COATED GLASS SUBSTRATE OR GLASS CERAMIC SUBSTRATE WITH RESISTANT MULTIFUNCTIONAL SURFACE PROPERTIES, METHOD FOR PRODUCTION THEREOF, AND USE OF THEREOF

Abstract

The invention relates to a coated glass substrate or glass ceramic substrate with resistant, multi-functional surface properties, including a combination of anti-microbial, anti-reflective and anti-fingerprint properties, or a combination of anti-microbial, anti-reflective and anti-fingerprint properties where the substrate is chemically pre-stressed, or a combination of anti-microbial and anti-reflective properties where the substrate is chemically pre-stressed. The coated glass substrate or glass ceramic substrate exhibits a unique combination of functions which are permanently present and do not exert a negative effect on each other.

Claims

1. A coated glass or glass ceramic substrate with resistant multifunctional surface properties, comprising: a glass or glass ceramic substrate; and a coating including at least one layer applied to said substrate, wherein said coated glass or glass ceramic substrate one of: displays a combination of antimicrobial, antireflective, and anti-fingerprint properties; displays a combination of antimicrobial, antireflective, and anti-fingerprint properties, wherein said coated glass or glass ceramic substrate is chemically prestressed; and displays a combination of antimicrobial and antireflective properties, wherein said coated glass or glass ceramic substrate is chemically prestressed.

2. The coated substrate according to claim 1, wherein said coated glass or glass ceramic substrate incorporates at least one antimicrobially effective metal ion therein, said chemical prestressing is produced through an ion exchange, and said coating includes an antireflective coating including at least one antireflective layer applied to said glass or glass ceramic substrate and an anti-fingerprint coating including at least one anti-fingerprint layer applied to said at least one antireflective layer.

3. The coated substrate according to claim 1, wherein said coated glass or glass ceramic substrate also displays antiglare properties.

4. The coated substrate according to claim 2, wherein said antireflective coating consists of one of: one antireflective layer which is an adhesion promoting layer; at least two antireflective layers with alternating high refractive index and low refractive index layers, wherein an uppermost layer is a low refractive index layer and an adhesion promoting layer; and at least three antireflective layers with alternating medium refractive index, high refractive index, and low refractive index layers, wherein an uppermost layer is a low refractive index layer and an adhesion promoting layer.

5. The coated substrate according to claim 4, wherein said antireflective coating one of: consists of one antireflective layer and has a refractive index in the range of 1.22 to 1.44; and includes a plurality of antireflective layers, said uppermost layer having a refractive index in the range of 1.22 to 1.70.

6. The coated substrate according to claim 4, wherein said antireflective coating comprises a plurality of antireflective layers and said uppermost layer is subdivided into at least one intermediate layer having substantially the same refractive index as one or more layers between said uppermost layer and said substrate.

7. The coated substrate according to claim 2, wherein said antireflective coating is an incomplete antireflective coating, said incomplete antireflective coating being configured to only form a complete antireflective effect in the spectral range in combination with at least one of an adhesion promoting layer and said at least one anti-fingerprint layer.

8. The coated substrate according to claim 2, wherein said adhesion promoting layer is a mixed oxide layer.

9. The coated substrate according to claim 8, wherein said mixed oxide layer is a silicon mixed oxide layer comprising an oxide of at least one of: aluminum, zinc, magnesium, phosphorus, cerium, zircon, titanium, cesium, barium, strontium, niobium, tin, boron, and magnesium fluoride and has a thickness greater than 1 nm.

10. The coated substrate according to claim 1, wherein said substrate is an alkali-aluminosilicate glass comprising the following in weight-%: TABLE-US-00015 SiO.sub.2 40-75;  Al.sub.2O.sub.3 10-30;  B.sub.2O.sub.3 0-20; Sum of Li.sub.2O + Na.sub.2O + K.sub.2O 4-30; Sum of MgO + CaO + SrO + BaO + ZnO 0-15; Sum of TiO.sub.2 + ZrO.sub.2  .sup.   0-15; and P.sub.2O.sub.5 0-10.

11. The coated substrate according to claim 1, wherein said substrate is a borosilicate glass comprising the following in weight-%: TABLE-US-00016 SiO.sub.2 60-85;  Al.sub.2O.sub.3 1-10; B.sub.2O.sub.3 5-20; Sum of Li.sub.2O + Na.sub.2O + K.sub.2O 2-16; Sum of MgO + CaO + SrO + BaO + ZnO 0-15; Sum of TiO.sub.2 + ZrO.sub.2  .sup. 0-5; and P.sub.2O.sub.5 0-2. 

12. The coated substrate according to claim 1, wherein said substrate is a soda-lime glass comprising the following in weight-%: TABLE-US-00017 SiO.sub.2 40-80; Al.sub.2O.sub.3 0-6; B.sub.2O.sub.3 0-5; Sum of Li.sub.2O + Na.sub.2O + K.sub.2O  5-30; Sum of MgO + CaO + SrO + BaO + ZnO  5-30; Sum of TiO.sub.2 + ZrO.sub.2  .sup.   0-7; and P.sub.2O.sub.5 0-2.

13. The coated substrate according to claim 1, wherein said substrate is a low alkali aluminosilicate glass comprising the following in weight-%: TABLE-US-00018 SiO.sub.2 50-75;  Al.sub.2O.sub.3 7-25; B.sub.2O.sub.3 0-20; Sum of Li.sub.2O + Na.sub.2O + K.sub.2O 1-4;  Sum of MgO + CaO + SrO + BaO + ZnO 5-25; Sum of TiO.sub.2 + ZrO.sub.2  .sup.   0-10; and P.sub.2O.sub.5 0-5. 

14. The coated substrate according to claim 1, wherein said substrate is a lead glass comprising the following in weight-%: TABLE-US-00019 PbO 20-80;  SiO.sub.2 20-60;  K.sub.2O 0-10; Na.sub.2O 1-10; BaO 0-20; SrO 0-20; Al.sub.2O.sub.3 0-10; CaO 0-10; F.sub.2O.sub.3 0-1;  Sb.sub.2O.sub.3 0-1;  ZnO 0-20; B.sub.2O.sub.3  .sup.   0-20; and ZrO.sub.2 0-10.

15. The coated substrate according to claim 1, wherein said substrate is a glass comprising the following in weight-%: TABLE-US-00020 SiO.sub.2 10-90;  Al.sub.2O.sub.3 0-40; B.sub.2O.sub.3 0-80; Na.sub.2O 1-30; K.sub.2O 0-30; CoO 0-20; NiO 0-20; Ni.sub.2O.sub.3 0-20; MnO 0-20; CaO 0-40; BaO 0-60; ZnO 0-40; ZrO.sub.2 0-10; MnO.sub.2 0-10; CeO 0-3;  SnO.sub.2 0-2;  Sb.sub.2O.sub.3 0-2;  TiO.sub.2 0-40; P.sub.2O.sub.5 0-70; MgO 0-40; SrO 0-60; Li.sub.2O 0-30; Li.sub.2O + Na.sub.2O + K.sub.2O 1-30; SiO.sub.2 + B.sub.2O.sub.3 + P.sub.2O.sub.5 10-90;  Nd.sub.2O.sub.5 0-20; V.sub.2O.sub.5 0-50; Bi.sub.2O.sub.3 0-50; SO.sub.3  .sup.   0-50; and SnO 0-70, wherein the content of SiO.sub.2+P.sub.2O.sub.5+B.sub.2O.sub.3 is 10-90 is weight-%.

16. The coated substrate according to claim 1, wherein said substrate is a lithium-aluminum-silicate glass comprising the following in weight-%: TABLE-US-00021 SiO.sub.2 55-69; Al.sub.2O.sub.3 19-25; Li.sub.2O 3-5; Sum of Na.sub.2O + K.sub.2O 0.5-15;  Sum of MgO + CaO + SrO + BaO 0-5; ZnO 0-4; TiO.sub.2 0-5; ZrO.sub.2 0-3; Sum of TiO.sub.2 + ZrO.sub.2 + SnO.sub.2 2-6; P.sub.2O.sub.5 0-8; F  .sup.   0-1; and B.sub.2O.sub.3 0-2.

17. The coated substrate according to claim 1, wherein said substrate is a glass and contains at least one of a coloring oxide, a rare earth oxide, and a refining agent.

18. The coated substrate according to claim 1, wherein said substrate is a glass ceramic or ceramizable glass with a starting glass comprising the following in weight-%: TABLE-US-00022 Li.sub.2O 3.2-5.0;.sup.  Na.sub.2O 0-1.5; K.sub.2O 0-1.5; Sum Na.sub.2O + K.sub.2O 0.2-2.0;.sup.  MgO 0.1-2.2;.sup.  CaO 0-1.5; SrO 0-1.5; BaO 0-2.5; ZnO 0-1.5; Al.sub.2O.sub.3 19-25;.sup.  SiO.sub.2 55-69;.sup.  TiO.sub.2 1.0-5.0;.sup.  ZrO.sub.2 1.0-2.5;.sup.  SnO.sub.2 0-1.0; Sum TiO.sub.2 + ZrO.sub.2 + SnO.sub.2  2.5-5.0; and P.sub.2O.sub.5 0-3.0.

19. The coated substrate according to claim 1, wherein said substrate is a glass ceramic or ceramizable glass with a starting glass comprising the following in weight-%: TABLE-US-00023 Li.sub.2O 3-5; Na.sub.2O .sup. 0-1.5; K.sub.2O .sup. 0-1.5; Sum Na.sub.2O + K.sub.2O 0.2-2;.sup.  MgO 0.1-2.5; CaO 0-2; SrO 0-2; BaO 0-3; ZnO .sup. 0-1.5; Al.sub.2O.sub.3 15-25; SiO.sub.2 50-75; TiO.sub.2 1-5; ZrO.sub.2 .sup. 1-2.5; SnO.sub.2 .sup. 0-1.0; Sum TiO.sub.2 + ZrO.sub.2 + SnO.sub.2  2.5-5; and P.sub.2O.sub.5 .sup. 0-3.0.

20. The coated substrate according to claim 1, wherein said substrate is a glass ceramic or ceramizable glass with a starting glass comprising the following in weight-%: TABLE-US-00024 Li.sub.2O 3-4.5; Na.sub.2O 0-1.5; K.sub.2O 0-1.5; Sum Na.sub.2O + K.sub.2O 0.2-2;    MgO 0-2;.sup.  CaO 0-1.5; SrO 0-1.5; BaO 0-2.5; ZnO 0-2.5; B.sub.2O.sub.3 0-1;.sup.  Al.sub.2O.sub.3 19-25;.sup.  SiO.sub.2 55-69;.sup.  TiO.sub.2 1.4-2.7;.sup.  ZrO.sub.2 1.3-2.5;.sup.  SnO.sub.2 0-0.4; Sum TiO.sub.2 + SnO.sub.2 less than 2.7; P.sub.2O.sub.5  0-3; and Sum ZrO.sub.2 + 0.87 (TiO.sub.2 + SnO.sub.2) 3.6-4.3..sup. 

21. The coated substrate according to claim 1, wherein said substrate is a glass ceramic containing high quartz mixed crystals or keatite mixed crystals as the predominant crystals phase and a crystal size is less than 70 nm.

22. The coated substrate according to claim 1, wherein said substrate has a textured surface.

23. The coated substrate according to claim 1, wherein said substrate is an alumino silicate glass or a glass-ceramic based upon an alumino silicate glass and is chemically prestressed such that said substrate has a compressive stress CS≧600 MPa and a depth of a compressive stress layer DoL≧20 μm.

24. The coated substrate according to claim 1, wherein said substrate is a soda-lime glass or a glass-ceramic based upon a soda-lime glass and is chemically prestressed such that said substrate has a compressive stress CS≧100 MPa and a depth of a compressive stress layer DOL≧5 μm.

25. The coated substrate according to claim 1, wherein said coated glass or glass ceramic substrate has an antimicrobial effectiveness of >90% against E. coli and S. aureus.

26. The coated substrate according to claim 1, wherein a thickness of said substrate is ≦20 mm.

27. A method of producing a coated glass or glass ceramic substrate with resistant multifunctional surface properties, comprising: applying an antireflective coating onto a glass or glass ceramic substrate; and immersing said glass or glass ceramic substrate with said antireflective coating in a salt bath such that an ion exchange occurs between said glass or glass ceramic substrate with said antireflective coating and said salt bath, wherein, in said immersing, one of: said salt bath contains at least one antimicrobial metal salt to provide said glass or glass ceramic substrate with antimicrobial properties; said salt bath contains at least one of potassium, rubidium, and cesium and at least one antimicrobial metal salt to provide said glass or glass ceramic substrate with antimicrobial properties and chemically prestress said glass or glass ceramic substrate at the same time; and said immersing comprises firstly immersing said glass or glass ceramic substrate in a first salt bath containing at least one of a potassium salt, a rubidium salt, and a cesium salt and secondly immersing said glass or glass ceramic substrate in a second salt bath containing at least one of a potassium salt, a rubidium salt, and a cesium salt and at least one antimicrobial metal salt to provide said glass or glass ceramic substrate with antimicrobial properties and chemically prestress said glass or glass ceramic substrate.

28. The method according to claim 27, wherein said at least one antimicrobial metal salt includes a metal salt of at least one of: silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium, and nickel.

29. The method according to claim 27, wherein said salt bath has a temperature between 350 and 500° C. and said immersing is for a duration between 0.5 and 48 hours.

30. The method according to claim 27, wherein said first salt bath has a temperature between 350 and 500° C. and said firstly immersing is for a duration between 0.5 and 48 hours, and said second salt bath has a temperature between 400 and 500° C. and said secondly immersing is for a duration between 0.25 and 2 hours.

31. The method according to claim 27, wherein said at least one antimicrobial metal salt is between 0.01 and 2 weight-% of said salt bath.

32. The method according to claim 27, wherein said applying comprises liquid phase coating and said glass or glass ceramic substrate is thermally tempered prior to said applying.

33. The method according to claim 32, wherein said liquid phase coating comprises Sol-Gel coating.

34. The method according to claim 27, further comprising the step of applying an anti-fingerprint coating onto an antireflective surface of said glass or glass ceramic substrate with said antireflective coating.

35. The method according to claim 34, wherein said anti-fingerprint coating is applied by at least one of thermal vacuum deposition, sputtering, liquid phase coating, spraying, dip coating, printing, rolling, and spin coating.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0177] The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:

[0178] FIG. 1 is a schematic illustration of one embodiment of a method in accordance with the present invention;

[0179] FIG. 2 is a schematic illustration of an embodiment of a glass or glass ceramic substrate with antireflective coating in the form of 3 layers formed in accordance with the present invention;

[0180] FIG. 3 is a schematic illustration of an embodiment of a glass or glass ceramic substrate with antireflective coating in the form of 4 layers formed in accordance with the present invention;

[0181] FIG. 4 is a schematic illustration of an embodiment of a glass or glass ceramic substrate with an antireflective coating in the form of a single layer which is an adhesion promoting layer formed in accordance with the present invention;

[0182] FIG. 5 is an illustration of the comparison of the various transmissions (in %), applied against the wavelength (in nm) of an untreated glass substrate, an antireflective coated glass substrate prior to ion exchange, as well as the glass substrate produced in accordance with one embodiment of a method of the present invention;

[0183] FIG. 6 is an illustration for comparison of the various transmissions (in %), applied against the wavelength (in nm) of an untreated glass substrate, as well as a glass substrate produced in accordance with another embodiment of a method of the present invention;

[0184] FIG. 7 is an illustration for comparison of the reflections (in %), applied against the wavelength (in nm) of a glass substrate produced according yet another embodiment of a method of the present invention, before and after ion exchange;

[0185] FIG. 8 is an illustration for comparison of the reflections (in %), applied against the wavelength (in nm) of a glass substrate produced according to yet another embodiment of a method of the present invention, before and after ion exchange;

[0186] FIG. 9 is an illustration for comparison of the various transmissions (in %), applied against the wavelength (in nm) of an untreated glass substrate, as well as a glass substrate produced in accordance with yet another embodiment of a method of the present invention; and

[0187] FIG. 10 is an illustration for comparison of the various transmissions (in %), applied against the wavelength (in nm) of an untreated glass substrate, as well as a glass substrate produced in accordance with yet another embodiment of a method of the present invention.

[0188] Corresponding reference characters indicate corresponding parts throughout the several views. The exemplification set out herein illustrate embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.

DETAILED DESCRIPTION OF THE INVENTION

[0189] FIG. 1 schematically illustrates one exemplary embodiment of a method according to the present invention. Here, a glass or glass ceramic substrate 2 is provided with a surface 20—which first of all is cleaned if necessary—onto which an antireflective coating is applied. Depending on the specific embodiment, the coating may also be applied on both surfaces (not illustrated) of the glass or glass ceramic substrate 2. The antireflective coating can be an arbitrary coating with antireflective properties. It may, for example, consist of one layer, at least 2 layers with alternating high and low refractive index, or at least 3 layers with alternating medium, high and low refractive index. In the illustrated examples, the antireflective coating is composed of one individual layer 5 (FIG. 4) or of at least 2 layers 3 and 4 (FIGS. 2 and 3) with high and low refractive index, wherein the outer or top layer 31, 41, 5 of the layer package has a low refractive index. According to one embodiment, layer 31, 41, 5 can be an adhesion promoting layer. The adhesion promoting layer can be a mixed oxide layer, such as a silicon mixed oxide layer.

[0190] The glass or glass ceramic substrate 2 that is provided with the antireflective coating is subjected to an ion exchange. Herein provision is made in accordance with one of the exemplary embodiments for either only antimicrobial properties or antimicrobial properties and chemical prestressing. Metal salts with antimicrobial effect are, for example, silver-, copper-, cadmium-, zinc-, iron-, tin-, cobalt-, cerium-, antimony-, selenium-, chromium-, magnesium- and nickel salts. For chemical prestressing, any suitable compounds can be used. Conventionally, potassium-, rubidium- and/or cesium salts are used. Provision of glass or glass substrate 2 with antimicrobial properties and chemical prestressing can be performed in one or two steps. If this is to be performed in one step, the metal salts that are suitable for chemical prestressing and the antimicrobial effective metal salts are mixed together in a salt bath and glass or glass ceramic substrate 2 is dipped into the salt bath. If this process is to be performed in two steps, then chemical prestressing can occur in a first step in a first salt bath and provision of the antimicrobial properties can occur only in a second step in a second salt bath. The second salt bath can contain a mixture of potassium-, rubidium- and/or cesium salt with one or several metal salts with antimicrobial effect. The ion exchange is performed through the antireflective coating, so that the entire substrate with the layer, or layers thereupon, is captured (this is expressed with the bracket in FIG. 1).

[0191] Following the ion exchange process or processes, an anti-fingerprint coating 6 can be applied to coated glass or glass ceramic substrate 2 that is equipped with antimicrobial properties and is chemically prestressed, if required. FIG. 2 is a schematic illustration of one exemplary embodiment of a glass or glass ceramic substrate 2 formed in accordance with the present invention with an antireflective coating in the form of 3 layers. Layer 33 has a medium refractive index (M-layer), layer 32 has a high refractive index (T-layer) and layer 31 has a low refractive index (S-layer). Layer 31 can be an adhesion promoting layer. Prior to the application of the antireflective coating, it can be useful to clean surface 20 of substrate 2. Glass or glass substrate 2 in the illustrated examples has antimicrobial properties and is chemically prestressed.

[0192] The production of such antireflective coating is explained in further detail herein with reference to the examples.

[0193] FIG. 3 is a schematic illustration of an additional embodiment of a glass or glass ceramic substrate 2 with an antireflective coating in the form of 4 layers (41, 42, 43, 44). The 4 layers have alternating high and low refractive indexes and together form the antireflective coating. Top layer 41 can be an adhesion promoting layer. In the illustrated example, glass or glass ceramic substrate 2 with coating 4 has antimicrobial properties and is chemically prestressed.

[0194] FIG. 4 is a schematic illustration of another embodiment of a glass or glass ceramic substrate 2 formed in accordance with the present invention with antireflective coating in the form of a single layer 5. This layer can be an adhesion promoting layer. Glass or glass ceramic substrate with the single layer has antimicrobial properties in the illustrated example and is chemically prestressed. Production of such a substrate is described further herein.

[0195] FIGS. 5 to 10 are individually discussed with the examples.

[0196] The present invention offers a special combination of characteristics that are simultaneously and durably integrated into a glass or glass ceramic substrate. The glass or glass ceramic substrates formed in accordance with the present invention, with durable multifunctional surface properties comprise antimicrobial, antireflective and anti-fingerprint functions, or a combination of antimicrobial, antireflective and anti-fingerprint functions, whereby the substrate is chemically prestressed, or a combination of antimicrobial and antireflective functions, whereby the substrate is chemically prestressed. A method to produce such a substrate is also an embodiment of the present invention.

[0197] The present invention provides characteristic combinations that, in this manner, have not been known previously in the art, wherein however each individual property or function is not negatively influenced by an additional property or function, but which instead complement each other and wherein each property is available to the full extent.

[0198] It was found that with simultaneous antimicrobial provision and chemical prestressing, values for the compressive stress (CS) of the surface and the depth of the compressive stress layer DoL (depth of ion exchanged layer) are maintained which are in the same range as for glasses or glass ceramics that were chemically prestressed through ion exchange, without providing them simultaneously with antimicrobial properties.

[0199] The presence of an AF coating has no negative influence upon the release of the ions from the glass or glass ceramic surface that provide an antimicrobial effect, so that the antimicrobial properties can develop fully and uninhibited. The application of an AF layer onto an AR coating moreover leads to an improvement of the abrasion resistance of the entire coating system.

[0200] The glass and glass ceramic substrates formed according to the present invention can be used everywhere where the characteristics combination in the form of high strength, antireflective behavior and antimicrobial properties as well as anti-fingerprint properties, if required, are useful and/or necessary.

[0201] The glass or glass ceramic substrate formed in accordance with the present invention can be used, for example, as cover glasses for all forms of touch screens of electronic devices and many devices in the home or in the industrial field, for example for mobile phones, smart phones, tablet-PCs, notebook PCs, TVs, ATMs, ticket machines and also for control-, information- and/or operating boards or windows in any possible shape and size as used for example in motor vehicles, hospitals, museums, shops, home building and transportation.

[0202] The substrates formed according to the present invention can be used in applications where many functions are integrated together, for example in touch screens of smart phones or tablet PCs. For this purpose, the substrates are chemically prestressed, have an AR and AF coating and possess antimicrobial properties: In this case the glass substrate according to the invention can be chemically prestressed so that the very thin glass substrates that are used in touch screens have a sufficiently high mechanical strength. In addition to avoiding disturbing or contrast reducing reflections, the AR coating provides the possibility of energy savings since, due to a reduction in the reflection at the glass/air interface, the display module can be operated with reduced brightness. The antimicrobial feature of the glass surface protects the user who is continuously in direct contact with the glass surface from bacteria that are present on the surface. Finally, the anti-fingerprint properties of the glass surface are very useful, because the appearance of the glass is improved and the screen is easier to clean. The described functions can be provided, in particular, with long-term durability.

[0203] The glass or glass ceramic substrates formed according to the present invention therefore, provide the surface with all functions in a durable manner, so that current industrial standards are met. The exemplary methods according to the present invention are suitable for mass production.

[0204] The present invention is explained below in further detail with reference to the examples, without being limited thereto:

Example 1

Glass Substrate: Soda-Lime Floated Glass

[0205] A carefully cleaned 100×200 mm soda-lime float glass was coated with an antireflective coating that was composed of a three-layer structure as illustrated in FIG. 2. The antireflective coating consisted of three layers with the following structure: glass substrate (2)+M-layer (33)+T-layer (32)+S-layer (31). S-layer (31) was at the same time an adhesion promoting layer. The three layers were applied onto the glass by dip coating.

[0206] The solutions for the three layers were produced as follows:

S-Layer:

Pre-Solution

[0207] A mixture of 60 ml TEOS and 125 ml ethanol was stirred for 15 minutes. Then, 30 ml distilled water and 12 ml 1 N nitric acid were added. After stirring for 5 minutes the solution was diluted with 675 ml ethanol.

(This Pre-Solution was Used for the M-Layer)

Mixed Oxide Solution:

[0208] In order to achieve the adhesion promoting layer properties, 10.9 g Al(NO.sub.3).sub.3.9H.sub.2O, dissolved in 95 ml ethanol, and 5 ml acetyl-acetonide, was added after 24 hours to the pre-solution.

T-Layer:

[0209] 68 ml titanium-n-butoxide, 918 ml ethanol (absolute), 5 ml acetylacetone and 9 ml ethyl-butyl-acetate were added and stirred for 2 hours.

M-Layer:

[0210] The coating solutions for the production of the M-layer with a medium refractive index were produced by mixing the S-pre-solution and the T-solution. The M-layer solution comprises a mixture of S- and T-solutions at a ratio to the weight-% of the oxides of 75:25.

[0211] The individual layers of example 1 were applied in separate dipping steps. The glass material was dipped into the dipping solution. Then it was pulled out at a rate of 6 mm/sec., whereby the moisture content of the ambient atmosphere was between 5 g/m.sup.3 and 12 g/m.sup.3, such as 8 g/m.sup.3. The solvent was then evaporated then at 90 to 100° C. The coated layer was then hardened at a temperature of 450° C. for 20 minutes.

[0212] The sample provided with the AR coating in the Sol-Gel method was subsequently dipped into a KNO.sub.3 salt bath that contained 0.01 weight-% AgNO.sub.3 and was treated for one hour at 430° C.

[0213] Then, the ion-exchanged AR coated sample was coated on one side with an AF coating by a liquid printing technology. AF coating solutions are products that are based on polyfluoro-polyethers known under the tradename “Fluorolink® PFPE”, for example “Fluorolink®S10” by Solvay Solexis or “Optool DSX™” or “Optool™ AES4-E” by Daikin Industries Ltd.

[0214] The glass substrate thus produced according to example 1 has an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0215] For comparison purposes, the measured transmissions of the uncoated soda-lime substrate, the AR coated substrate before the ion exchange and the substrate that was produced according to example 1 are illustrated in FIG. 5.

[0216] FIG. 5 shows a clear increase in the transmission of the glass substrate formed in accordance with the present invention that was maintained despite the various functionalities of the glass surface.

[0217] The compressive stress (CS) of the obtained glass substrate according to example 1 was 332 MPa and the DoL (depth of ion exchanged layer) was 5.3 μm.

[0218] The antimicrobial effectiveness of the glass substrate according to example 1 on its AF coated surface was >99.9% against E. coli and also S. aureus.

[0219] The water contact angle of the AF coated surface of the glass substrate from example 1 was 112° C. The resistance of the glass substrate was examined in the neutral salt spray test. After the glass substrate was subjected for 10 weeks to water and sodium chloride at 35° C., the measured water contact angle was still 105°. This confirms that the durability of the applied coating on the glass substrate is very high.

Example 2

Glass Substrate: Aluminosilicate Glass

[0220] A carefully cleaned 100×60×0.5 mm aluminosilicate glass was coated with an antireflective coating that was a single-layer structure as illustrated in FIG. 4. The single AR layer was at the same time an adhesion promoting layer.

[0221] The solution for the single layer was produced as follows:

[0222] 100 ml TEOS was mixed with 200 ml ethyl alcohol and 15 ml 0.1 N HCl. The mixture was stirred for 3 hours at 40° C. The solution was then diluted with 300 ml ethyl alcohol and 16 g Al(NO.sub.3).sub.3.9H.sub.2O was also added and stirring was continued for an additional half hour. After maturing the solution for 24 hours at room temperature, the solution was used as dip solution.

[0223] The substrate glass was coated with the aforementioned solution on both sides in a dip coating process. The removal speed of the substrate from the liquid was 9 mm/min. The fresh coating was preheated for 2 minutes at 200° C. and the coated glass substrate was then tempered at 450° C. for 1 hour.

[0224] The coated glass substrate was then dipped into a salt bath for the ion exchange process that was conducted for 4 hours at a temperature of 430° C. The molten salt in the salt bath was KNO.sub.3, mixed with 0.02 weight-% AgNO.sub.3.

[0225] After the ion exchange the glass substrate was cleaned and an AF coating was applied by a conventional spray coating process.

[0226] The glass substrate produced according to example 2 has thus an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0227] The transmission of the untreated glass substrate in contrast to the glass substrate from example 2 is illustrated in FIG. 6.

[0228] FIG. 6 shows a high transmission of the glass substrate that was produced according to example 2 in contrast to the untreated glass substrate.

[0229] The compressive stress (CS) of the glass substrate according to example 2 was 840 MPa and the DoL was 35 μm.

[0230] The antimicrobial effectiveness of example 2 on its AF coated surface was >99.9% against E. coli and 99.5% against S. aureus.

[0231] The water contact angle on the AF coated surface of example 2 was 115°.

Example 3

[0232] Glass Substrate: A Glass with the Following Composition:

TABLE-US-00011 Composition Weight-% SiO.sub.2 58.1 Al.sub.2O.sub.3 19.7 Na.sub.2O 8.2 K.sub.2O 2.5 MgO 1.9 B.sub.2O.sub.3 9.6

[0233] A carefully cleaned 100×200×3 mm glass of above composition was coated with an antireflective coating consisting of three layers according to FIG. 2. The antireflective coating consisted of three layers with the following structure: glass substrate (2)+M-layer (33)+T-layer (32)+S-layer (31). The S-layer was at the same time an adhesion promoting layer. The three layers were applied onto the glass by means of dip coating.

[0234] The solutions for the three layers were produced as follows:

S-Layer:

Pre-Solution

[0235] A mixture of 60 ml TEOS and 125 ml ethanol was stirred for 15 minutes. Then, 30 ml distilled water and 12 ml 1 N nitric acid were added. After stirring for 10 minutes the solution was diluted with 750 ml ethanol. (This pre-solution was used for the M-layer)

Mixed Oxide Solution:

[0236] In order to achieve the adhesion promoting layer properties, 10.9 g Al(NO.sub.3).sub.3.9H.sub.2O, dissolved in 95 ml ethanol and 5 ml acetyl-acetonate, was added after 24 hours to the pre-solution.

T-Layer:

[0237] 109 g amorphous TiO.sub.2 powder was added into the solvent mixture consisting of 802 g ethanol and 89 g 1.5-pentanediol. The synthesis of the TiO.sub.2 powder was as follows: 1 mol titanium tetra-ethylate was mixed with 1 mol acetyl-acetone and was then hydrolyzed with 5 mol H.sub.2O. After removal of the solvent, the powder was dried for 5 hours at 125° C. The amorphous powder had a TiO.sub.2 content of approximately 58 weight-%.

M-Layer:

[0238] The coating solutions to produce the M-layer with a medium refractive index were produced by mixing the S-pre-solution and the T-solution. The M-layer solution can comprise a mixture of S- and T-solution at a weight ratio of the oxides of 65:35.

[0239] Subsequently, the glass substrate was then dipped into a salt bath to perform the ion exchange process that was conducted for 6 hours at a temperature of 420° C. The molten salt in the salt bath was KNO.sub.3, mixed with 0.02 weight-% AgNO.sub.3.

[0240] After the ion exchange the glass substrate was cleaned and an AF coating was applied by a conventional thermal vacuum deposition method.

[0241] The glass substrate thus produced per example 3 has an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0242] The compressive stress (CS) of the glass substrate per example 3 was 712 MPa and the DoL was 30 μm.

[0243] The antimicrobial effectiveness of the glass substrate per example 3 on its AF coated surface was >99% against E. coli and against S. aureus.

[0244] The water contact angle on the AF coated surface of example 3 was 115°.

[0245] The reflections of the glass substrate of example 3 before and after the ion exchange are illustrated in FIG. 7. FIG. 7 shows that the reflection of the glass substrate of example 3 is in fact not negatively influenced by the ion exchange.

Example 4

[0246] Glass Substrate: Soda-Lime Glass with the Following Composition:

TABLE-US-00012 Composition Weight-% SiO.sub.2 70 TiO.sub.2 0.3 Na.sub.2O 8.36 K.sub.2O 8.46 CaO 5.74 ZnO 4.53 BaO 2.11 Sb.sub.2O.sub.3 0.5

[0247] A carefully cleaned 100×200 mm soda-lime glass substrate was coated with an antireflective coating that was composed of three layers as illustrated in FIG. 2. The antireflective coating consisted of the following structure: glass substrate (2)+M-layer (33)+T-layer (32)+S-layer (31). S-layer (31) was at the same time an adhesion promoting layer. The three layers were applied onto the glass by dip coating.

[0248] The solutions for the three layers were produced as follows:

S-Layer:

[0249] A mixture of 45 ml TEOS and 125 ml ethanol was stirred for 15 minutes. Then, 38 ml distilled water and 1.7 g 37% HCl were added. After stirring for 10 minutes, the solution was diluted with 675 ml ethanol. Then, 10 g SnCl.sub.4.6H.sub.2O, dissolved in 95 ml ethanol and 5 ml acetyl-acetone, was added to the solution.

T-Layer:

[0250] 70 ml titanium-m-butoxide, 920 ml ethanol (absolute) 5 ml acetyl-acetone and 10 ml ethyl-butyl-acetate were mixed together and stirred for 2 hours.

M-Layer:

[0251] The M-layer was produced as described in example 3.

[0252] The glass substrate was dipped into a clean KNO.sub.3 salt bath for chemical prestressing at a temperature of 420° C. for 8 hours. Then, the glass substrate was subjected to an ion exchange in an additional silver-containing salt bath at a temperature of 430° C. for 0.5 hours. The molten salt in the second salt bath was KNO.sub.3, mixed with 0.1 weight-% AgNO.sub.3.

[0253] After the ion exchange, the glass substrate was cleaned and an AF coating was applied by a conventional liquid printing process.

[0254] The glass substrate thus produced per example 4 has an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0255] The compressive stress (CS) of the glass substrate per example 4 was 339 MPa and the DoL was 14 μm.

[0256] The antimicrobial effectiveness of the glass substrate per example 4 on its AF coated surface was >99.9% against E. coli and against S. aureus.

[0257] The water contact angle on the AF coated surface of the glass substrate of example 4 was 113°.

[0258] The reflections of the glass substrate produced per example 4 are illustrated in FIG. 8, before and after the ion exchange—performed in two steps. FIG. 8 shows that the reflections of the glass substrate per example 4 before and after the ion exchange show practically no difference, so that the antireflective coating was not negatively influenced by the strengthening process and the provision of the antimicrobial properties.

Example 5

[0259] Glass Substrate: Borosilicate Glass without Antimony

TABLE-US-00013 Proportion- Oxide weight-%] SiO.sub.2 65 B.sub.2O.sub.3 7 Al.sub.2O.sub.3 3 Na.sub.2O 9 K.sub.2O 8 ZnO 5 TiO.sub.2 2 CaO 1

[0260] A carefully cleaned 135×70×0.7 mm glass substrate of above composition was coated with an antireflective coating that was composed of a three-layer structure per FIG. 2. The antireflective coating consisted of three layers with the following structure: glass substrate (2)+M-layer (33)+T-layer (32)+S-layer (31). The S-layer (31) was at the same time an adhesion promoting layer. The three layers were applied onto the glass by dip coating.

[0261] The solutions for the three layers were produced as follows:

S-Layer:

Pre-Solution

[0262] 60 ml TEOS were mixed with 125 ml ethanol and 10 ml 0.1 N HCl and were stirred for 3 hours at 40° C. Then, 9.5 g Al(NO.sub.3).sub.3, 270 ml ethanol and 50 ml ethyl-acetone were stirred for an additional 30 minutes.

T-Layer:

[0263] 30 ml Titanium-oxide-isopropoxide was mixed with 36 ml acetic acid and stirred for 1 hour. Then, 400 ml ethanol was added and stirred for 1 hour. Finally, 100 ml acetyl-acetone were added into the solution and stirred for 1 hour.

[0264] The glass substrate was then dipped into a salt bath for the ion exchange process that was conducted for 3 hours at a temperature of 410° C. The molten salt in the salt bath was KNO.sub.3, mixed with 0.5 weight-% AgNO.sub.3.

[0265] After the ion exchange, the glass substrate was cleaned and an AF coating was applied by a conventional spray coating process.

[0266] The glass substrate thus produced according to example 5 has an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0267] The compressive stress (CS) of the obtained glass substrate according to example 5 was 407 MPa and the DoL was 14 μm.

[0268] The antimicrobial effectiveness of the glass substrate according to example 5 on its AF coated surface was >99.9% against E. coli and also against S. aureus.

[0269] The water contact angle on the AF coated surface of example 5 was 114°.

[0270] The transmission of the same, but untreated glass substrate in contrast to the glass substrate produced in accordance with example 5 is illustrated in FIG. 9.

[0271] FIG. 9 shows that the transmission of the glass substrate according to example 5 is clearly higher and shows a maximum at a wavelength in the rage of 450 and 500 nm, in contrast to an untreated glass substrate:

Example 6

[0272] Glass Substrate: Borosilicate Glass with the Following Composition:

TABLE-US-00014 Composition Weight-% SiO.sub.2 80.8 Al.sub.2O.sub.3 2.4 B.sub.2O.sub.3 12.7 Na.sub.2O 3.5 K.sub.2O 0.6

[0273] A carefully cleaned 100×200 mm borosilicate glass was coated with an antireflective coating that was a single-layer structure as illustrated in FIG. 4. The single AR layer was at the same time an adhesion promoting layer.

[0274] The solution for the single layers was produced as follows:

[0275] 56 g of a 30% aqueous SiO.sub.2 solution, stabilized with NH.sub.4OH, wherein the SiO.sub.2 had a medium particle size of 8 nm, were mixed with 120 ml ethanol and 10 ml 0.1 N HCl and were stirred for 3 hours at 40° C. Then, 9.5 g Al(NO.sub.3).sub.3, 270 ml ethanol and 50 ml ethyl-acetone were added and stirred for an additional 30 minutes.

[0276] The borosilicate glass substrate was coated with the aforementioned solution on both sides in a dip coating process. The fresh coating was preheated for 2 minutes at 200° C. and the coated glass substrate was then tempered at 450° C. for 1 hour.

[0277] The coated glass substrate was then dipped into a salt bath for the ion exchange process that was conducted for 4 hours at a temperature of 450° C. The molten salt in the salt bath was KNO.sub.3, mixed with 0.05 weight-% AgNO.sub.3.

[0278] After the ion exchange, the sample was cleaned and an AF coating was applied by a conventional liquid printing coating process.

[0279] The glass substrate thus produced according to example 6 has an AR coating, is chemically prestressed, possesses antimicrobial properties and has an AF coating.

[0280] The compressive stress (CS) of the obtained glass substrate according to example 6 was 213 MPa and the DoL was 12 μm.

[0281] The antimicrobial effectiveness of the glass substrate according to example 6 on its AF coated surface was >99% against E. coli and also against S. aureus.

[0282] The water contact angle on the AF coated surface of the glass substrate in example 6 was 112°.

[0283] The transmission of the untreated glass substrate in contrast to the glass substrate produced according to example 6 is illustrated in FIG. 10. FIG. 10 shows that the transmission of the glass substrate that was produced according to example 6 is clearly higher than that of the same untreated glass substrate.

[0284] While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.

REFERENCE IDENTIFICATION LISTING

[0285] 2 glass or glass ceramic substrate [0286] 20 surface of the glass or glass ceramic substrate [0287] 3 layer with low refractive index of the antireflective coating [0288] 4 layer with high refractive index of the antireflective coating [0289] 5 antireflective coating in the embodiment of a single layer [0290] 31 layer with low refractive index of the antireflective coating [0291] 32 layer with high refractive index of the antireflective coating [0292] 33 layer with medium refractive index of the antireflective coating [0293] 41, 42,43,44 layers with alternating high and low refractive index of the antireflective coating