of the glass substrate results in aesthetically unpleasant amounts of
<img file="MX338872B_D0037.tif" />
MPI<sup>;</sup> ~, INSTITUTO MEXICANO T.-A.,<sub>r</sub> ¿»Fogging, especially after treatment Mi ^ ffifcjg ^ béjiaft ^ gfr (eg thermal strengthening or thermal tempering) and removal of the sacrificial release layer (s).
The inventors have discovered that this increase in fogging may be due to the fact that tin, tin oxide and / or other contaminants can accumulate on the tin side of the substrate while it is in the tin bath during the flotation process and / or when it is being carried by transport rollers (for example, throughout the line). In some cases, this accumulation of tin and / or tin oxide may be similar to a thin film comprising tin and / or tin oxide that has been deposited on a substrate. In reality, tin and / or tin oxide deposits can result in a continuous or discontinuous layer that contributes to fogging, especially after heat treatment. The accumulation of tin and / or tin oxide is believed to be at least partially responsible for fogging, as is the presence of contaminants in the bath and / or rollers, where rollers and contaminants potentially cause other surface defects resulting in fogging results after heat treatment.
It will be appreciated that in some situations it would be
<img file="MX338872B_D0038.tif" />
INDUSTRIAL desirable to reduce thermal post fogging.
It has been surprisingly and unexpectedly discovered that the onset and / or severity of post heat treatment fogging can be reduced by reconditioning the tin side of the substrate prior to deposition of the layers in the stack of protective layers (including, for example,
<td>example,</td><td>one</td><td>or</td><td>plus</td><td>of</td><td>the</td><td>materials</td><td>dielectrics</td>
<td>optional</td><td> 6,</td><td>the</td><td>cap</td><td colspan="2">inclusive</td><td>from DLC 11 and</td><td>the movie</td>
<td>protective</td><td> 17)</td><td colspan="3">. For example,</td><td>the</td><td>inventors have</td><td>discovered</td>
that the occurrence and / or severity of post-heat fogging can be reduced by corrosion and / or fine milling of the tin side of the substrate with an ion beam. It is believed that corrosion and / or fine ion beam milling can aid in the removal of at least a portion of tin, tin oxide and / or other contaminant accumulating on that surface, thereby eliminating a potential cause of fogging. . Ion beam corrosion can be performed using any suitable ion. For example, it has been surprisingly and effectively discovered that corrosion with suitably pure Ar or N2 on the tin side of a substrate reduces post heat treatment fogging when a protective coating is applied to the air side of the substrate. It is difficult to accurately measure the fogging of the coating on a final product because the attack with
INDUSTRIAL a camouflage. However, an indexing fluid can be used to flatten the etched surface with acid. When this is done, the fogging for non-ion beam treated glass was above 1%, while the fogging for ion beam treated glass was less than 0.5%.
As alluded to above, in certain exemplary embodiments, the tin side of the glass substrate 1 can be finely milled with an ion beam before layers 6, 11 and 17a and 17b are disposed thereon. Fine ion beam milling of the glass substrate can remove or reduce the tin, tin oxide and / or other contaminant accumulated on the glass, thereby resulting in a final product with a reduced amount of fogging to the glass. heat treatment. For example, any of the exemplary ion beam fine milling techniques described in US Patent No. 6,368,664 can be used to finely ion-glass mill the glass substrate 1 in this regard, the disclosure of the '664 patent is incorporated herein by reference.
Naturally, other techniques are also possible. For example, ion beams, ion sources, ion beam treatments, and the like are disclosed, by r
<img file="MX338872B_D0039.tif" />
example, in the Es £ ac Patents
6,808,606; 7,030,390;
7,311,975; 7,405,411;
7,183,559; 7, IQfifiQQ, 7 ooo rtt<sub>F</sub>
7,488,951 and 7,563,347, and
United States Publications Nos. 2005/0082493; 5 2008/0017112; 2008/0199702, the complete contents of each of which are incorporated by this act in this document as a reference. Corrosion or fine ion beam milling using these and other techniques can advantageously help reduce fogging i
after heat treatment.
FIG. 10 is a schematic view of an ion beam used for reconditioning a substrate that has a silky smooth appearance, in accordance with an exemplary embodiment of this invention. Ion beam source 102 provides ions 104 that contact the tin side surface Ib of substrate 1. The force with which the ions contact the tin side surface Ib causes at least a portion of the substrate 1 and / or contaminants thereon to be finely milled or corroded. This leaves the substrate 1 with a finely milled surface with ions as a first main surface on the tin side. The acid-etched Ib surface opposite the finely milled or ion beam corroded surface remains intact.
CITY OF MEXICAN TUTE CE LA PXOHEDares
<img file="MX338872B_D0040.tif" />
In certain exemplary embodiments, fine or ion beam corrosion can be used to remove at least about 2A of glass from the substrate, more preferably at least about 5A and possibly at least about 10A. Thereafter, one or more thin film layers in the protective coating can be disposed thereon. For example, one or more of the optional dielectric materials 6 and / or the DLC inclusive layer 11 can be deposited using ion spray (eg, using plane and / or magnetron targets) or via beam-assisted deposition ion (IBAD) in different modalities. The stack configurations can be produced by means of a one-pass online deposition in a suitably configured system or in any other suitable way in different exemplary modalities.
In some cases, SatinDeco related features<sup>MR</sup> they can be provided on the air side of a glass substrate. Thus, in certain examples, any additional coatings will be applied to the tin side as outlined above. In some cases, therefore, the inclusive DLC coating can be applied to the tin side of a glass substrate. In other exemplary modalities, however,
<img file="MX338872B_D0041.tif" />
-t THE “ROHEDAO 'ss * INDUSTRIAL inclusive of DLC described in this document can be applied on the air side of a glass substrate.
In any of the embodiments discussed above (eg, see Figures 1-9 above), it is also possible to provide an optional scratch resistant layer (eg, of or including SiC or DLC) over layer 17b.
In certain other exemplary embodiments, it may be advantageous to provide coatings as described herein on a major surface of a glass substrate, while another major surface is treated differently.
Figure 11 is a schematic cross-sectional view of a coated article having a silky smooth appearance and low post-heat fogging, in accordance with another exemplary embodiment of this invention. A glass substrate 1 is shown in Figure 11. The glass substrate 1 includes an acid etched air side surface la which creates an appearance similar to a smooth, silky matte finish that provides privacy while at the same time also allowing light to pass through the substrate. The tin side of substrate 1 has been finely corroded or milled with an ion beam. Corroded surface or MEXICAN PROPERTY INSTITUTE
INDUSTRIAL
<img file="MX338872B_D0042.tif" />
Finely milled with ion beam le, prior to heat treatment, supports one or more optional dielectric layers or barrier 6, for example, of or including silicon oxide, silicon nitride, silicon oxynitride, zirconium, tin oxide, oxide Titanium or multi-layer for optical purposes (eg high / low index layer stacks, high / low / medium index layer stacks etc.). One or more of the optional dielectric or barrier layers. A layer comprising DLC 11 is provided on one or more of the optional dielectric or barrier layers 6 and a zinc inclusive release layer 17a is provided on top of the layer comprising DLC 11. The zinc inclusive release layer 17a may be of or can include zinc oxide, zinc oxynitride or zinc nitride in different embodiments of this invention. A layer comprising aluminum nitride 17b can be provided on top of the zinc inclusive release layer 17a. Optionally, in certain exemplary embodiments, a temporary protective layer (TPF) 17c may be provided as an outer layer. To better protect coated glass sheets at various processing stages, temporary protective coatings have been developed. See, for example, United States Publications Nos. 2010/0178850;
IMPI
<img file="MX338872B_D0043.tif" />
MEXICAN INSTITUTE
2010/0024953; 2009/0068350; 2009/0044897; 2¾ 4 ^ 2 -aÁj
2005/0210921, the complete contents of each of which are incorporated by this act in this document as a reference. Temporary protective coatings can be applied in solid or liquid forms and are designed in such a way that they can be easily removed, typically by peeling.
TPF 17c can be removed by peeling or by abrasive means prior to heat treatment in certain exemplary modalities. However, in certain other exemplary embodiments, TPF 17c can be removed by virtue of the high temperatures associated with heat treatment. In either case, the zinc-inclusive release layer 17a and the layer comprising aluminum nitride 17b can also be removed after heat treatment. An inclusive zirconium layer can be used as one or more of the optional dielectric or barrier layers 6 in certain exemplary embodiments and this layer can change with heat treatment. For example, a ZrN inclusive layer can become a ZrOx inclusive layer with heat treatment. In certain exemplary embodiments, the layer may consist essentially of ZrN prior to heat treatment and may consist essentially of ZrO after heat treatment. It will be appreciated that the
Ι · MEXICAN INSTITUTE LA '' '“/« jáThe conversion from ZrN to ZrOx can be complete<sup>Gave</sup>ój.j ^^ á £ La'i22r certain exemplary modalities, the layer may include more than 0 before heat treatment and may include more than 0 after N heat treatment. After heat treatment, the coated article exhibits good fogging properties. The good observable fogging on the coated article as shown and described herein, for example in connection with the exemplary embodiment of Figure 11, provides superior fogging values compared to articles lacking the finely milled or surface treated surface. ion beam on the tin side of the substrate.
It should be noted that the textured surface of the substrate 1 may have a prismatic surface, a matte finish surface or the like in different exemplary embodiments of this invention. The textured surface of substrate 1 may have peaks and valleys defined therein, with sloping portions interconnecting peaks and valleys. This surface of the substrate 1 can be corroded (for example, by corrosion with HF using HF mordant or the like) and / or stamped by way of rollers or the like during the manufacture of the glass for the purpose of forming a textured surface ( and / or stamped) the. In some cases, corrosion can be done using a: IMPIfeí and INSTITUTO MEXICANO fX '<sup>4</sup>'
DE FL. & PÍF.OAD mordant of single or multiple agents, pdiff ^^ femp 'of or including a weak acid. For example-p ·, -—- s'e - you can use HCI, H<sub>2</sub>SW<sub>4</sub>, formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CC1<sub>3</sub>COOH), hydrofluoric acid (HF), hydrocyanic acid (HCN), hydrogen sulfide (H<sub>2</sub>S), and the like.
Figure 12 is a schematic cross-sectional view of another coated article having a silky smooth appearance and low post-heat fogging, in accordance with another exemplary embodiment of this invention. Figure 12 is similar to Figure 11 in that the air side of Substrate 1 has been corroded with a strong acid mordant to produce the steep peaks and deep valleys schematically shown therein. The ion beam reconditioned tin side le of substrate 1 also supports a layer comprising zirconium nitride and an inclusive layer of DLC 11 thereon. However, preferably than providing a separate sacrificial protective film 17 (eg, as in the exemplary embodiment of Figure 11), the DLC inclusive layer 11 itself is used as the sacrificial or protective layer. In this way, as shown in Figure 12, the inclusive layer of DLC 11 is removed as a result of heat treatment and the layer comprising ZrN 6 is
THE
MEXICAN INSTITUTE
Dt THE PROPERTY f
Converts to a layer comprising ZrOx from heat treatment.
It should be noted that a TPF material similar to that described above in relation to Figure 11 can be provided in connection with the embodiment of Figure 12. As before, the TPF material can be removed (eg, via from detachment, exposure to a removal liquid and / or abrasive media) prior to heat treatment, or TPF material may be removed as a result of heat treatment.
Figure 13 compares coated articles that have been corroded with ion beam according to certain exemplary modalities (left side) with coated articles that have not been corroded with ion beam (right side). The images on both the right and left sides share the layer stack illustrated in Figure 12. However, the example on the left side has an ion beam textured main surface on the le side, while the example on the right side does not. As can be seen in Figure 13, the ion beam finely milled substrate on the left side had less post-temper fogging than the non-finely milled substrate on the right side. In this way, it is clear that corrosion or fine milling with
<img file="MX338872B_D0044.tif" />
tin side ions of the substrate d structural difference in the glass that can be seen in the form of a lack of fogging after heat treatment compared to a situation where corrosion or fine milling with ion beam is not carried out on the tin side of the substrate.
As explained above, by finely milling with an ion beam the tin side of the substrate first before a protective coating is placed on it, the fogging of the final product (eg after processing and / or heat treatments) can be reduced . This is advantageous in that fogging can be kept low while still providing a scratch resistant article that also looks similar to a smooth, silky matte finish, providing privacy with light transmission.
As indicated above, it is possible to attack with acid one or both sides with a soft or intense mordant. Also as indicated above, it is possible to provide protective coatings of or comprising DLC on one or both surfaces of a glass substrate. That is, it has been surprisingly and unexpectedly discovered that the arrangement of a layer comprising DLC to a gently corroded glass substrate on the acid etched side
IMPI »;
MEXICAN PROPERTY INSTITUTE greatly improves scratch resistance<sup>I</sup>’<sup>UST</sup>Sfta p &? Ee · of the reason this is surprising or · <sup>1</sup> iaeapetfade ea that the arrangement of a layer comprising DLC on an intensely corroded side of a glass substrate does not result in a significant improvement. Both the topology of the underlying substrate surface and the hard coating disposed thereon are believed to affect scratch resistance. The smoother peaks of gently corroded glass thus help to provide better coating coverage as well as overall scratch resistance.
In certain exemplary embodiments, an optional diffusion or barrier layer can be provided on the corroded surface. As alluded to above, this optional barrier or diffusion layer can help reduce the likelihood of sodium migration from the glass substrate within the layer comprising DLC. The optional diffusion or barrier layer can also help adhere the DLC-comprising layer to the substrate and / or can serve as index matching characteristics.
Figure 14 is a schematic cross-sectional view of a coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention. As shown in Figure 14, a glass substrate 1 has a
<img file="MX338872B_D0045.tif" />
MEXICAN INSTITUTE Vj;
surface gently corroded Id. This superS ^^^ í ^ r gently Id may be the air side of substrate 1 in certain exemplary embodiments, although the tin side may be additionally or alternatively corroded in different exemplary embodiments. The smoothly corroded surface Id supports one or more optional dielectric materials 6, as well as the protective layer comprising DLC 11. When the coated article of the Figure is to be used in its annealed state, protective outer covering layers are not necessary. However, in certain exemplary modalities, a TPF can be applied on top of the layer comprising DLC 11 in certain other exemplary modalities.
Figure 15 is similar to Figure 14, except that Figure 15 is a schematic cross-sectional view of a heat treatable coated article having a silky smooth appearance and improved scratch resistance in accordance with certain exemplary embodiments of this invention. The removable, protective outer covering film 17 may include, for example, the release layer (s) 17a and the oxygen barrier layer (s) 17b as discussed above. For example, in certain exemplary embodiments, the release layer 17a may include an inclusive zinc layer (eg, zinc oxide, zinc nitride or £
of.____.____ _ . ,
MEXICANC; S INSTITUTE OF PROPERTY! · INDUSTRIAL 'aluminum, nitride
<img file="MX338872B_D0046.tif" />
«WcrtTl ΪΤΟ MEXICANO zinc oxynitride) and the barrier layer include aluminum (eg aluminum oxide or aluminum oxynitride).
In certain exemplary embodiments, the optional dielectric layer 6 can assist by serving as a barrier (eg, for migration blocking effects), while also improving the optical and / or adhesion characteristics of the coated article. An inclusive layer of silicon or other high index material that is neutral in color (or imparts color neutrality to annealed or heat treated articles) can be used. Silicon nitride, silicon oxide, silicon oxynitride, hafnium oxide and / or other materials can be used for optional dielectric layer 6.
In the embodiment of Figure 15, as in the embodiments described above, the optional dielectric layer 6 may, for example, be 1-500 nm thick, more preferably 5-300 nm thick, and even more preferably 15 -150 nm thick. In the embodiment of Figure 15, as in the embodiments described above, the inclusive layer of DLC 11 may be, for example, 1-25 nm thick, more preferably 3-10 nm thick, and sometimes about 5 nm thick. In the embodiment of Figure 15, as in the embodiments described above, the layer of IMPI peeling 17a can be, for example
DE LA MONEDAD • industrial thickness, more preferably 100-30U nm thick and sometimes approximately 150 nm thick. In the embodiment of Figure 15, as in the embodiments described above, the oxygen barrier layer 17b may, for example, be 20-100 nm thick, more preferably 35-75 nm thick, and sometimes about 50 nm thick.
Similar to the above, a TPF material can be applied and removed before or as a result of heat treatment. Also similar to the above, the protective film 17 can be removed by heat treatment, for example, such that at least a portion of the DLC inclusive layer 11 is exposed as an outer layer of the coated article after of heat treatment.
Please note that the steps outlined in this document may be performed by one or more different parties. For example, the part that provides a matte finish glass substrate may or may not be the same part as the part that supplies the DLC inclusive protective coating and / or the part that performs the heat treatment. In certain exemplary embodiments, one part can acid etch a substrate, a second part can provide the protective coating
<img file="MX338872B_D0047.tif" />
IMPI 61
INSTITUTO MEXICANO inclusive of DLC and a third party thermally raSaS this intermediate part. Other comhinaHnnpg actors are also covered in this document.
While the invention has been described in relation to what is currently considered to be the most practical and preferred embodiments, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements that are included within the spirit and scope of the appended claims.
1.
IMPI
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL
<img file="MX338872B_D0048.tif" />
Contents36
56 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56
83 members in 9 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 13174310 | United States of America | – | |
| 201113174310 | United States of America | A | |
| 2012043498 | United States of America | W | |
| 13174310 | – | – | – |
| US1243498 | – | – | – |
| US201113174310 | – | – | – |
| WO2012US43498 | – | – | – |
Members83
| Document | Office | Kind | |
|---|---|---|---|
| US2008178632A1 | United States of America | A1 | |
| US2008182032A1 | United States of America | A1 | |
| US2008182033A1 | United States of America | A1 | |
| US2008182123A1 | United States of America | A1 | |
| CA2673609A1 | Canada | A1 | |
| WO2008094382A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2008199702A1 | United States of America | A1 | |
| CA2684411A1 | Canada | A1 | |
| WO2008143756A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2008147488A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2008150328A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2009123654A1 | United States of America | A1 | |
| WO2009067133A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2109592A1 | European Patent Office (EPO) | A1 | |
| EP2146937A1 | European Patent Office (EPO) | A1 | |
| EP2152643A1 | European Patent Office (EPO) | A1 | |
| EP2155623A1 | European Patent Office (EPO) | A1 | |
| WO2010024960A1 | World Intellectual Property Organization (WIPO) | A1 | |
| MX2010005478A | Mexico | A | |
| EP2220007A1 | European Patent Office (EPO) | A1 | |
| US7833574B2 | United States of America | B2 | |
| US2011027471A1 | United States of America | A1 | |
| US2011027595A1 | United States of America | A1 | |
| RU2009132524A | Russian Federation | A | |
| US7914857B2 | United States of America | B2 | |
| EP2323956A1 | European Patent Office (EPO) | A1 | |
| US7964238B2 | United States of America | B2 | |
| RU2009146824A | Russian Federation | A | |
| RU2009148839A | Russian Federation | A | |
| US8003167B2 | United States of America | B2 | |
| US8071166B2 | United States of America | B2 | |
| RU2010125209A | Russian Federation | A | |
| US2012015195A1 | United States of America | A1 | |
| US2012015196A1 | United States of America | A1 | |
| US2012040160A1 | United States of America | A1 | |
| SA08290732B1 | Saudi Arabia | B1 | |
| SA2880B1 | Saudi Arabia | B1 | |
| US2012052212A1 | United States of America | A1 | |
| US8132426B2 | United States of America | B2 | |
| US2012137734A1 | United States of America | A1 | |
| CA2684411C | Canada | C | |
| US8221832B2 | United States of America | B2 | |
| RU2459772C2 | Russian Federation | C2 | |
| RU2459773C2 | Russian Federation | C2 | |
| RU2011111692A | Russian Federation | A | |
| RU2469002C2 | Russian Federation | C2 | |
| WO2013003130A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2013003186A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2013003188A1 | World Intellectual Property Organization (WIPO) | A1 | |
| RU2471732C2 | Russian Federation | C2 | |
| US8354178B2 | United States of America | B2 | |
| US2013111954A1 | United States of America | A1 | |
| WO2013003130A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US8440255B2 | United States of America | B2 | |
| US8443627B2 | United States of America | B2 | |
| CA2673609C | Canada | C | |
| US8580336B2 | United States of America | B2 | |
| MX2013015029A | Mexico | A | |
| MX2013015030A | Mexico | A | |
| EP2726286A2 | European Patent Office (EPO) | A2 | |
| EP2726429A1 | European Patent Office (EPO) | A1 | |
| BRPI0808380A2 | Brazil | A2 | |
| BRPI0812117A2 | Brazil | A2 | |
| BRPI0812283A2 | Brazil | A2 | |
| BRPI0812789A2 | Brazil | A2 | |
| BRPI0819294A2 | Brazil | A2 | |
| RU2014102992A | Russian Federation | A | |
| RU2014102993A | Russian Federation | A | |
| BRPI0917132A2 | Brazil | A2 | |
| MX338872BThis record | Mexico | B | |
| BR112013033594A2 | Brazil | A2 | |
| BR112013033741A2 | Brazil | A2 | |
| EP2109592B1 | European Patent Office (EPO) | B1 | |
| RU2633009C2 | Russian Federation | C2 | |
| RU2635312C2 | Russian Federation | C2 | |
| PL2109592T3 | Poland | T3 | |
| BRPI0808380B1 | Brazil | B1 | |
| BRPI0812117B1 | Brazil | B1 | |
| EP2146937B1 | European Patent Office (EPO) | B1 | |
| MX366254B | Mexico | B | |
| EP2726286B1 | European Patent Office (EPO) | B1 | |
| PL2146937T3 | Poland | T3 | |
| PL2726286T3 | Poland | T3 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 338872
- Publication, DOCDB
- 338872
- Publication, EPODOC
- MX338872
- Application
- 2013015030
- Application, DOCDB
- 2013015030
- Application, EPODOC
- MX202013015030
Titles2
- English
- METHOD OF MAKING HEAT TREATED AND ION-BEAM ETCHED/MILLED COATED ARTICLE USING DIAMOND-LIKE CARBON (DLC) PROTECTIVE FILM.
- Spanish
- METODO PARA HACER UN ARTICULO RECUBIERTO TRATADO TERMICAMENTE Y ATACADO/MOLIDO CON HAZ DE IONES UTILIZANDO UNA PELICULA PROTECTORA DE CARBON TIPO DIAMENTE (DLC).
Classification
- CPC, 24
- C03C17/3441
- C03C17/22
- C03C15/00
- C03C17/27
- C03C2217/22
- C03C2217/282
- C03C2217/77
- C03C2217/78
- C03C2217/91
- C03C2218/15
- C03C2218/31
- C03C2218/322
- C03C2218/328
- C03C2218/33
- C03C2218/355
- C03C2218/36
- Y10T428/2495
- Y10T428/265
- B05D3/104
- C03C15/02
- C03C17/225
- C03C17/23
- C03C17/3411
- C03C23/0055