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.

What is claimed is: 
     
         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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   40-75;  
                 
                     
                   Al 2 O 3   
                   10-30;  
                 
                     
                   B 2 O 3   
                   0-20; 
                 
                     
                   Sum of Li 2 O + Na 2 O + K 2 O 
                   4-30; 
                 
                     
                   Sum of MgO + CaO + SrO + BaO + ZnO 
                   0-15; 
                 
                     
                   Sum of TiO 2  + ZrO 2   
                         0-15; and 
                 
                     
                   P 2 O 5   
                   0-10. 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         11 . The coated substrate according to  claim 1 , wherein said substrate is a borosilicate glass comprising the following in weight-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   60-85;  
                 
                     
                   Al 2 O 3   
                   1-10; 
                 
                     
                   B 2 O 3   
                   5-20; 
                 
                     
                   Sum of Li 2 O + Na 2 O + K 2 O 
                   2-16; 
                 
                     
                   Sum of MgO + CaO + SrO + BaO + ZnO 
                   0-15; 
                 
                     
                   Sum of TiO 2  + ZrO 2   
                       0-5; and 
                 
                     
                   P 2 O 5   
                   0-2.  
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         12 . The coated substrate according to  claim 1 , wherein said substrate is a soda-lime glass comprising the following in weight-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   40-80; 
                 
                     
                   Al 2 O 3   
                   0-6; 
                 
                     
                   B 2 O 3   
                   0-5; 
                 
                     
                   Sum of Li 2 O + Na 2 O + K 2 O 
                    5-30; 
                 
                     
                   Sum of MgO + CaO + SrO + BaO + ZnO 
                    5-30; 
                 
                     
                   Sum of TiO 2  + ZrO 2   
                         0-7; and 
                 
                     
                   P 2 O 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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   50-75;  
                 
                     
                   Al 2 O 3   
                   7-25; 
                 
                     
                   B 2 O 3   
                   0-20; 
                 
                     
                   Sum of Li 2 O + Na 2 O + K 2 O 
                   1-4;  
                 
                     
                   Sum of MgO + CaO + SrO + BaO + ZnO 
                   5-25; 
                 
                     
                   Sum of TiO 2  + ZrO 2   
                         0-10; and 
                 
                     
                   P 2 O 5   
                   0-5.  
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         14 . The coated substrate according to  claim 1 , wherein said substrate is a lead glass comprising the following in weight-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   PbO 
                   20-80;  
                 
                     
                   SiO 2   
                   20-60;  
                 
                     
                   K 2 O 
                   0-10; 
                 
                     
                   Na 2 O 
                   1-10; 
                 
                     
                   BaO 
                   0-20; 
                 
                     
                   SrO 
                   0-20; 
                 
                     
                   Al 2 O 3   
                   0-10; 
                 
                     
                   CaO 
                   0-10; 
                 
                     
                   F 2 O 3   
                   0-1;  
                 
                     
                   Sb 2 O 3   
                   0-1;  
                 
                     
                   ZnO 
                   0-20; 
                 
                     
                   B 2 O 3   
                         0-20; and 
                 
                     
                   ZrO 2   
                   0-10. 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         15 . The coated substrate according to  claim 1 , wherein said substrate is a glass comprising the following in weight-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   10-90;  
                 
                     
                   Al 2 O 3   
                   0-40; 
                 
                     
                   B 2 O 3   
                   0-80; 
                 
                     
                   Na 2 O 
                   1-30; 
                 
                     
                   K 2 O 
                   0-30; 
                 
                     
                   CoO 
                   0-20; 
                 
                     
                   NiO 
                   0-20; 
                 
                     
                   Ni 2 O 3   
                   0-20; 
                 
                     
                   MnO 
                   0-20; 
                 
                     
                   CaO 
                   0-40; 
                 
                     
                   BaO 
                   0-60; 
                 
                     
                   ZnO 
                   0-40; 
                 
                     
                   ZrO 2   
                   0-10; 
                 
                     
                   MnO 2   
                   0-10; 
                 
                     
                   CeO 
                   0-3;  
                 
                     
                   SnO 2   
                   0-2;  
                 
                     
                   Sb 2 O 3   
                   0-2;  
                 
                     
                   TiO 2   
                   0-40; 
                 
                     
                   P 2 O 5   
                   0-70; 
                 
                     
                   MgO 
                   0-40; 
                 
                     
                   SrO 
                   0-60; 
                 
                     
                   Li 2 O 
                   0-30; 
                 
                     
                   Li 2 O + Na 2 O + K 2 O 
                   1-30; 
                 
                     
                   SiO 2  + B 2 O 3  + P 2 O 5   
                   10-90;  
                 
                     
                   Nd 2 O 5   
                   0-20; 
                 
                     
                   V 2 O 5   
                   0-50; 
                 
                     
                   Bi 2 O 3   
                   0-50; 
                 
                     
                   SO 3   
                         0-50; and 
                 
                     
                   SnO 
                   0-70, 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
       wherein the content of SiO 2 +P 2 O 5 +B 2 O 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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   SiO 2   
                   55-69; 
                 
                     
                   Al 2 O 3   
                   19-25; 
                 
                     
                   Li 2 O 
                   3-5; 
                 
                     
                   Sum of Na 2 O + K 2 O 
                   0.5-15;  
                 
                     
                   Sum of MgO + CaO + SrO + BaO 
                   0-5; 
                 
                     
                   ZnO 
                   0-4; 
                 
                     
                   TiO 2   
                   0-5; 
                 
                     
                   ZrO 2   
                   0-3; 
                 
                     
                   Sum of TiO 2  + ZrO 2  + SnO 2   
                   2-6; 
                 
                     
                   P 2 O 5   
                   0-8; 
                 
                     
                   F 
                         0-1; and 
                 
                     
                   B 2 O 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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   Li 2 O 
                   3.2-5.0;     
                 
                     
                   Na 2 O 
                   0-1.5; 
                 
                     
                   K 2 O 
                   0-1.5; 
                 
                     
                   Sum Na 2 O + K 2 O 
                   0.2-2.0;     
                 
                     
                   MgO 
                   0.1-2.2;     
                 
                     
                   CaO 
                   0-1.5; 
                 
                     
                   SrO 
                   0-1.5; 
                 
                     
                   BaO 
                   0-2.5; 
                 
                     
                   ZnO 
                   0-1.5; 
                 
                     
                   Al 2 O 3   
                   19-25;     
                 
                     
                   SiO 2   
                   55-69;     
                 
                     
                   TiO 2   
                   1.0-5.0;     
                 
                     
                   ZrO 2   
                   1.0-2.5;     
                 
                     
                   SnO 2   
                   0-1.0; 
                 
                     
                   Sum TiO 2  + ZrO 2  + SnO 2   
                    2.5-5.0; and 
                 
                     
                   P 2 O 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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   Li 2 O 
                   3-5; 
                 
                     
                   Na 2 O 
                       0-1.5; 
                 
                     
                   K 2 O 
                       0-1.5; 
                 
                     
                   Sum Na 2 O + K 2 O 
                   0.2-2;     
                 
                     
                   MgO 
                   0.1-2.5; 
                 
                     
                   CaO 
                   0-2; 
                 
                     
                   SrO 
                   0-2; 
                 
                     
                   BaO 
                   0-3; 
                 
                     
                   ZnO 
                       0-1.5; 
                 
                     
                   Al 2 O 3   
                   15-25; 
                 
                     
                   SiO 2   
                   50-75; 
                 
                     
                   TiO 2   
                   1-5; 
                 
                     
                   ZrO 2   
                       1-2.5; 
                 
                     
                   SnO 2   
                       0-1.0; 
                 
                     
                   Sum TiO 2  + ZrO 2  + SnO 2   
                    2.5-5; and 
                 
                     
                   P 2 O 5   
                       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-%: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   Li 2 O 
                   3-4.5; 
                 
                     
                   Na 2 O 
                   0-1.5; 
                 
                     
                   K 2 O 
                   0-1.5; 
                 
                     
                   Sum Na 2 O + K 2 O 
                   0.2-2;    
                 
                     
                   MgO 
                   0-2;     
                 
                     
                   CaO 
                   0-1.5; 
                 
                     
                   SrO 
                   0-1.5; 
                 
                     
                   BaO 
                   0-2.5; 
                 
                     
                   ZnO 
                   0-2.5; 
                 
                     
                   B 2 O 3   
                   0-1;     
                 
                     
                   Al 2 O 3   
                   19-25;     
                 
                     
                   SiO 2   
                   55-69;     
                 
                     
                   TiO 2   
                   1.4-2.7;     
                 
                     
                   ZrO 2   
                   1.3-2.5;     
                 
                     
                   SnO 2   
                   0-0.4; 
                 
                     
                   Sum TiO 2  + SnO 2   
                   less than 2.7; 
                 
                     
                   P 2 O 5   
                    0-3; and 
                 
                     
                   Sum ZrO 2  + 0.87 (TiO 2  + SnO 2 ) 
                   3.6-4.3.     
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         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.