Coated glass substrate or glass ceramic substrate with resistant multi-functional surface properties, method for production thereof and use thereof

0001The present invention relates to a coated glass or glass-ceramic substrate having stable, that is permanently present, multi-functional surface properties, a process for its preparation and its use.

Background of the Prior Art

0002Glass is the world due to its special properties, in particular the excellent mechanical strength, optical properties and durability against chemicals, one of the most commonly used materials, and is also still relatively inexpensive to produce. Glasses are almost everywhere in the building industry, used in the electronic field, transportation, daily necessities, in laboratory applications, scientific equipment and the like. For such a versatile application fields and the properties of glass used in each case are very different. For example, is used in building have high mechanical strength. Glass, which is used in medical or accessible in public areas should have antimicrobial properties. Window glass or glass in display devices to show high transparency and high anti-reflective properties. For so-called touch screens, showcase or exhibit space, which are made of glass, it is expedient if this anti-fingerprint or so-called easy-to-clean properties. In many cases it is not necessary to develop new lenses to meet any of the requirements mentioned above. The desired functions are usually only properties of the glass surface, so that in the course of time many surface treatments and coating methods have been developed to impart new functions to the known glass products.

0003For example, numerous publications of the prior art are known for antimicrobial (AM) glass surfaces: To describe the documents <patcit><text>US 2007/0172661 A1</text></patcit>. <patcit><text>JP 2011-133800A</text></patcit> and the <patcit><text>US 2012/0034435 A1</text></patcit> different paths, the glass surface, for example, by the silver-alkali ion exchange technology, to impart antimicrobial properties. According to this prior art is an ion exchange between silver ions and contained in the glass alkali metal ions, usually sodium ions, instead, so that the silver ions diffuse into the glass surface and present at a depth of several hundred nanometers to several tens of micrometers. Silver ions have a well-known cytotoxic effect on microorganisms by inhibiting their growth and cell death.

0004Antimicrobial glass surfaces can also be made with other technologies. In principle, all kinds of known antimicrobial agents, in particular metals, such as silver or copper, metal compounds, such as silver salts, or nanoparticles can be deposited of complex organic compounds to glass surfaces as antimicrobial coatings. Antimicrobial glass surfaces may also be produced using thermal annealing.

0005For example, the <patcit><text>US 2008/0145625 A1</text></patcit> a process for producing a glass substrate having a sol-gel-layer, wherein a silver-containing antimicrobial sol-gel layer can be used.

0006The <patcit><text>US 2014/0017462 A1</text></patcit> describes a transparent and antimicrobial cover glass containing nanoparticles of Cu or Cu₂O on the surface of the glass, as well as methods for making these glass articles.

0007The <patcit><text>US 2009/0162695 A1</text></patcit> describes a method for producing a substrate having antimicrobial properties, comprising depositing a mixed layer on a substrate by sputtering under vacuum, wherein the mixed layer comprises at least one antimicrobial agent and a binder.

0008The <patcit><text>WO 2007/108514 A1</text></patcit> describes a glass plate with an antibacterial film.

0009The <patcit><text>US 6,921,546 B2</text></patcit> describes a glass or a glass-like substrate having antimicrobial activity. The antimicrobial substrate is prepared by providing a metal ion precursor, comprising at least a source of antimicrobial metal ions dissolved, or otherwise dispersed in a carrier material; Depositing the precursor onto at least one surface of the substrate; Drying the substrate at a temperature of about 20 ° C to about 105 ° C, removing the volatile constituents from the precursor metal ions, and heating the resulting substrate to a temperature of about 600 ° C to about 650 ° C for 2to 5 minutes in order to exchange the antimicrobial metal ions from the precursor with the glass or glass-like substrate or engage in some other way.

0010The <patcit><text>WO 2007/147842 A2</text></patcit> describes a method for producing a substrate having antimicrobial properties, wherein a metal layer comprising an inorganic antimicrobial agent is applied, and the agent diffuses into at least one surface of the substrate, which is subjected to a thermal treatment. Alternatively, the substrate may be first coated with a subbing layer, wherein the diffusion occurs in the lower layer.

0011The <patcit><text>US 2012/0219792 A1</text></patcit> describes a glass substrate as a cover glass for a display, which not only has excellent strength and antibacterial properties but also high transparency and high visible transmission. The method comprises the chemical tempering of the glass substrate in an at least KNO₃-containing molten salt, the cleaning of the glass substrate, forming a silver film on the surface of the cleaned glass substrate, subjecting the glass substrate with the formed thereon silver film to a heat treatment to diffuse the silver ions from the glass substrate surface to the inside, as well as the washing and removing of the remaining on the surface and not diffused silver from the glass substrate.

0012To equip properties a glass surface with antireflective (AR), an AR coating is the conventional choice. The AR coating is a kind of optical coating that is applied to the surface in order to reduce the reflection and thereby to improve the light transmittance at a specific wavelength range. IR, visible or UV frequencies are often selected.

0013The simplest interference AR coating consists of a single quarter-wave layer of transparent material whose refractive index is the square root of the refractive index of the substrate. This results in theoretically a zero reflectance at the center wavelength and decreased reflectance for the wavelengths in a broad band around the center. AR coatings in the form of multiple layers consist for example of transparent thin film structures with alternating layers of contrasting refractive indices. The layer thicknesses are chosen to produce destructive interference in the beam reflected from the interfaces, and constructive interference in the corresponding transmitted rays. AR coatings are used in a wide variety of applications where light passes through an optical surface and a low loss or low reflectance are desired.

0014According to the interference mechanism in AR coatings can be used as an antireflection coating, in principle, any known coating, provided its refractive index is suitable. The coating can be applied by means of a liquid phase coating, for example by printing technology, spray technology or a sol-gel process. The anti-reflection coating can be applied at atmospheric pressure by means of a CVD coating, such as a PECVD, PICVD, low pressure CVD, or chemical vapor deposition. The anti-reflective coating can also be applied with a PVD coating, which can be, for example, sputtering, thermal evaporation, laser beam, electron beam or arc evaporation.

0015Numerous proposals for anti-reflective coatings are known from the prior art: So describes the <patcit><text>US 5,847,876</text></patcit> an antireflective layer, is applied onto a glass substrate, which is preferably a first layer of high refractive index of Al₂O₃And a second layer of low refractive index, preferably of MgF₂, describes.

0016The <patcit><text>EP 2103965 A1</text></patcit> describes an antireflective layer, applied to a substrate made of glass or plastic. The first layer of high refractive index comprises an oxide of at least one of the elements tin, gallium or indium and cerium; the second layer is constructed of a metal such as silver and palladium; the third layer corresponds to the first layer with a high refractive index and the fourth and uppermost layer has a low refractive index and is composed of silica, magnesium fluoride or potassium fluoride. The layers are deposited by sputtering, respectively.

0017The <patcit><text>US 2011/0052815 A1</text></patcit> describes a composition comprising for the preparation of an AR coating is a condensate obtainable by the condensation of silicon compounds of the general formula R_nSiX_4-nWherein the X groups are the same or different and represent hydrolyzable groups or hydroxyl groups, the R groups are the same or different and represent non-hydrolysable groups, and n is 0, 1, 2 or 3, wherein the composition comprises at least one polymeric means of controlling having rheology, and at least one solvent having a boiling point of at least 150 ° C. This document also describes the method of making and using the present composition. In particular, the composition may be applied by screen printing onto the substrates.

0018The <patcit><text>CN 102923969 A</text></patcit> describes a dual function in the form of antireflection and oleophobbeschichtetem glass and its manufacturing method. The film structure of the coated glass is as follows: a glass substrate, a base film, a buffer film and a surface film, wherein the base film contains a silicon compound, the buffer film, a silicon fluoride compound and the surface film has a silicon fluoride organic compound. The films are applied mainly by spraying techniques.

0019The <patcit><text>CN 103013189 A</text></patcit> discloses an anti-reflective glass coating liquid prepared by Siliciumoxidsole that are applied to the surface of the glass by a roll coating method, dip coating or spraying method, and a hardening treatment at temperatures of not more than 100 ° C is performed.

0020The <patcit><text>WO 2008/099061 A1</text></patcit> describes a method for coating an optical product including an AR coating which is deposited by chemical vapor deposition (CVD).

0021An anti-fingerprint (AF) surface, which is also sometimes referred to as the easy-to-clean (ETC) or amphiphobe surface, ensures that dirt and impurities as a result of fingerprints are substantially not visible and therefore the surface is in use also clean appear without purification. The AF-surface must be resistant, caused by using the user, for example, residues of fingerprints and are applied to the surface against water, salts and fat. The wetting properties of a surface-AF must be both hydrophobic and oleophobic.

0022The majority of known AF-coatings based essentially on organic fluorine compounds with high water contact angle. In some cases, specially designed structures are created on the glass surface to increase the contact angle with oil or water on.

0023From the prior art to AF surfaces of glass articles, for example, the following documents are known: So describes the <patcit><text>DE 198 48 591 A1</text></patcit> for producing a protective layer of this type, the use of organo-fluorine compounds of the formula R_f-V In the form of a liquid system comprising the organofluorine compound in a carrier liquid, wherein R_f in the formula is an aliphatic hydrocarbon residue which is partially or completely fluorinated and may be straight, branched, or is cyclic. The hydrocarbon radical can be interrupted by one or more oxygen, nitrogen or sulfur atoms. V represents a polar or dipolar group selected from -COOR, -COR, -COF, -CH₂OR, -OCOR, -CONR₂, -CN, -CONH-NR₂, -CON = C (NH₂)₂, -CH = NOR, -NRCONR₂, -NO₂COR, NR_W, -SO₃R, -OSO₂R, -OH, -SH, ≡B, -OP (OH)₂, OPO (OH)₂, - OP (ONH₄)₂, OPO (ONH₄)₂, -CO-CH = CH₂Wherein R in group V may be the same or different and represent hydrogen, a phenyl radical, a straight-chain or branched alkyl or alkyl ether group having up to 12, preferably up to 8 carbon atoms, is, and is partially or completely fluorinated or chlorofluorinated, and w is 2 or 3, or is -R_v-V-. In the formula -R_v-V- Is V, the above-mentioned polar or dipolar group and R_v represents a straight-chain or branched alkylene radical having up to 12, preferably up to 8 carbon atoms which may be partially or completely fluorinated or chlorofluorinated.

0024The <patcit><text>EP 0844265 A1</text></patcit> describes a silicon-containing organic fluoropolymer for coating substrate surfaces, such as metal, glass and plastic materials, to provide a surface with sufficient and long-lasting antifouling properties, sufficient weather resistance, lubricity, anti-adhesion properties, water repellency and resistance to oily dirt and fingerprints. Also disclosed is a treatment solution for a surface treatment method comprising a silicon-containing organic fluoropolymer, a fluorine-containing organic solvent and a silane compound.

0025The <patcit><text>US 2010/0279068 A1</text></patcit> describes a method for providing hydrophobic and oleophobic glass surfaces. The process consists of heating a glass article at temperatures close to the glass softening point and pressing a structured form in the glass article to obtain a surface texture.

0026The <patcit><text>US 2010/0285272 A1</text></patcit> discloses a glass substrate having at least one machined surface, which is hydrophobic and oleophobic, having non-stick properties, is fingerprint-resistant, has durability, and is transparent. The surface has at least one kind of topological features, which with a special geometry prevents the decrease of the contact angle and adhesion of water and oil drops. For example, for the application of an AF-blown sand coating the glass surface and the coating thereon by means of physical or chemical vapor deposition may be applied.

0027The <patcit><text>US 2009/0197048 A1</text></patcit> describes an AF or easy-to-clean coating on a glass cover which is present as an outer coating with Fluorendgruppen as Perfluorkohlenstoffresten or a perfluorocarbon-containing radical, whereby the glass cover hydrophobic and oleophobic and thus the wetting of the glass surface with water and oils is minimized. Under the AF-coating may be an AR coating, consisting of silica, quartz glass, fluorine-doped silicon dioxide, fluorine-doped quartz glass, MgF₂, HfO₂, TiO₂, ZrO₂, Y₂O₃ or Gd₂O₃ is constructed. On the glass surface, prior to the AF coating also generates a pattern, or a structure ascending or be introduced, with an etching, lithography or particle coating method is used. The glass cover can after the ion exchange and etched prior to the AF coating ..

0028The hardening or tempering glass is also a known surface treatment. The principle of the thermal and chemical curing or chemical tempering of glass is to form a compressive stress layer in the glass surface with a depth of about several 10 microns. This compressive stress layer causes the tempered glass has an increased strength. This is attributed to that surface defects are pressed together by the compressive stress forces. Otherwise, an extension of these defects could lead to a crack.

0029The chemical tempering or hardening is a long-known technology. Glass is typically immersed in a bath containing molten potassium nitrate, at a temperature around 400 ° C. This causes the sodium ions in the glass surface are replaced with potassium ions from the bath solution. The potassium ions are larger than the sodium ions, the sodium ions migrate from the glass into the potassium nitrate melt and potassium ions squeeze into the abandoned by the smaller sodium ions gaps. This exchange of ions causes the surface of the glass builds up a voltage, and the interior of the lens tries to compensate for the voltage. The surface compressive stress of a chemically tempered glass can reach more than 600 MPa.

0030There are numerous documents of the prior art, which describe the chemical hardening or toughening: Thus discloses <patcit><text>US 3,778,335</text></patcit> Glass compositions from Natriumaluminosilikatglas with a surface compressive stress layer, which increases the strength of a glass article, such as the chemical toughening of glass.

0031The <patcit><text>US 2013/0202715 A1</text></patcit> describes an aluminosilicate glass for a touch screen as well as the chemical toughening the glass.

0032It has been shown in the art that there are for each property, such as antimicrobial, anti-reflective, anti-fingerprint property and increased glass strength, many different approaches to impart these a glass surface. However, in some cases, the combination of several of these properties are desired.

0033The cover glass of a touch screen smart phones and tablet PCs is a typical example in which many functions should be integrated together. The units are very thin and must have high mechanical strength, so that a tempered glass is necessary. Simultaneously, a surface provided with anti-reflective properties such that energy can be saved, because the display module can operate with lower brightness when the reflection is reduced at the glass-air interface. Furthermore, a very large amount of bacteria on such screens are present, so that an antimicrobial surface could protect the health of the user. Finally, such screens are touched each day often, so that the anti-fingerprint property would be very useful.

0034Showcase glass or at exhibitions, eg picture framing in museums, or in shops window glass used is another typical example. The high mechanical strength is an obvious requirement for such glasses. The antireflective surface in these windows could lead to the best effects. Conventional glass reflects about 8% of the incident light. The antireflectiveCoating reduces reflection, allowing a look. These discs are often touched by the visitors, especially children, if such be displayed behind glass. B. particularly beautiful objects, for example, in museums. Therefore, an antimicrobial surface may be advantageous in terms of public health, and the provision of anti-fingerprint surfaces could the frequency with which these discs must be cleaned decrease.

0035Although there is a high demand and a large need for such combinations of properties, there is currently no such technology or an object which integrates all of these properties on the same glass surface. This is probably because it is relatively difficult to provide the desired property profile in combination, because each of these features and functions has a number of own implementation paths and difficulties. Furthermore, all the glass surface conferred functions must be durable enough to meet the current industry quality standards, and the process should be suitable for mass production.

0036To all the properties of interest in fact be included in the glass surface, there are therefore only two options: to develop a treatment process that gives many features in one step or to develop a multi-step process, which may cause a function in each step, except that the foregoing of a step obtained functions after the subsequent treatment still should be available. Neither of these options is feasible, however, in a simple manner.

0037some very limited function combinations are already known from the prior art: So describes the <patcit><text>WO 2012/163946 A1</text></patcit> a substrate member for coating with an easy-to-clean coating comprising a substrate and an antireflective coating is applied to the substrate, wherein the uppermost layer of the antireflective coating is an adhesive layer, which is capable of, with an easy-to -Clean coating to contact Wechselwelwirkung. It is also mentioned in this document that the anti-reflective coated glass substrate, without appreciably affecting the coating may be thermally cured, so that an AR function, AF function and the thermal toughening of glass are combined.

0038The <patcit><text>DE 10 2007 009 785 B4</text></patcit> discloses a sol-gel coated glass article which is chemically biased after coating, so that a combination of an AR coating and chemically strengthened glass is provided.

0039The <patcit><text>CN 102923966 A</text></patcit> describes an antimicrobial and anti-reflective sol-gel coating. A metal compound having antimicrobial activity is doped to the coating, wherein the metal is selected from the group consisting of silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium and nickel. It is also mentioned that the thermal treatment of the coating can be performed together in one step with the thermal tempering of the glass substrate whereby the glass antimicrobial and anti-reflective function can be imparted and the glass is thermally cured.

0040The <patcit><text>US 2012/0034435 A1</text></patcit> describes a chemically tempered glass having antimicrobial properties and a method for manufacturing this glass. In particular, a chemically strengthened glass is disclosed having antimicrobial properties, which has a coating with low surface energy on the glass, which does not affect the antimicrobial properties of the glass. Therefore, a combination of anti-microbial and anti-fingerprint capabilities and chemically tempered glass is provided.

0041Finally, describes the <patcit><text>US 2014/0017462 A1</text></patcit> comprises a transparent cover glass for applications such as, for example, touch screen devices, the antimicrobial properties. The antimicrobial glasses contain nanoparticles of Cu or Cu₂O on the surface of the glass. The antimicrobial glasses may further comprise a fluorosilane coating or other coating on the surface, so that an easy-to-clean surface is provided. Therefore, the glass-microbial and anti-fingerprint capabilities are awarded.

0042The known prior art, are described in the multifunctional glass surfaces, does not consider that the layers should be designed for a chemical tempering. Furthermore, the anti-fingerprint (AF) coatings, provided, so that the desired improvement in properties is present not sufficiently resistant usually at best temporarily available. Also, a film or a layer / layers, the / has been applied to the glass surface, blocking the ion exchange, ifthe film or the layer was applied to the glass surface prior to the chemical tempering. For chemically-strengthened glass can lead to a relaxation of the pressure built up tension in a subsequent heating of the glass, especially if the temperature is above 200 ° C. Many coating technologies require the heating at the film production or post-treatment, which is why the coating of biased substrates is limited. However, the chemical tempering is in certain applications an important feature, because thin glass that is particularly for cover glasses of touch screens in consumer electronics for use, the only way is to increase the strength of the glass. This plays an important role, for example in mobile phones, smart phones, tablet PCs, laptops, televisions, ATM machines, ticket vending machines or control or control display in any devices or in a motor vehicle.

0043Thin glasses can not be thermally toughened because of their thinness. Furthermore, has not been investigated which combinations with anti-fingerprint (AF) coatings are even possible and whether an AF coating with other functions, such as an antimicrobial (AM) function is at all compatible and do not affect each other adversely or even block. Another important aspect is that the glass surface conferred several functions should be of sufficient stability to be used wisely in practice.

0044The present invention is therefore based on the object of overcoming the disadvantages of the prior art and to provide a glass or glass ceramic substrate having a plurality of the properties or functionality described unites in itself, where the properties are permanently present. It should also be possible to provide additional features or functionality. Furthermore, a method is provided that allows in a simple way, the manufacture of the glass or glass ceramic substrate of the invention.

Description of the Invention

0045The above-described object is achieved by a coated glass or glass ceramic substrate with resistant multifunctional surface properties comprising <ul list-style="bullet"><li>- A combination of antimicrobial, anti-reflective and anti-fingerprint properties, or</li><li>- A combination of antimicrobial, anti-reflective and anti-fingerprint properties, wherein the substrate is chemically biased or</li><li>- A combination of antimicrobial and anti-reflective properties, wherein the substrate is chemically prestressed.</li></ul>

0046The coated glass or glass ceramic substrates resistant multifunctional surface properties according to the present invention find versatile application, such as a cover glass for any form of touch screens, for example, in the consumer electronics, especially in mobile phones, smart phones, tablet PCs, notebook PCs, TVs, ATM machines and the like. Other applications are found in hospitals, museums, shops, in construction and transport, at ticket counters, Indicators of equipment or motor vehicles, billboards and the like, wherever antimicrobial properties, low light reflection, and, optionally, ease of cleaning and high mechanical strength appropriate and are required.

0047So far there is no such technology or a coated glass or glass ceramic substrate which combines all of these properties or functions in one and the same glass surface. This is not easy to achieve, because each function is introduced in a completely different way in the glass surface and each of these functions and thus each of the manufacturing process used has completely own conditions.

0048There are several ways in which the various functions can be realized in or on a glass or glass ceramic surface. According to the invention, the antimicrobial function is achieved by ion exchange, where one or more antimicrobial metal ions in an antimicrobially effective amount, preferably selected from silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium and / or nickel ions are present. It is not a coating, for example in the form of a single layer of antimicrobial metal salts, applied to the glass or glass ceramic surface or the anti-reflective coated glass or glass ceramic surface. The anti-reflective coating and also the anti-fingerprint function are preferably applied in each case by providing a coating of one or more layers on the glass or glass ceramic substrate. The anti-fingerprint function or coating is regularly the top layer on the glass orGlass ceramic substrate in order to fulfill its function. The chemical tempering, if desired, is carried out by ion exchange with the glass or glass ceramic substrate and the antireflective coating situated thereon.

0049Surprisingly it has now been found that combinations of properties of the invention do not affect each other adversely. In particular, it is unexpected that the antimicrobial properties may be obtained according to the invention, without adversely affecting other functionalities of the coated glass or glass ceramic surface. The antimicrobial functionality is also not adversely affected when an anti-fingerprint coating is applied to the coated glass or glass ceramic surface. This is particularly the case when the AF coating, is preferably based on a liquid phase coating is applied.

0050The invention further relates to a method for producing a coated glass or glass-ceramic substrate with durable multi-functional surface properties, comprising the steps of: <ul list-style="bullet"><li>- Applying an anti-reflective coating to a glass or glass-ceramic substrate;</li><li>- Performing one of the three subsequent ion exchange method with the anti-reflective coated glass or glass-ceramic substrate in a salt bath, (1) wherein the salt bath comprises one or more metal salts having an antimicrobial action, preferably selected from the group consisting of silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, to give selenium, chromium, magnesium and / or nickel salts to the glass or glass-ceramic substrate antimicrobial properties; or (2) where the salt bath comprises a mixture of potassium, rubidium and / or cesium salt containing one or more metal salts having an antimicrobial action, preferably selected from the group consisting of silver, copper, cadmium, zinc, iron, to give tin, cobalt, cerium, antimony, selenium, chromium, magnesium and / or nickel salts to the glass or glass ceramic substrate and antimicrobial properties of this chemically bias the same time; or (3) wherein in a first step, the first salt bath potassium, rubidium and / or cesium salt and contains, in a second step, the second salt bath containing a mixture of potassium, rubidium and / or cesium salt containing one or more metal salts having antimicrobial activity , preferably selected from the group consisting of silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium and / or nickel salts to the to impart glass or Glaskeramiksubnstrat antimicrobial properties and this chemically bias; and</li><li>- Optionally applying an anti-fingerprint coating on the obtained anti-reflective coated glass or glass ceramic surface.</li></ul>

0051In the present specification, the term "anti-reflective" as "AR", the term "antimicrobial" as "ON" and the term "anti-fingerprint" as "AF".

0052According to the invention is thus at first an antireflective (AR) coating provided which is preferably based on the sol-gel technology, and is suitable for ion exchange, and thus a chemical tempering of the glass or glass ceramic surface.

0053The uppermost layer of the AR coating, especially sol-gel AR coating is preferably an adhesive layer, to apply a permanent AF coating thereon can. The glass or glass ceramic surface provided with the AR coating may then be in accordance with the inventive method, with a corresponding metal salt melt with antimicrobial ions, such as silver ions, equipped (Ionenautauschverfahren (1)), or it may be simultaneously antimicrobial finish in the same step and chemically prestressed (ion exchange method (2)) or chemical tempering and imparting antimicrobial properties can be carried out in two steps (ion exchange method (3)). Thereafter may optionally an anti-fingerprint coating can be applied, whereby the glass or glass ceramic surface antimicrobial (AM), anti-reflective (AR) and anti-fingerprint (AF) has properties and can be chemically biased simultaneously.

0054In applications where enhanced strength is of lesser importance, such as picture frames, window display or thicker window glasses, the ion exchange method is only used to impart antimicrobial functionality to the glass. The increase in strength by doping with larger alkaline ions, particularly potassium ions, is not required in this case. The anti-fingerprint coating is only applied when this is appropriate for the specific use, such as touch screen applications.

0055Thus, glass or glass ceramic substrates with durable multi-functional surface and different combinations of properties are provided according to the invention.

0056Below are the individual properties or functions with which the glass or glass ceramic substrate is fitted, are explained in detail:

Antireflective (AR) coating

0057The AR coated substrate, which is prepared in the first step of the method according to the invention, comprises a substrate of glass or glass ceramic and an antireflective coating.

0058The antireflective coating according to an embodiment consists of one or at least two layers. The one layer or the top layer of at least two layers is preferably an adhesive layer, which can interact with a thereto applied anti-fingerprint or easy-to-clean coating, making a long-term stability of the anti-fingerprint coating results. The adhesive layer is a layer that provides improved adhesion between the underlying and the overlying layer. This occurs with an applied anti-fingerprint coating such interacting, the long-term durability of the anti-fingerprint coating is increased due to a chemical, in particular a covalent bond between the adhesive layer of the novel substrate and coated thereon anti-fingerprint coating.

0059The function of the anti-reflective layer (s) (s) is (are) by the performed ion exchange process to obtain the antimicrobial properties (eg. B. Ionenautausch of sodium ions for silver ions) and by carried out the ion exchange method of chemical tempering (z. B. Ion exchange sodium ions for potassium ions), surprisingly not adversely affected. Conversely, it was also found that the ion exchange does not affect the anti-reflective coating has the function of an optional adhesive layer is negative both for chemical tempering and the antimicrobial finish.

0060The adhesion promoter layer, which preferably represents the top layer of anti-reflective coating, preferably has a low refractive index.

0061When the antireflective coating is a single layer, which is preferably embodied in the form of an adhesion promoter layer, the refractive index is preferably in the range from 1.22 to 1.44, preferably in the range from 1.28 to 1.44. When an AR coating, which is composed of multiple layers and wherein preferably the uppermost layer is an adhesive layer, the refractive index of the region of the uppermost layer is preferably in the range from 1.22 to 1.70, more preferably in the range of 1.28 to 1.60, particularly preferably in the range from 1.28 to 1.56.

0062The antireflective coating is preferably constructed such that it constitutes an incomplete antireflective coating and after application of an AF coating is present a complete optically antireflective coating. However, the optical contribution of AF coating is generally low, because it is very thin. In some cases, therefore, may also be optically inactive, the AF-coating.

0063The antireflective coating may also be constructed in such a way that an incomplete antireflective coating and is present only by the presence of an adhesive layer and optionally an AF coating is present a full anti-reflective coating.

0064The antireflective coating is according to another embodiment of three or more layers with alternating middle, high and low refractive indices. Also in this case, the uppermost layer is preferably an adhesive layer, and preferably has a low refractive index.

0065According to a further embodiment, the antireflective coating of two or more layers with alternating low and high refractive index. Also in this case, the uppermost layer is preferably an adhesive layer, and preferably has a low refractive index.

0066At least one layer of antireflective coating, particularly preferably the top or adhesive layer may be divided into sub-layers, which may be one or more intermediate layers. Preferably, then, the one or more intermediate layers on practically the same refractive index as the lower layers.

0067The adhesive layer is particularly advantageous and displays its function especially true if it represents a mixed oxide. The adhesion promoter layer is therefore in accordance with a preferred embodiment of the invention, a mixed oxide, more preferably a Siliciummischoxidschicht, in particular a silicon oxide layer, mixed with an oxide of at least one of the elements aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, boron, hafnium and / or magnesium fluoride, preferably at least one oxide of the element aluminum.

0068Among silicon oxide according to this invention also each silicon oxide and silicon dioxide between Siliziummono- is understood. Silicon within the meaning of the invention is understood as a metal and as a semi-metal. Siliziummischoxid is a mixture of a silicon oxide with an oxide of at least one other element, which can be homogeneous or non-homogeneous, stoichiometric or non-stoichiometric.

0069The adhesive layer preferably has a thickness greater than 1 nm, more preferably greater than 10 nm, more preferably greater than 20 nm.

0070In principle, any coating as antireflective coating, preferably an adhesion promoter layer used. An antireflective coating may be applied by printing technology, spray technology or technology vapor deposition, preferred is a liquid phase coating, more preferably a sol-gel coating. The anti-reflective coating, preferably comprising or consisting of the adhesive layer can be obtained by CVD technology, for example by PECVD, PICVD, low pressure CVD, or chemical vapor deposition at atmospheric pressure (AVD, atomic vapor deposition, ALD atomic layer deposition) are applied. The antireflective coating may also by PVD technology, such as sputtering, thermal evaporation, laser beam or electron beam or arc evaporation, are applied. The adhesive layer may alternatively be deposited by Flammpyrolysetechnologie. The adhesive layer and the other layers of the antireflective coating can alternatively be produced by combinations of various methods.

0071A sol-gel coating process to produce an anti-reflective coating will be described by way of example: First, the surface to be coated is preferably cleaned. The cleaning with liquids of glass or glass ceramic substrates is a widely used method. A variety of cleaning liquids is used herein, such as demineralized water or aqueous systems, such as dilute alkaline solutions (pH> 9) and acids, detergent solutions or non-aqueous solvent, such as, for example, alcohols or ketones.

0072The glass or glass ceramic substrate can be activated prior to coating. Activation method include, for example oxidation, corona discharge, flame treatment, UV treatment, plasma activation and / or mechanical methods such as a roughening, sandblasting and plasma treatments or other treatments of the substrate surface for activation with an acid and / or alkali.

0073A preferred sol-gel method utilizes the reaction of metallo-organic starting materials in a dissolved state to form the layers. As a result, a controlled hydrolysis and condensation reaction of organometallic starting materials a Metalloxidnetzwerkstruktur is established, that is, a structure in which the metal atoms are linked by oxygen atoms, at the same time. With elimination of the reaction products, such as alcohol and water The hydrolysis reaction can be accelerated by addition of catalysts.

0074The inorganic sol-gel material from which the sol-gel layers are formed, is preferably a condensate, in particular comprising one or more hydrolyzable and condensable or condensed silanes and / or metal, preferably from Si, Ti, Zr, Al, . Nb, Hf, Ge, B, Sn and / or Zn Preferably, the crosslinked by inorganic hydrolysis and / or condensation in the sol-gel process groups may be, for example, the following functional groups: TiR₄, ZrR₄, SiR₄, AlR₃, TiR₃(OR), TiR₂(OR)₂, ZrR₂(OR)₂, ZrR₃(OR), SiR₃(OR), SiR₂(OR)₂, TiR (OR)₃, ZrR (OR)₃, AlR₂(OR), AlR (OR)₂, Ti (OR)₄, Zr (OR)₄, Al (OR)₃, Si (OR)₄, SiR (OR)₃ and / or Si₂(OR)₆, The group OR can be for example: alkoxy such as preferably methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, isopropoxyethoxy, methoxypropoxy, phenoxy, acetoxy, propionyloxy, ethanolamine, diethanolamine, triethanolamine, methacryloxypropyl, acrylate, methyl acrylate, acetylacetone, ethyl acetoacetate, ethoxyacetate , methoxyacetate, Methoxyethoxyacetat and / or Methoxyethoxyethoxyacetat. The radical R can be, for example: Cl, Br, F, Metyhl, ethyl, phenyl, n-propyl, butyl, allyl, vinyl, Glycidylpropyl, methacryloyloxypropyl, aminopropyl and / or fluorooctyl.

0075A common feature of all the sol-gel reactions is that the molecularly precursor of a hydrolysis-condensation polymerization reactions and are subject to form particulate disperse or colloidal systems. Depending on the selected conditions, the "primary particles" that are initially formed, continue to grow, may combine to form clusters or may rather form linear chains. The resulting units result in microstructures that arise as a result of the removal of the solvent. Ideally, the material can be thermally fully densified, but often in reality remains a degree of porosity exist, in some cases even a considerable residual porosity. The chemical conditions during the sol-generation have a critical impact on the properties of the sol-gel coatings, as described in<nplcit><text>P. Löbmann, "Sol-gel coatings", training course 2003 "surface refinement of glass", Cottage Technical Association of the German Glass Industry</text></nplcit>,

0076The Si raw materials were today examined very closely. In this regard, reference is made to<nplcit><text>C. Brinker, G. Scherer, "Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing (Academic Press, Boston, 1990)</text></nplcit>. <nplcit><text>R. Iller, The Chemistry of Silica (Wiley, New York, 1979)</text></nplcit>, The Si starting materials that are used most frequently, are silicon alkoxides having the formula Si (OR)₄Which hydrolyze with the addition of water. Under acidic conditions, linear aggregates are formed preferably. Under basic conditions react the silicon alkoxides to form highly crosslinked "globular" particles. The sol-gel coatings containing precondensed particles and clusters.

0077To produce a silica-dipping solution for the glass or glass ceramic substrate according to the present invention, the dipping solution is preferably prepared as follows: The starting silicon compound (s) is (are) dissolved in an organic solvent. The solvents used may be all organic solvents which dissolve the starting silicon compound (s) and are capable of a sufficient amount to dissolve in water, which is necessary for the hydrolysis of the starting silicon compounds. Suitable solvents include toluene, cyclohexane, or acetone, but in particular C_1-6Alcohols. Examples are methanol, ethanol, propanol, butanol, pentanol, hexanol or isomers thereof. It is advantageous to use lower alcohols, especially methanol and ethanol, as these are easy to handle and have a relatively low vapor pressure.

0078The employed starting silicon compound is in particular a C_1-4Alkyl esters of silicic acid, ie, silica methyl esters, ethyl, propyl or butyl. Silicic acid methyl ester is preferred.

0079The concentration of the starting silicon compound in the organic solvent is conventionally set at 0.05 to 1 mol / liter. For the hydrolysis of the starting silicon compound this solution in the example described the case with 0.05 to 12 wt .-% water, preferably distilled water, and mixed with 0.01 to 7 wt .-% of an acid catalyst. For this purpose, organic acids are preferably added, such as acetic acid, methoxyacetic acid, polyether carboxylic acids (eg. B. ethoxyethoxyacetic acid), citric acid, para-toluenesulfonic acid, lactic acid, methacrylic acid or acrylic acid or mineral acids such as HNO₃, HCl or H₂SO₄,

0080The pH of the solution should preferably be about ≤. 3 If the solution is not sufficiently acidic is (pH> 3), there is a danger that the polycondensates / clusters are too large.

0081In a further embodiment, the solution can be prepared in two steps. The first step is carried out as described above. This solution is then allowed to stand (mature). The maturation period is achieved, that the matured solution is diluted with further solvent and / or the tire is terminated under shifting the pH of the solution in the strongly acidic range. Moving in a pH range of 1.5 to 2.5 is preferred. The shifting of the pH in the strong acid region is preferably formed by adding an inorganic acid, more preferably achieved by adding hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, or any organic acid such as oxalic acid or the like. The strong acid is preferably added in an organic solvent, preferably in the solvent in which the starting silicon compound is already dissolved. It is here also possible to add the acid in an amount sufficient, together with the solvent, preferably so that the dilution of the starting solution and the cancel of the maturation process to take place again in alcoholic solution, in one step.

0082The sol-gel coatings include precondensed particles and clusters, which can have various structures. These structures can be determined using light scattering experiments. By means of the process parameters, such as temperature, rate of addition, stirring speed, but in particular by the pH, it is possible that these structures are produced in the sols. It hasshown that the use of small silica polycondensates / clusters with a diameter of ≤ 20 nm, preferably ≤ 4 nm, more preferably in the range of 1 to 2 nm, allows to produce dip-layers, which are packed more densely than conventional silicon oxide layers , This leads, for example, to an improvement of the chemical resistance of the layer.

0083A further improvement of chemical resistance and the function as a bonding layer is achieved in that the solution is mixed with small amounts of a Zumischungsmittels or more additives which are present homogeneously distributed in the solution and also in the subsequent layer, forming a mixed oxide. Suitable additives are hydrolyzable or dissociating inorganic salts, optionally containing water of crystallization, selected from the salts of tin, aluminum, phosphorus, boron, cerium, zirconium, titanium, cesium, barium, strontium, niobium and / or magnesium. Examples include SnCl₄, SnCl₂, AlCl₃, Al (NO₃)₃, Mg (NO₃)₂, MgCl₂, MgSO₄, TiCl₄, ZrCl₄, CeCl₃, Ce (NO₃)₃ and the same. These inorganic salts can be used either in hydrated form as well as water of crystallization.

0084According to a further embodiment of the invention the or the additives used may be selected from one or more metal alkoxides of tin, aluminum, phosphorus, boron, cerium, zirconium, titanium, cesium, barium, strontium, niobium and / or magnesium, preferably titanium, zirconium, aluminum or niobium. Also suitable are esters of phosphoric acid such as phosphoric acid, methyl acetate or ethyl acetate, phosphorus halides, such as chlorides and bromides, boric acid esters, such as ethyl, methyl, butyl or propyl esters, boric anhydride, BBr₃, BCl₃, Magnesium methylate or ethylate, and the like.

0085According to another embodiment of the invention the additives may also be selected as inorganic fluorides, z. B. MgF₂, CaF₂ etc., which are preferably present in the form of nanoparticles &lt;200 nm.

0086Particular preference is given the additives used when the anti-reflective coating or parts of the antireflective coating is present as a sol-gel coating in the form of an adhesive layer.

0087These one or more additives, for example, in a concentration of about 0.5 to 20 wt .-%, calculated as the oxide (or fluoride), based on the silicon content of the solution, calculated as SiO₂Added. The additive or additives may be used in combination.

0088If the dip is to be stored or used in other ways than through a prolonged period, it may be advantageous if this solution by adding one or more complexing agents is stabilized. This complexing agent should be soluble in the dipping solution and may correspond to the solvent of the dipping solution.

0089Complexing agents, which can be used include, for example ethyl acetoacetate, 2,3-pentanedione (acetylacetone), 3,5-heptanedione, 4,6-nonanedione, 3-Metyhl-2,4-pentanedione, 2-methylacetylacetone, triethanolamine, Diethynolamin, ethanolamine, 1,3-propanediol, 1,5-pentanediol, carboxylic acids, such as acetic acid, propionic acid, ethoxyacetic acid, methoxyacetic acid, polyether carboxylic acids (eg. B. ethoxyethoxyacetic acid), citric acid, lactic acid, methyl acrylic acid and acrylic acid and the like.

0090The molar ratio of complexing agent to Halbmetalloxidvorläufer and / or metal oxide precursor may be in the range of 0.1 to fifth

0091In a preferred embodiment, the glass or glass ceramic material during the sol-gel coating with a target speed of about 50-1500 mm / min., Preferably from 200 to 1000 mm / min., More preferably about 300-1,000 mm / min. pulled out of the solution, wherein the moisture content of the ambient air is between about 4 g / m³ and about 12 g / m³, More preferably at about 8 g / m³ lies.

0092The dip-coated layer may be dried after application in order to obtain greater mechanical strength. The drying may, for example, in a high temperature furnace can be performed in a very wide temperature range. Typically, drying times of a few minutes ago, at temperatures ranging from 100-200 ° C.

0093The formation of the deposited layer takes place in a high-temperature step, during which the organic components of the gel are preferably burned out. Finally the mixed oxide layer, preferably to form Siliciummischoxidschicht, which can for example act as an adhesion promoter layer, this below the softening temperature of the glass or glass-ceramic material, preferably atTemperatures of less than 550 ° C, more preferably between 350 and 500 ° C, more preferably between 400 and 500 ° C, heated. It is also possible to use temperatures of more than 550 ° C, but the time should be preferably selected short so that it is not to deform the glass substrate (depending on the thickness of the glass substrate). However, such temperatures are not usually lead to a further improvement of the adhesion strength of the layer.

Antimicrobial (AM) property and chemical tempering by ion exchange

0094Using an ion exchange process of the coated glass or glass ceramic surface are imparted antimicrobial properties. For this purpose, one or more antimicrobial salts, in particular one or more antimicrobial metal salts in the substrate, and probably introduced the then present (s) layer (s) in an antimicrobially effective amount, wherein the metal is preferably selected from the group consisting of silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium and / or nickel. Particularly preferred are silver salts, particularly silver nitrate, silver chloride, silver fluoride, silver bromide, silver oxide, silver sulfate, silver carbonate, silver cyanide, silver tetrafluoroborate, silver sulfide, silver acetate, silver lactate, silver benzoate, Silbercyclohexanbutyrat, Silberdiethyldithiocarbamat, silver trifluoromethanesulfonate, and mixtures thereof. Particularly preferred are AgCl / AgNO₃- And / or ZnCl- and / or ZnNO₃-containing mixtures. The imparting antimicrobial properties is inventively by ion exchange in a salt or molten, wherein the ion exchange is performed with the glass or the glass ceramic and the present on the antireflective coating. The ion exchange for the finishing of glass or glass-ceramic substrate having antimicrobial properties is carried out as the ion exchange to the chemical tempering.

0095The glass or glass ceramic substrate of the present invention can-depending on the desired property profile - be chemically biased so as to have higher mechanical strength and Kratzbeständigeit as without chemical tempering. The chemical tempering is in the context of the present invention also known by ion exchange, as in the prior art, carried out, according to the invention, however, the ion exchange performed by the anti-reflective coating present on the glass or the glass ceramic therethrough. The ion exchange of smaller alkali metal ions, eg., Sodium and / or lithium ions from the glass by more alkali metal ions such as potassium, rubidium and / or cesium ions, resulting in a compressive stress layer, the mechanical damage, such as scratching or abrasion , prevented, thus making the glass or the glass ceramics more resistant to damage. The chemical tempering can be carried out in the context of the present invention depending on the desired application and the required property combinations or omitted.

0096The chemical tempering is carried out for example by immersion in a potassium-containing, preferably potassium nitrate-containing molten salt. There is also the possibility of an aqueous potassium silicate solution, paste or dispersion use, such as in the<patcit><text>WO 2011/120656</text></patcit> described in detail. The chemical tempering can be characterized by the depth of penetration (DoL, depth of ion Exchanged layer) and the compressive stress (CS, compressive strength).

0097When the glass or glass ceramic surface having antimicrobial properties and at the same time should be chemically prestressed, the glass or glass ceramic substrate is treated, for example, in two successive steps, that is, the glass or the glass ceramic can be chemically prestressed in a first step and provided with antimicrobial in a second step ,

0098In the present invention, it has however been found to be particularly advantageous when both treatments simultaneously in one step durchgefü be HRT (process variant (2)), or if two steps are performed, wherein in the first step, chemically prestressed and provided with antimicrobial in the second step becomes. Preferably, in the second step a mixture of antimicrobial (s) compound (s) and suitable chemical tempering (s) alkali metal salt (s) is used in a salt bath (process variant (3)). The ion-exchange in the first step is then carried out for example in a potassium nitrate salt bath and the second step is carried out for example with a mixture of potassium salt (s) and silver salt (s), z. B. a mixture of KNO₃ and AgNO₃,

0099If only one step is carried out or carried out of the first ion exchange step to chemical tempering, so the ion exchange method is preferably carried out in a salt bath at a temperature between 350 and 500 ° C for a period of preferably 0.5 to 48 hours. If aluminum silicate and Boroaluminosilikatgläser or glass ceramics based thereon are used as substrates, isthe temperature is preferably at 400 to 450 ° C and the time 1-8 hours. If a soda-lime glass or a glass ceramic based thereon is used, the temperatures are preferably at 390 to 480 ° C for a period of between 2 and 24 hours. Borosilicate glass ceramics or based thereon to be treated for example at temperatures 440-500 ° C for a life of 4 to 48 hours.

0100Is chemical tempering and antimicrobial finishing in a single ion exchange step (to variant (2)) is performed, the concentration of the one or more antimicrobial metal salts in the salt bath, for example in the form of one or more silver salts, preferably from 0.01 to 2 wt %, more preferably 0.01 to 0.5 wt .-%. When the ion exchange step for the antimicrobial finishing the second step (variant (3)), which is performed after chemical tempering, the ion exchange process is carried out at a temperature between 400 and 500 ° C for 0.25 to 2 hours. The concentration of the one or more antimicrobial metal salts in the second salt bath, for example in the form of one or more silver salts, also is preferably 0.01 to 2 wt .-%, more preferably 0.01 to 0.5 wt .-%.

0101It has been surprisingly found that by carrying out the ion exchange process, whether obtained by one or two steps, the desired anti-microbial properties and corresponding to the same characteristics of a chemically tempered glass or glass ceramic substrate. For example, for aluminosilicate and Boroaluminosilikatgläser and then glass ceramics based found that the compressive stress of the surface CS (Compressive stress) is ≥ 600 MPa and the depth of compressive stress layer DoL (depth of ion Exchanged layer) ≥ 20 microns. For soda-lime glasses and based thereon glass ceramics has been found that the compressive stress of the surface CS ≥ 100 MPa, preferably ≥ 200 MPa, more preferably is ≥ 300 MPa, and the depth of the surface compression stress DoL is ≥ 5 microns. These values ​​are in the same range as for glasses or glass-ceramics which have been chemically biased only by ion exchange, without this at the same time provide antimicrobial.

0102Furthermore, it was found that the glass or glass-ceramic substrates produced by the method according to the invention preferably an antimicrobial efficacy of> 90% compared to E. coli and S. aureus have, more preferably greater than 99%, more preferably> 99.9%, particularly preferably> 99, 99%. The method for measuring the antimicrobial activity is carried out in accordance with the<nplcit><text>Standard JIS Z 2801</text></nplcit> or <nplcit><text>ISO 22196</text></nplcit>, The values ​​for the antimicrobial activity in the same range as for glasses or glass ceramics, which are antimicrobial equipped only.

0103The glass and / or glass ceramic substrates according to the present invention moreover have an antimicrobial activity against other bacteria, such as K.pneumoniae and P.aeruginosa. It is known that, for example, silver ions have an antimicrobial effect against about 650 types of bacteria and other microorganisms, including viruses, bacteria, fungi, algae and the like, so that the antimicrobial substrates about this range of properties of the invention may fully equipped.

Anti-fingerprint (AF) coating

0104The ion-exchanged anti-reflective coated glass and / or glass-ceramic substrate may be in accordance with an embodiment of the present invention, provided with an AF-coating, which is also referred to as easy-to-clean coating or amphiphobe coating.

0105An AF coating has hydrophobic and oleophobic, ie amphiphobe, characteristics such that the wetting of the surface by water and oils is minimized. The wetting characteristics of a surface having an AF coating must therefore be such that the surface is both hydrophobic, ie, the contact angle between the surface and water is preferably greater than 90 °, as is also oleophobic, ie, the contact angle between the surface and oil is preferably greater than 50 °.

0106The AF coating may be a surface layer comprising containing a silane, the alkyl and / or fluoroalkyl groups, such as. For example, 3,3,3-trifluoropropyltrimethoxysilane or pentyltriethoxysilane.

0107The AF-coating may also be a surface layer of fluorine-based, based on compounds containing hydrocarbon groups, wherein the CH bonds have been partially or preferably substantially all replaced by CF bonds. Such compounds are preferably perfluorocarbons, for example, the formula (R_F)_nSiX_4-n , said R_F a C₁- To C₂₂-Alkylperfluorkohlenwasserstoff Or -Alkylperfluorpolyether, preferably C₁- To C₁₀-Alkylperfluorkohlenwasserstoff Or -represents Alkylperfluorpolyether, n is an integer from 1 to 3, X is a hydrolyzable group such as halogen or an alkoxy group -OR, in which R, for example, represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms. In this case, the hydrolyzable group X for example, react with a terminal OH group of the coating of the glass substrate and so bind to this by forming a covalent bond. Perfluorocarbons be advantageously used to reduce the surface energy of the surface due to the low polarity of the terminal fluorine surface bonds.

0108The AF coating may for example also consist of a monolayer of a molecular chain with Fluorendgruppen, a fluoropolymer coating or of silica soot particles derived previously provided with Fluorendgruppen or treated with these.

0109AF-coatings are for example in the <patcit><text>DE 19848591</text></patcit>. <patcit><text>EP 0844265</text></patcit>. <patcit><text>US 2010/0279068</text></patcit>. <patcit><text>US 2010/0285272</text></patcit>. <patcit><text>US 2009/0197048</text></patcit> and the <patcit><text>WO 2012/163947 A1</text></patcit> the disclosure of which is incorporated herein by reference in the present invention. Known AF coatings are for example products based on perfluoropolyether under the name "Fluorolink^® PFPE "as" Fluorolink^® S10 ", Fa. Solvay Solexis or" Optool^TM DSX "or" Optool^TM ÄS4-E "the Fa. Daikin Industries LTD," Hymocer^® ECG 6000N "from the company ETC Products GmbH or Fluorosilanes under the name" FSD "as" FSD 2500 "or" FSD 4500 "by Cytonix LLC or Easy Clean Coating" ECC "products as" ECC 3000 "or" ECC 4000 " by the company. 3M Germany GmbH. It is applied in liquid form layers. AF-coatings, for example, as nano coating systems which are applied by means of physical vapor deposition, offered for example by the company. Cotec GmbH under the name "DURALON UltraTec".

0110The coating may be suitable to the surface by dipping, vapor coating, spraying, applying with a roller or a roller or a doctor blade, by thermal vacuum deposition or sputtering, preferably by liquid phase method, such as spraying, dip coating, printing, rolling, spin coating or other The method can be applied. Dipping or spraying are particularly preferred. After the coating was applied, this is preferably cured at a suitable temperature for a suitable period of time.

0111The water contact angle of the AF coating is preferably> 90 °, more preferably> 100 °, in particular preferably> 110 °.

0112In the present invention it was found that the coating applied to the glass or glass ceramic substrate in the form of the AF coating has no adverse influence on the release of the antimicrobial ions from the glass or glass ceramic surface and therefore do not adversely antimicrobial on the effectiveness of the obtained antimicrobial glass and / or glass ceramic surface impact.

0113According to the invention it was also found that the application of an AF layer regularly leads to an AR coating to improve the abrasion resistance of the entire coating system.

Antiglare property

0114Additionally or alternatively, one of the properties described, the glass or glass ceramic substrate of the invention may also have anti-glare properties.

0115An anti-glare surface describes a surface that can physically transform the light radiation in a diffuse reflection instead of a specular reflection. An anti-glare surface is useful in situations where a high transmission is not as important by a surface, but rather a low reflectivity is required. The anti-glare function may be present in the present invention, for example combined with the AM, AR, AF properties and optionally a chemical tempering in a glass or glass ceramic surface.

0116There are several ways to make a glass surface matt. Eg embossing structures during a hot molding or etching the glass surface by acid. Subsequently, the surface can more AR layers are coated with one or. It is also small particles are incorporated into an AR coating, excluding the top layer of AR coating, or it may be aTexture or a pattern can be incorporated into the surface or applied to this in order to enhance the surface diffusion of light. Furthermore, the features described may also already at an antiglare glass substrate, such as Xensation Cover AG, sold by Schott AG, with the multi-functionality such as AM, AR, optional AF and possibly. Chemical tempering, be combined.

0117An anti-glare coating may therefore, for. Example, be produced by embossing a sol-gel layer or adding nanoparticles into the sol-gel solution so that the roughness is increased, and preferably in the range of 5 nm to 5 microns.

0118It has an anti-glare surface, which is obtained for example in the form of a matte and / or etched and / or structured surface, the specular reflection is transformed into gloomy reflection. This so-called spread of reflected light makes reflected images blurred, so that different shapes and reflected light sources not detract from the behind the glass or the glass ceramic sitter. The scattering of the light does not reduce the total reflection or the absorption of the irradiated light to the glass or glass ceramic surface or glass or glass-ceramic substrate. Rather, the light is not only directed, but scattered in all directions. The total amount of light remains the same.

0119Etched surfaces have the following advantages: The diffuse scattering bright reflected light enables a better identification of transferred images and text. Sometimes structured surfaces are also used as an alternative to anti-reflection coatings. The shine directly reflected light sources is reduced here. The surface displays because of their structure reduced coefficient of static friction in contact with a variety of fabrics and finishes. The concomitant better feel makes them particularly attractive for use in touch screen applications. The reduced effective area of ​​contact between such a structured surface and other surfaces in contact leads to a purely mechanically induced "anti-fingerprint" functionality. This also motivates often use in touch screen applications. However, let contaminants which have found their way into the structures of the surface only once, heavier remove than a corresponding smooth surface.

0120In one embodiment of the present invention, the anti-reflective layer, for example be used in combination with an anti-glare coating. The anti-reflective layer and an AF layer which is applied to, take over the roughness of the antiglare layer, while the AF and antireflective properties are maintained.

The glass or glass ceramic substrate

0121Any glass or glass ceramic composition in which the desired ion exchange, for example sodium to potassium ions for chemical tempering, and / or sodium can be against silver ions for antimicrobial finishing of the glass or glass ceramic, conducted can be used according to the present invention. The glass or glass ceramic material that is provided with the AR coating is any ion exchangeable glass or a glass-ceramic ion-exchangeable. Preferably, the glass is selected from: silicate glass, phosphate glass, borosilicate glass, aluminosilicate glass, Boraluminosilikatglas, Zinnphosphatglas, Borphosphatglas, Titanatglas, barium, preferably alkali metal-containing silicate glass, and more preferably sodium-containing silicate glass.

0122The glass is, for example, an alkali-aluminosilicate glass with the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">40-75</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">10-30</entry></row><row><entry colname="col1">8203</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">Sum of Li₂O + Na₂O + K₂O</entry><entry colname="col2">4-30</entry></row><row><entry colname="col1">Sum of MgO + CaO + SrO + BaO + ZnO</entry><entry colname="col2">0-15</entry></row><row><entry colname="col1">Sum of TiO₂ + ZrO₂</entry><entry colname="col2">0-15</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-10</entry></row></tbody></tgroup></table></tables>

0123The glass material is for example a borosilicate glass with the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">60-85</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">1-10</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">5-20</entry></row><row><entry colname="col1">Sum of Li₂O + Na₂O + K₂O</entry><entry colname="col2">2-16</entry></row><row><entry colname="col1">Sum of MgO + CaO + SrO + BaO + ZnO</entry><entry colname="col2">0-15</entry></row><row><entry colname="col1">Sum of TiO₂ + ZrO₂</entry><entry colname="col2">0-5</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-2</entry></row></tbody></tgroup></table></tables>

0124The glass material is for example a soda-lime glass having the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">40-80</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">0-6</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">0-5</entry></row><row><entry colname="col1">Sum of Li₂O + Na₂O + K₂O</entry><entry colname="col2">5-30</entry></row><row><entry colname="col1">Sum of MgO + CaO + SrO + BaO + ZnO</entry><entry colname="col2">5-30</entry></row><row><entry colname="col1">Sum of TiO₂ + ZTO₂</entry><entry colname="col2">0-7</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-2</entry></row></tbody></tgroup></table></tables>

0125The glass material is for example an aluminosilicate glass with low alkali content with the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">50-75</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">7-25</entry></row><row><entry colname="col1">6203</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">Sum of Li₂O + Na₂O + K₂O</entry><entry colname="col2">1-4</entry></row><row><entry colname="col1">Sum of MgO + CaO + SrO + BaO + ZnO</entry><entry colname="col2">5-25</entry></row><row><entry colname="col1">Sum of TiO₂ + ZrO₂</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-5</entry></row></tbody></tgroup></table></tables>

0126The glass material is preferably a lead glass having the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">PbO</entry><entry colname="col2">20-80</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">20-60</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">1-10</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">SrO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">F₂O₃</entry><entry colname="col2">0-1</entry></row><row><entry colname="col1">Sb₂O₃</entry><entry colname="col2">0-1</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">0-10</entry></row></tbody></tgroup></table></tables>

0127The glass material is preferably a glass having the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">10-90</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">0-40</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">0-80</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">1-30</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0-30</entry></row><row><entry colname="col1">CoO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">NiO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">Ni₂O₃</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">MnO</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">0-40</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">0-60</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-40</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">MnO₂</entry><entry colname="col2">0-10</entry></row><row><entry colname="col1">CeO</entry><entry colname="col2">0-3</entry></row><row><entry colname="col1">SnO₂</entry><entry colname="col2">0-2</entry></row><row><entry colname="col1">Sb₂O₃</entry><entry colname="col2">0-2</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">0-40</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-70</entry></row><row><entry colname="col1">MgO</entry><entry colname="col2">0-40</entry></row><row><entry colname="col1">SrO</entry><entry colname="col2">0-60</entry></row><row><entry colname="col1">Li₂O</entry><entry colname="col2">0-30</entry></row><row><entry colname="col1">Li₂O + Na₂O + K₂O</entry><entry colname="col2">1-30</entry></row><row><entry colname="col1">SiO₂ B +₂O₃ + P₂O₅</entry><entry colname="col2">10-90</entry></row><row><entry colname="col1">Nd₂O₅</entry><entry colname="col2">0-20</entry></row><row><entry colname="col1">V₂O₅</entry><entry colname="col2">0-50</entry></row><row><entry colname="col1">Bi₂O₃</entry><entry colname="col2">0-50</entry></row><row><entry colname="col1">SO₃</entry><entry colname="col2">0-50</entry></row><row><entry colname="col1">SnO</entry><entry colname="col2">0-70</entry></row></tbody></tgroup></table></tables> wherein the content of SiO₂ + P₂O₅ B +₂O₃ 10-90 .-% is.

0128The glass material is preferably a lithium-aluminum silicate glass having the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">55-69</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">19-25</entry></row><row><entry colname="col1">Li₂O</entry><entry colname="col2">3-5</entry></row><row><entry colname="col1">Sum of Na₂O + K₂O</entry><entry colname="col2">0.5-15</entry></row><row><entry colname="col1">Sum of MgO + CaO + SrO + BaO</entry><entry colname="col2">0-5</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-4</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">0-5</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">0-3</entry></row><row><entry colname="col1">Sum of TiO₂ + ZrO₂ + SnO₂</entry><entry colname="col2">2-6</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-8</entry></row><row><entry colname="col1">F</entry><entry colname="col2">0-1</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">0-2</entry></row></tbody></tgroup></table></tables>

0129The above glass compositions may optionally contain additives of coloring oxides, such. As Nd₂O₃, Fe₂O₃, CoO, NiO, V₂O₅, MnO₂, TiO₂, CuO, CeO₂, Cr₂O₃, Rare earth oxides in amounts of 0-5 wt .-% and for "Black Glass" of 0-15 wt .-%, and refining, such as As₂O₃, Sb₂O₃, SnO₂, SO₃, Cl, F, CeO₂, Wt .-% in grades 0-2.

0130The components of the glass compositions always 100 wt .-%.

0131The glasses can be prepared by float technology or from a cast or rolled glass, for example by means of a drawing process, as Updraw- or downdraw drawing process, overflow fusion. Particularly in a casting or rolling process or a floated glass, it may be that a polishing technology the necessary optical quality of the surface is achieved, which is required, for example, for a display-viewing pane.

0132In a further aspect of the present invention, the substrate may also be a glass-ceramic which is obtained by converting the glass using a thermal treatment. Glass ceramics is a kind of crystallized glass. The glass can be crystallized completely or partially, for example, only the upper part of the surface and / or a lower portion of the surface to be crystallized. The glass-ceramic material has different properties than glass and other properties than ceramic. Glass-ceramic has an amorphous phase and one or more crystalline phases, which is produced by "crystallization control" as opposed to spontaneous crystallization, which is not desirable in a glass product. Glass-ceramic typically has 30-90 Vol .-% on of crystalline phase and can thus be used to prepare a series of materials with interesting mechanical properties.

0133The ceramic used in the invention can be prepared for example by the following method: During the glass manufacturing process, the raw materials are initially at a high temperature higher than 1000 ° C, 1200 ° C, 1300 ° C, 1400 ° C, 1500 ° C, 1550 ° C, 1600 ° C or 1650 ° C is melted to form glass, wherein the glass melt is formed after the homogenization and is then carried out at a predetermined temperature after the cooling, a nucleation and crystallization in order with homogeneous structure to obtain a glass-ceramic article with fine grains. The resulting ceramic has no pores generally.

0134Typically suitable crystallization agents can be used for crystallization (nucleation), such as TiO₂, ZrO₂, HfO₂ or other known components, the total amount of the crystallization agent than 5 wt .-%, preferably at most 3 wt .-% and more preferably at most 2 wt .-%, based on the total amount of the glass composition.

0135The glass ceramic can be a silicate, aluminosilicate, fluorosilicate glass ceramic z. B.. In the glass-ceramic, the predominant crystal phase may be selected from the group consisting of lithium, enstatite, wollastonite, filled β-quartz, β-spodumene, cordierite, mullite, Kaliumrichterit, canasite, solid Spinelllösung and quartz.

0136The glass ceramic according to the present invention is preferably transparent. This can, as already described for the glass having a multi-functional surface comprising comprise according to an embodiment of the invention durable antimicrobial, anti-reflective, anti-fingerprint characteristics optionally antimicrobial together with chemical tempering or according to a further embodiment of the invention and antireflective functions, wherein the substrate is biased chemically is.

0137The glass-ceramic preferably has a crystalline phase of at least 30 vol .-%.

0138The thickness of the glass ceramic is preferably less than 20 mm, more preferably less than 15 mm, less than 10 mm, less than 5 mm, less than 3 mm, less than 1 mm, less than 0.7 mm, less than 0.5 mm or less than 0.1 mm.

0139in one embodiment, the substrate is a glass-ceramic of a ceramized aluminosilicate glass or lithium alumino-silicate glass.

0140Preferred is a glass ceramic or a ceramizable glass with the following composition of the starting glass used (in wt .-%): <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">Li₂O</entry><entry colname="col2">3.2 to 5.0</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">Total Na₂O + K₂O</entry><entry colname="col2">0.2-2.0</entry></row><row><entry colname="col1">MgO</entry><entry colname="col2">0.1 to 2.2</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">SrO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">0-2.5</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">19-25</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">55-69</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">1.0-5.0</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">1.0-2.5</entry></row><row><entry colname="col1">SnO₂</entry><entry colname="col2">0-1.0</entry></row><row><entry colname="col1">Total TiO₂ + ZrO₂ + SnO₂</entry><entry colname="col2">2.5-5.0</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-3.0.</entry></row></tbody></tgroup></table></tables>

0141In another embodiment, a glass ceramic or a ceramizable glass with the following composition of the starting glass is preferably used (in wt .-%): <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">Li₂O</entry><entry colname="col2">3-5</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">Total Na₂O + K₂O</entry><entry colname="col2">0.2-2</entry></row><row><entry colname="col1">MgO</entry><entry colname="col2">0.1-2.5</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">0-2</entry></row><row><entry colname="col1">SrO</entry><entry colname="col2">0-2</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">0-3</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">15-25</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">50-75</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">1-5</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">1-2,5</entry></row><row><entry colname="col1">SnO₂</entry><entry colname="col2">0-1.0</entry></row><row><entry colname="col1">Total TiO₂+ ZrO₂ + SnO₂</entry><entry colname="col2">2,5-5</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-3.0.</entry></row></tbody></tgroup></table></tables>

0142In a further embodiment, a glass ceramic or a ceramizable glass with the following composition of the starting glass is preferably used (in wt .-%): <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">Li₂O</entry><entry colname="col2">3-4,5</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">Total Na₂O + K₂O</entry><entry colname="col2">0.2-2</entry></row><row><entry colname="col1">MgO</entry><entry colname="col2">0-2</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">SrO</entry><entry colname="col2">0-1.5</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">0-2.5</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">0-2.5</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">0-1</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">19-25</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">55-69</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">1.4 to 2.7</entry></row><row><entry colname="col1">ZrO₂</entry><entry colname="col2">1.3-2.5</entry></row><row><entry colname="col1">SnO₂</entry><entry colname="col2">0-0.4</entry></row><row><entry colname="col1">Total TiO₂ + SnO₂</entry><entry colname="col2">less than 2.7</entry></row><row><entry colname="col1">P₂O₅</entry><entry colname="col2">0-3</entry></row><row><entry colname="col1">Total ZrO₂ + 0.87 (TiO₂ + SnO₂)</entry><entry colname="col2">3.6-4.3.</entry></row></tbody></tgroup></table></tables>

0143The glass ceramic preferably contains high quartz mixed crystals or keatite mixed crystals as the predominant crystal phase. The crystallite size is preferably less than 70 nm, particularly preferably less than or equal to 50 nm, very particularly preferably less than or equal 10 nm.

0144The surface of the glass or glass ceramic substrate can be polished, or be provided with patterned texture, such as by acid / alkali etching, depending on the required surface characteristics, to meet the desired application conditions such. As good tactile properties.

0145The glass or glass ceramic substrates of the invention find use everywhere Ver where the combinations of properties in the form of anti-reflective behavior, anti-microbial properties and optionally increased strength and scratch resistance, and optionally anti-fingerprint properties are appropriate and necessary.

0146possible to use the present with multifunctional properties of glass or glass-ceramic substrates of the invention, for example, for all kinds of display applications, such as display applications with touch screen function as a single-, dual- or multi-touch displays, 3D displays and flexible displays. The substrates of the invention to avoid interfering or contrast-reducing reflections can for example be used as substrates for all types of interactive input elements that are especially designed with touch function, preferably with resistive, capacitive, optical, by infrared or surface acoustic wave acting touch technology. In this area, the provision of anti-microbial properties is particularly advantageous because one or more users repeatedly come into direct contact with the substrate. The chemically tempered substrate has higher strength and is more scratch resistant and is therefore used to particular advantage in this area.

0147Systems which operate with light injection, such as infrared or optical effect touch technologies, are sensitive to the presence of dirt and debris on the touch surface, because it may give rise to additional reflections due to deposits. Therefore, it is expedient if, in this region on the substrate an additional AF-coating is provided.

0148Other applications for avoiding disruptive or contrast-reducing reflections with the same permanent antimicrobial properties and possibly anti-fingerprint properties are, for example, windows in indoor and outdoor applications, such as shop windows, glazing pictures, display cases, counters or cooling furniture, decorative glass elements, especially in areas exposed to higher risk of contamination, such as kitchens, bathrooms, or laboratories or covers of solar modules.

0149Applications are also in the household, especially in kitchens, bathrooms, components on / in the fridge, component in / on the hob, particularly in cooktops and the like.

0150It may be advantageous if, in addition AR and AM properties simultaneously present long-term stable AF properties. In particular, decorative items, having a printing on the back of the glass or the glass ceramic or have a reflective coating, benefit from an AF coating. These elements, which are used for example as a cooker front panels or in other kitchen appliances, occur in use repeatedly with fingerprints or greasy substances in contact. The surface looks very unsightly and unsanitary quickly in these cases from. The AF-coating improves the visual appearance and is easier to clean. The simultaneous provision of anti-microbial properties protects the user from bacteria, when the substrates are touched.

0151The glass or glass ceramic substrates of the invention may also be in the medical field, such as hospitals, doctors' practices or pharmacies, and generally in the pharmaceutical industry, can be advantageously used, where it is essential that the occurrence of germs already on existing surfaces such as shelves, containers, washers and the like is suppressed.

0152Find use glass or glass-ceramic substrates of the invention also in glazing of all kinds, in particular slices in the indoor and outdoor use, such as shop windows, glazing pictures, display cases, counters, windows, such windows, especially fire protection windows, automobile windows, train, airplane windows, insulating glass doors for cupboards , indicating or advertising boards, photo frames, architectural glass, for example for use in an exhibition, generally for the protection of any works of art or objects on display.

0153Preferred embodiments of the present invention are described below with reference to the drawings in greater detail, without restricting the present invention thereto. Specifically:

0154<figref>1</figref> a schematic representation of an embodiment of the invention the method of the present invention;

0155<figref>2</figref> a schematic representation of an embodiment of the invention a glass or Glaskermiksubstrats with an antireflective coating in the form of three layers;

0156<figref>3</figref> a schematic representation of an embodiment of the invention a glass or Glaskermiksubstrats with an antireflective coating in the form of four layers;

0157<figref>4</figref> a schematic representation of an embodiment of the invention a glass or Glaskermiksubstrats with an antireflective coating in the form of a single layer which is an adhesive layer in the present case;

0158<figref>5</figref> the representation of the comparison of the different transmissions (in%), plotted against the wavelength (in nm) of the untreated glass substrate, the anti-reflective coated glass substrate prior to the ion exchange as well as the glass substrate according to the invention prepared according to Example 1;

0159<figref>6</figref> a diagram for comparison of the different transmissions (in%), plotted against the wavelength (in nm) of the untreated glass substrate and the glass substrate according to the invention prepared according to Example 2. FIG.

0160<figref>7</figref> a diagram for comparison of the reflections (in%), plotted against versus wavelength (in nm) of the glass substrate prepared according to Example 3 and after ion exchange;

0161<figref>8th</figref> a diagram for comparison of the reflections (in%), plotted against versus wavelength (in nm) of the glass substrate prepared in Example 4 and after ion exchange;

0162<figref>9</figref> a diagram for comparison of the different transmissions (in%), plotted against the wavelength (in nm) of the untreated glass substrate and the glass substrate according to the invention prepared according to Example 5; and

0163<figref>10</figref> a diagram for comparison of the different transmissions (in%), plotted against the wavelength (in nm) of the untreated glass substrate and the glass substrate according to the invention prepared according to Example 6. FIG.

0164In <figref>1</figref> is a schematic representation of an inventive embodiment of the method of the present invention is illustrated. Here, first, a glass or glass-ceramic substrate<figref>2</figref> provided. On the surface<figref>20</figref>Which is optionally purified first, an antireflective coating is applied. Depending on the embodiment, the coating may also on both surfaces (not shown) of glass or glass-ceramic substrate<figref>2</figref> be applied. The antireflective coating can represent any coating with antireflective properties. For example, this from a layer at least 2 layers with alternating high and low refractive index or at least 3 layers be constructed with alternating medium, high and low refractive index. In the illustrated embodiment, the antireflective coating of a single layer<figref>5</figref> (<figref>4</figref>) Or of at least 2 layers <figref>3</figref> and <figref>4</figref> (<figref>2</figref> and <figref>3</figref>) Constructed of high and low refractive index, wherein the outer or top layer <figref>31</figref>. <figref>41</figref>. <figref>5</figref> the layer packet having a low refractive index. The layer<figref>31</figref>. <figref>41</figref>. <figref>5</figref> may be an adhesion promoter layer according to a preferred embodiment. The adhesive layer is preferably an oxide layer, preferably a Siliciummischoxid layer.

0165Hereinafter, the present antireflective coating with the glass or glass ceramic substrate <figref>2</figref> then subjected to an ion exchange. For this purpose, according to one of the variants of the invention either equipped only antimicrobial, or provided with antimicrobial and chemically biased. Metal salts having antimicrobial activity are, for example, silver, copper, cadmium, zinc, iron, tin, cobalt, cerium, antimony, selenium, chromium, magnesium and / or nickel salts. For chemical tempering any purpose suitable compounds can be used. Conventionally, potassium, rubidium and / or cesium salt are used. When the glass or glass ceramic substrate<figref>2</figref> to be treated anti-microbially and chemically prestressed, this may be carried out in one or two steps. If this is to be carried out in one step, which is suitable for the chemical tempering metal salts and the antimicrobial metal salts are mixed with each other in a salt bath, and the glass or glass ceramic substrate<figref>2</figref> dipped in the salt bath. If this is to be carried out in two steps, is preferably chemically prestressed in the first step in a first salt bath and provided with antimicrobial in a second salt bath until the second step. It is particularly advantageous if the second salt bath containing a mixture of potassium, rubidium and / or cesium salt containing one or more metal salts having antimicrobial activity. The ion exchange takes place through the antireflective coating through, so that it is the entire substrate with the or gathers thereto existing layers (this with the bracket in<figref>1</figref> expressed).

0166Following the one or more ion exchange method, an anti-fingerprint coating <figref>6</figref> to the coated, antimicrobial finishes and, optionally, chemically tempered glass or glass ceramic substrate <figref>2</figref> be applied. <figref>2</figref> shows a schematic representation of an embodiment according to the invention of a glass or glass ceramic substrate <figref>2</figref> with an antireflective coating in the form of 3 layers. The layer<figref>33</figref> has an average refractive index (M layer), the layer <figref>32</figref> has a high refractive index (T) layer and the layer <figref>31</figref> has a low refractive index (S-layer). The layer<figref>31</figref> may be an adhesive layer. Before applying the antireflective coating, it may be expedient to the surface<figref>20</figref> the substrate <figref>2</figref> to clean. The glass or glass ceramic substrate<figref>2</figref> has in the example shown antimicrobial properties and is chemically biased.

0167The production of such anti-reflective coating is explained below in Examples in detail.

0168<figref>3</figref> illustrates a schematic representation of a further embodiment according to the invention of a glass or glass ceramic substrate <figref>2</figref> with an antireflective coating in the form of 4 layers (<figref>41</figref>. <figref>42</figref>. <figref>43</figref>. <figref>44</figref>). The 4 layers have alternately a high and a low refractive index and together form the antireflective coating. The top layer<figref>41</figref> is preferably an adhesive layer. The glass or glass ceramic substrate<figref>2</figref> with the coating <figref>4</figref> has in the example shown antimicrobial properties and is chemically biased.

0169<figref>4</figref> shows a schematic representation of another embodiment according to the invention of a glass or glass ceramic substrate <figref>2</figref> with an antireflective coating in the form of a single layer <figref>5</figref> present. This is preferably an adhesive layer. The glass orCeramic substrate <figref>2</figref> has the single layer <figref>5</figref> in the illustrated example case, antimicrobial properties and is chemically prestressed. The production of such a substrate is described in the examples.

0170The <figref>5</figref> to <figref>10</figref> are explained in detail in the examples.

0171The advantages of the present invention are very complex: The present invention provides a unique combination of properties that are present simultaneously and permanently integrated into a glass or glass ceramic substrate. The glass or glass ceramic substrates resistant multifunctional surface properties of the invention include a combination of antimicrobial, anti-reflective and anti-fingerprint functionality, or a combination of anti-microbial, anti-reflective and anti-fingerprint functionality, wherein the substrate is chemically biased, or a combination of anti-microbial and anti-reflective functions, wherein the substrate is chemically prestressed. The invention also provides a process for preparing such substrates.

0172The present invention provides combinations of properties available that are not yet known in this type of the prior art, each individual property or function is not adversely affected by another feature or function, but these rather complement advantageous and any property in full screen is available.

0173It was found that with simultaneous antimicrobial finishing and chemical tempering values ​​for the compressive stress of the surface CS (Compressive stress) and depth of compressive stress layer DoL (depth of ion Exchanged layer) are obtained, which are in the same range as for glasses or glass ceramics, that were chemically pre-stressed only by ion exchange, without this at the same time provide antimicrobial.

0174The presence of an AF coating has has no adverse influence on the release of antimicrobial ions from the glass or glass ceramic surface, so that the antimicrobial properties can freely unfold fully. The application of an AF layer on an AR coating also leads to an improvement in the abrasion resistance of the entire coating system.

0175The glass or glass ceramic substrates of the invention find use everywhere where the property combinations in the form of high strength, anti-reflective properties and antimicrobial properties, and optionally anti-fingerprint properties are appropriate and necessary. The features disclosed in the present invention, glass or glass ceramic substrate can be used for example as a cover glass for any form of touch-screen electronic devices and many devices in the home or industrial applications, such as mobile phones, smart phones, tablet PCs, notebook PCs, televisions, ATM machines, ticket vending machines and can also control, information and / or control panels or windows in every possible shape and size, which are used for example in motor vehicles, hospitals, museums, shops, housing and transport, etc. use.

0176Advantageously, substrates of the invention are used in applications where many functions are present integrated together, such as touch screens of smartphones or tablet PCs. To this end, substrates of the invention are chemically biased exhibit AR and AF-coating and have antimicrobial properties: The glass substrate according to the invention is preferably chemically biased in this case, so that the very thin glass substrates, which are used in touch screens, have sufficiently high mechanical strength. The AR coating enables not only avoidance of disturbing or contrast-reducing reflections to save energy, since due to a reduction of reflections at the glass-air interface, the display module can be operated at a lower brightness. The antimicrobial properties of the glass surface protects the user who continually comes to the glass surface in direct contact, from bacteria that reside 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. In particular, the functions described can be provided with a long shelf life.

0177The inventively prepared glass or glass ceramic substrates give the surface therefore all the functions in a permanent manner, such as that current industry quality standards are met. The inventive method is also suitable for mass production.

0178Hereinafter, the present invention will be explained in more detail by way of examples without limiting it thereto.

Examples

example 1

Glass substrate: soda-lime float glass

0179A carefully cleaned soda lime float glass in a size of 100 × 200 mm was coated with an antireflective coating which was composed of a three-layer structure, such as under <figref>2</figref> shown. The antireflective coating consisted of three layers and had the following structure: glass substrate (<figref>2</figref>) + M layer (<figref>33</figref>) + T-layer (<figref>32</figref>) + S-layer (<figref>31</figref>). The S-layer (<figref>31</figref>) Was also an adhesive layer. The three layers were applied to the glass by dip coating.

0180The solutions for the three layers were prepared as follows:

S-layer:

preliminary solution

0181A mixture of 60 ml of TEOS and 125 ml of ethanol was stirred for 15 minutes. Then 30 ml of distilled water and 12 ml of 1N nitric acid was added. After stirring for 10 minutes the solution was diluted with 675 ml of ethanol. (This pre-solution was used for the M-layer.)

Oxide solution:

0182To Hafvermittlerschicht properties was reached after 24 hours, 10.9 g Al (NO₃)₃· 9H₂O dissolved in 95 ml of ethanol, and added 5 ml acetylacetonate in the preliminary solution.

T-layer:

018368 ml of titanium n-butoxide, 918 ml of ethanol (absolute), 5 ml of acetylacetone and 9 ml ethylbutyl acetate were mixed together and stirred for 2 hours.

M-layer:

0184The coating solutions for the production of the M layer having an average refractive index were prepared by mixing the S-T and pre-solution solution. The M-layer solution comprised a mixture of S and T solutions in the ratio of weight .-% of oxides of 75:25.

0185The individual layers of Example 1 were applied by separate dipping steps. The glass material was immersed in the dipping solution. Then, this was at a rate of 6 mm / sec. pulled out, wherein the moisture content of the ambient atmosphere between 5 g / m³ and 12 g / m³, Preferably 8 g / m³ was. The solvent was then evaporated at 90 to 100 ° C. Thereafter, the coated layer was cured at a temperature of 450 ° C for 20 minutes.

0186The sample provided by the sol-gel process with the AR coating was subsequently in a KNO₃-Salzbad Which 0.01 .-% AgNO₃ contained immersed and treated for one hour at 430 ° C.

0187Then, the ion-exchanged AR-coated specimen was coated with an AF coating on one side by a fluid pressure equipment. The AF-coating solutions are products based on Polyfluorpolyethern, known under the trade name "Fluorolink^® PFPE ", such as" Fluorolink^® S10 "from Solvay Solexis or" Optool DSX^TM"Or" Optool^TM ÄS4-E "by Daikin Industries LTD.

0188The glass substrate thus produced in accordance with Example 1 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0189For comparison purposes, the measured transmittances of the uncoated Kalknatronsubstrats, the AR-coated substrate before the ion exchange, and the glass substrate prepared according to Example 1 are shown in <figref>5</figref> shown.

0190<figref>5</figref> shows a significant increase in the transmittance of the glass substrate according to the invention, which was obtained in spite of the different functionalities of the glass surface.

0191The compressive stress (CS) of the resultant glass substrate as in Example 1 was 332 MPa and the DoL (depth of ion Exchanged layer) was 5.3 microns.

0192The antimicrobial activity of the glass substrate of Example 1 on the AF-coated surface was> 99.9% against both E.coli and S.aureus.

0193The water contact angle of the AF-coated surface of the glass substrate of Example 1 was 112 ° C. The resistance of the glass substrate was examined in Neutralsalzsprühtest. After the glass substrate 10 weeks of water and sodium chloride was suspended at 35 ° C, the measured water contact angle was still 105 ° C. This demonstrates that the durability of the coating applied to the glass substrate is very high.

example 2

Glass substrate: aluminosilicate

0194A carefully cleaned Aluminosilikatgals as glass material with the size of 100 × 60 × 0.5 mm was provided with an antireflective coating, which had a single layer, as in <figref>4</figref> shown. The single-layer AR was also an adhesive layer.

0195The solution for the single layer was prepared as follows: 100 ml of TEOS were mixed with 200 ml of ethyl alcohol and 15 ml of 0.1N HCl. The mixture was stirred at 40 ° C for 3 hours. Then, the solution was diluted with 300 ml of ethyl alcohol and 16 g of Al (NO₃)₃· 9H₂O were also added and stirring was continued for a further half hour. After aging the solution for 24 hours at room temperature the solution was used as a dip coating.

0196The substrate glass was coated on both sides with a dip coating method with the above solution. The takeoff of the substrate from the liquid was 9 mm / min. The fresh coating was pre-heated for 2 minutes at 200 ° C and then cured, the coated glass substrate at 450 ° C for 1 hour. Then, the coated glass substrate was immersed in a salt bath for the ion exchange method, which was carried out at a temperature of 430 ° C for 4 hours. The molten salt in the salt bath was KNO₃ mixed with 0.02 wt .-% AgNO₃,

0197After the ion exchange, the glass substrate was cleaned and coated an AF coating using a conventional Sprühabscheidungsverfahrens.

0198The glass substrate thus produced according to Example 2 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0199The transmittance of the untreated glass substrate opposite to the glass substrate of Example 2 is in <figref>6</figref> shown.

0200<figref>6</figref> shows the high transmittance of the glass substrate prepared according to Example 2 compared to the untreated glass substrate.

0201The compressive stress (CS) of the product obtained from Example 2 glass substrate was 840 MPa and the DoL was 35 microns.

0202The antimicrobial efficacy of Example 2 on the AF-coated surface was> 99.9% compared to E. coli and 99.5% against S.aureus.

0203The water contact angle on the AF-coated surface of Example 1 was 115 ° C. Example 3 Glass Substrate: a glass having the following composition: <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">58.1</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">19.7</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">8.2</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">2.5</entry></row><row><entry colname="col1">MgO</entry><entry colname="col2">1.9</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">9.6</entry></row></tbody></tgroup></table></tables>

0204A carefully cleaned glass having the above composition was used as a glass material in a size of 100 × 200 × 3 mm, the accordance with an antireflective coating consisting of three layers <figref>2</figref>was coated. The antireflective coating consisted of three layers and had the following structure: glass substrate (<figref>2</figref>) + M layer (<figref>33</figref>) + T-layer (<figref>32</figref>) + S-layer (<figref>31</figref>). The S-layer was simultaneously an adhesive layer. The three layers were applied by using a dip coating technique to the glass.

0205The solutions for the three layers were prepared as follows:

S-layer:

preliminary solution:

0206A mixture of 60 ml of TEOS and 125 ml of ethanol was stirred for 15 minutes.

0207Then 30 ml of distilled water and 12 ml of 1N nitric acid was added.

0208After stirring for 10 minutes the solution was diluted with 750 ml of ethanol. (This pre-solution was used for the M-layer.)

Oxide solution:

0209To Hafvermittlerschicht properties was reached after 24 hours, 10.9 g Al (NO₃)<figref>3</figref>· 9H₂O dissolved in 95 ml of ethanol, and added 5 ml acetylacetonate in the preliminary solution.

T-layer:

0210109 g of amorphous TiO₂Powder was added to the solvent mixture of 802 g ethanol and 89 g of 1,5-pentanediol. The synthesis of the TiO₂Powder was as follows: 1 mole of titanium tetraethylate was reacted with 1 mol of acetylacetone and then with 5 mol H₂O hydrolyzed. After removal of the solvent, the powder was dried at 125 ° C for 5 hours. The amorphous powder had a content of TiO₂ from about 58 wt .-%.

M-layer:

0211The coating solutions for the production of the M layer having an average refractive index were prepared by mixing the S-T and pre-solution solution. The M-layer solution may comprise a mixture of S- and T-solution in a weight ratio of oxides of 65:35.

0212Subsequently, the glass substrate was immersed in a salt bath for carrying out the ion exchange process at a temperature of 420 ° C for 6 hours. The molten salt in the salt bath was KNO₃Mixed with 0.02 wt .-% AgNO₃,

0213After carrying out the ion exchange, the sample was purified and applied an AF coating by a conventional thermal vacuum deposition technique.

0214The glass substrate thus produced in accordance with Example 3 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0215The compressive stress (CS) of the glass substrate of Example 3 was 712 MPa and the DOL was 30 microns.

0216The antimicrobial activity of the glass substrate of Example 3 on the AF-coated surface was> 99% against both E. coli and S. aureus.

0217The water contact angle on the AF-coated surface of Example 3 was 115 ° C.

0218The reflections of the glass substrate of Example 3 before and after the ion exchange are in <figref>7</figref> shown. <figref>7</figref> shows that the reflection of the glass substrate of Example 3 by the ion exchange is not actually adversely affected. Example 4: glass substrate: soda lime glass having the following composition:<tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">70</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">0.3</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">8.36</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">8.46</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">5.74</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">4.53</entry></row><row><entry colname="col1">BaO</entry><entry colname="col2">2.11</entry></row><row><entry colname="col1">Sb₂O₃</entry><entry colname="col2">0.5</entry></row></tbody></tgroup></table></tables>

0219A carefully cleaned soda lime glass substrate of the above composition with a size of 100 × 200 mm was provided with an antireflective coating according to three layers <figref>2</figref> was constructed. The antireflective layer had the following structure: glass substrate (<figref>2</figref>) + M layer (<figref>33</figref>) + T-layer (<figref>32</figref>) + S-layer (<figref>31</figref>). The S-layer (<figref>31</figref>) Was also an adhesive layer. The three layers were applied by dip coating on the glass.

0220The solutions for the three layers were prepared as follows:

S-layer:

0221A mixture of 45 ml of TMOS and 125 ml of ethanol was stirred for 15 minutes.

0222Then 38 ml of distilled water and 1.7 g of 37% HCl were added. After stirring for 10 minutes the solution was diluted with 675 ml of ethanol. Then, 10 g of SnCl₄· 6H₂O dissolved in 95 ml of ethanol, and added 5 ml of acetylacetone to the solution.

T-layer:

022370 ml of titanium n-butoxide, 920 ml of ethanol (absolute), 5 ml of acetylacetone and 10 ml ethylbutyl acetate were mixed together and stirred for 2 hours.

M-layer:

0224The M layer was prepared as described in Example 3. FIG.

0225The glass substrate was immersed in a pure KNO₃-Salzbad For biasing chemical process at a temperature of 420 ° C immersed for 8 hours. Then, the glass substrate was subjected to a further silver-containing salt bath at a temperature of 430 ° C for 0.5 hour to an ion exchange. The molten salt in the second salt bath was KNO₃ mixed with 0.1 wt .-% AgNO₃,

0226After the ion exchange, the sample was purified and applied an AF coating liquid by a printing technology.

0227The glass substrate thus produced in accordance with Example 4 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0228The compressive stress (CS) of the glass substrate of Example 4 was 339 MPa, and the PDR was 14 microns.

0229The antimicrobial activity of the glass substrate of Example 4 on its AF-coated surface was> 99.9% against both E. coli and S. aureus.

0230The water contact angle on the AF-coated surface of the glass substrate of Example 4 was 113 ° C.

0231The reflections of the glass substrate prepared according to Example 4 before and after the ion exchange, carried out in two steps in <figref>8th</figref> shown. <figref>8th</figref> shows that the reflections of the glass substrate according to Example 4 before and virtually indistinguishable after ion exchange, so that the antireflective coating was not adversely affected by biasing and antimicrobial finishing. Example 5: glass substrate: Borosilika tglas without antimony<tables><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">oxide</entry><entry colname="col2">Fraction [wt .-%]</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">65</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">7</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">3</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">9</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">8th</entry></row><row><entry colname="col1">ZnO</entry><entry colname="col2">5</entry></row><row><entry colname="col1">TiO₂</entry><entry colname="col2">2</entry></row><row><entry colname="col1">CaO</entry><entry colname="col2">1</entry></row></tbody></tgroup></table></tables>

0232A carefully cleaned glass substrate having the above composition with a size of 135 × 70 × 0.7 mm was coated with an antireflective coating which was composed of a three-layer structure as shown in <figref>2</figref> shown. The antireflective coating consisted of three layers and had the following structure: glass substrate (<figref>2</figref>) + S-layer (<figref>33</figref>) + T-layer (<figref>32</figref>) + S-layer (<figref>31</figref>). The S-layer (<figref>31</figref>) Was an adhesive layer. The three layers were applied by dip coating on the glass technology.

0233The solutions for the three layers were prepared as follows:

S-layer:

023460 ml of TEOS were mixed with 120 ml of ethanol and 10 ml of 0.1N HCl and stirred for 3 hours at 40 ° C. Then, 9.5 g of Al (NO were₃)₃, 270 ml of ethanol and 50 ml Ethylaceton added and stirred for further 30 minutes.

T-layer:

023530 ml Titanoxidisopropoxid was mixed with 36 ml of acetic acid and stirred for 1 hour. Then, 400 ml of ethanol was added and stirred for 1 hour. Finally, 100 ml of acetylacetone was added to the solution and stirred for 1 hour.

0236The glass substrate was immersed in a salt bath for an ion exchange method at a temperature of 410 ° C for 3 hours. The molten salt in the salt bath was KNO₃ mixed with 0.5 wt .-% AgNO₃,

0237After the ion exchange, the glass substrate was cleaned and coated an AF coating by a conventional commercial Sprühabscheidungstechnologie.

0238The glass substrate thus produced in accordance with Example 5 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0239The compressive stress (CS) of the glass substrate, prepared according to Example 4, was 407 MPa, and the PDR was 14 microns.

0240The antimicrobial activity of the glass substrate according to Example 5 on the AF-coated surface was> 99.9% against both E. coli and S. aureus.

0241The water contact angle on the AF-coated surface of the glass substrate of Example 5 was 114 ° C.

0242The transmission of the same, but untreated glass substrate opposite to the glass substrate prepared in Example 5 is in <figref>9</figref> shown.

0243<figref>9</figref> shows that the transmittance of the glass substrate according to Example 5 is significantly higher and a maximum at a wavelength in the range 450-500 nm, in contrast to an untreated glass substrate. Example 6: glass substrate: borosilicate glass with the following composition:<tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="col1" colwidth="1*" /><colspec colname="col2" colwidth="1*" /><tbody><row><entry colname="col1">composition</entry><entry colname="col2">Wt .-%</entry></row><row><entry colname="col1">SiO₂</entry><entry colname="col2">80.8</entry></row><row><entry colname="col1">Al₂O₃</entry><entry colname="col2">2.4</entry></row><row><entry colname="col1">B₂O₃</entry><entry colname="col2">12.7</entry></row><row><entry colname="col1">N / A₂O</entry><entry colname="col2">3.5</entry></row><row><entry colname="col1">K₂O</entry><entry colname="col2">0.6</entry></row></tbody></tgroup></table></tables>

0244A carefully cleaned borosilicate glass of the above composition with the size of 100 × 200 mm was provided with an antireflective coating according to a single layer <figref>4</figref> exhibited. The single-layer AR was an adhesive layer.

0245The solution for the single layer was prepared as follows: 56 g of a 30% aqueous solution of SiO₂Solution stabilized with NH₄OH, wherein the SiO₂ an average particle size of 8 nm had been mixed with 120 ml of ethanol and 10 ml of 0.1N HCl and stirred for 3 hours at 40 ° C. Then, 9.5 g of Al (NO were₃)₃, 270 ml of ethanol and 50 ml Ethylaceton added and stirred for further 30 minutes.

0246The borosilicate glass substrate was coated on both sides in a dip coating process with the above solution. The fresh coating was first preheated for 2 minutes at 200 ° C, then cured, the coated glass substrate at 450 ° C for 1 hour.

0247Then, the coated glass substrate was immersed in a salt bath for carrying out an ion exchange process at a temperature of 450 ° C for 4 hours. The molten salt in the salt bath was KNO₃Mixed with 0.5 wt .-% AgNO₃,

0248After the ion exchange, the sample was purified and applied an AF coating by a liquid pressure method.

0249The glass substrate thus produced in accordance with Example 6 has an AR coating on, is chemically prestressed, has antimicrobial properties and has an AF coating.

0250The compressive stress (CS) of the glass substrate, prepared according to Example 6, was 213 MPa and the DoL was 12 microns.

0251The antimicrobial activity of the glass substrate of Example 6 on its AF-coated surface was> 99% against both E. coli and S. aureus.

0252The water contact angle on the AF-coated surface of the glass substrate of Example 6 was 112 ° C.

0253The transmittance of the untreated glass substrate opposite to the glass substrate prepared according to Example 6 is shown in <figref>10</figref> shown. <figref>10</figref> shows that the transmittance of the glass substrate, which was prepared according to Example 6, significantly higher than that of the untreated same glass substrate.

LIST OF REFERENCE NUMBERS

<dl><dt>2</dt><dd>Glass or glass ceramic substrate</dd><dt>20</dt><dd>Surface of the glass or glass-ceramic substrate</dd><dt>3</dt><dd>Layer with a low refractive index of the antireflective coating</dd><dt>4</dt><dd>Layer having a high refractive index of the antireflective coating</dd><dt>5</dt><dd>antireflective coating in the form of a single layer</dd><dt>31</dt><dd>Layer with a low refractive index of the antireflective coating</dd><dt>32</dt><dd>Layer having a high refractive index of the antireflective coating</dd><dt>33</dt><dd>Layer with middle refractive index of the antireflective coating</dd><dt>41, 42, 43, 44</dt><dd>Layers with alternating high and low refractive index of the antireflective coating</dd></dl>

QUOTES INCLUDED IN THE DESCRIPTION

0254This list of references cited by the applicant is generated automatically and is included solely to inform the reader. The list is not part of the German patent or utility model application. The DPMA assumes no responsibility for errors or omissions.

Cited patent literature

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Cited non-patent literature

0256<ul list-style="bullet"><li>P. Löbmann, "Sol-gel coatings", training course 2003 "surface refinement of glass", Cottage Technical Association of the German Glass Industry <b>[0075]</b></li><li>C. Brinker, G. Scherer, "Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing (Academic Press, Boston, 1990) <b>[0076]</b></li><li>R. Iller, The Chemistry of Silica (Wiley, New York, 1979) <b>[0076]</b></li><li>Standard JIS Z 2801 <b>[0102]</b></li><li>ISO 22196 <b>[0102]</b></li></ul>