EP1909971B1 - Substrate comprising at least one entire surface or partial surface macrostructured layer, method for the production thereof and its use - Google Patents

Abstract

A method for producing a substrate including a layer includes providing that the layer is a full or a partial surface macro-structured layer, applying a sol-gel solution in already structured form onto the substrate, and drying and/or baking, resulting in a sol-gel layer.

Description

The invention relates to a substrate comprising at least one fully or partially macrostructured layer, processes for their preparation and their use.

To produce many functional layers or layer systems, in particular on glasses and glass ceramics as substrate materials, the sol-gel technology is often used. Examples of such sol-gel layers are: Layer function: Layer / System Examples of used sol-gel solutions anti-reflective multilayer system: SiO ₂ -TiO ₂ alcoholic Si and Ti alkoxide solutions photocatalytic TiO ₂ layer (Anatase) colloidal TiO ₂ solution anti-microbial Ag-containing layer colloidal Ag solution Decorative colored SiO ₂ layer SiO ₂ sol with dye (s) or pigments easy-to-clean Silanized glass surface with hydrophobic carbon side chains Solution with fluoroalkylsiloxanes Electro chrome WO ₃ layer on TCO-coated substrate alcoholic WO ₃ sol

Depending on the application, the sol-gel solutions used have different viscosities. Often, however, this is in the order of magnitude of aqueous solutions and is therefore very low. Usually, the application of the layers takes place over the entire surface using common Application methods, such as dipping, flooding, spraying, spraying, pouring, brushing, rolling or spinning. As a rule, the layers are cured by a subsequent tempering step.

A particular challenge is the structuring of such functional layers, since the classical printing processes, such as offset or screen printing, fail here because of the low viscosities of the solutions used. However, the production of colored, transparent layers on glass substrates by means of digital printing technology is known. This can be assumed, for example, SiO ₂ sols containing organic dyes.

Furthermore, there are already some suggestions for applying structured sol-gel layers in the prior art:

According to the WO 97/38810 A1 discloses a process for producing a sintered structure on a substrate, wherein a particle-containing liquid such as a sol-gel solution is applied to a substrate by an ink jet printer and the applied liquid is evaporated by a laser pulse to build a sintered structure in layers ,

The WO 02/17347 A1 discloses a method for consolidating and patterning a sol-gel composition on a surface of a substrate, wherein a layer of a sol-gel composition is deposited on a surface of a substrate, an electron beam is directed to selected areas of the sol-gel film, to cure the sol-gel film and the uncured areas are removed with a solvent again.

Furthermore, the EP 0 329 026 A1 to an ink-jet ink and printing method, wherein the ink comprises 90 to 99.9% by weight of an aqueous sol-gel medium, preferably a mixture of carrageenan and water, and 0.1 to 10% by weight of a colorant , and the ink represents a thermally reversible sol-gel ink that is a gel at ambient temperature and is a sol at temperatures between about 40 ° C and 100 ° C. The ink is applied as a sol to the substrate where it forms a gel upon cooling. The substrate used is almost exclusively paper into which the ink penetrates.

The disclosure of US Pat. No. 5,970,873 relates to an imaging process comprising imagewise applying a mixture of a sol precursor and a liquid as a thin layer to a substrate and removing the liquid from the thin layer to imagewise form an insoluble, crosslinked, polymeric sol-gel matrix. An imaging element made by the process, such as a lithographic printing plate, will also be described. The image area created in the sol-gel matrix therefore serves as a "negative" to which ink is applied, which is then transferred to a suitable receptor material to reproduce the image.

Further, the WO 99/33760 a method of providing an article with visually-visible patterns, wherein first at least a surface area of a substrate is masked, then at least one thin layer is applied to the masked and unmasked areas of the surface, and the mask is removed to produce the desired pattern. The article produced therewith has at least a first portion carrying a generally transparent thin film selected from metal-containing, semi-metal-containing coatings and combinations thereof, which when viewed under reflected light exhibits a first color and exhibits a second color under light passing therethrough , as well as a second section, visibly different in contrast to the first. The sol-gel technology is mentioned, but no explanation is given how this can be done.

Finally, that describes DE 100 19 822 A1 a lift-off method for microstructuring thin films, wherein a mask on a substrate is deposited, which contains recesses at the points to be coated, a sol is applied over the entire surface of the substrate covered with the mask, the sol-cured film, the mask removed together with the present on the mask surface hardened sol and the cured sol-film Supplying energy is converted to the desired solid state. There is also described a micro-structured thin-film device manufactured by this method, such as a semiconductor device.

The present invention is based on the object, in a development of the prior art, to provide a flexible, non-expensive and cost-effective method by means of which structures can be produced on a substrate in a simple manner. In particular, it should be possible to provide any substrate with a desired structure.

The present object is achieved by a substrate according to claim 1.

• Aufbringen einer Sol-Gel-Lösung in strukturierter Form auf das Substrat nach Anspruch 7.

The invention also provides 3 process variants for the production of the substrate according to the invention, which according to variant (a) has the following steps:

• Application of a sol-gel solution in structured form to the substrate according to claim 7.

The present invention accordingly comprises substrates with a structured coating, wherein a sol-gel solution is used to produce the structured coating. The term "structure" is to be construed as broad as possible according to the invention and includes, for example, a pattern, logo, image (s), words, a marker, hatching, marking, labels, in one or more defined optical manifestations, functionalities or the like. This structure can be provided over the whole area or only part of the area on a substrate.

The basis for the structure is a sol-gel system, i. a sol which forms a thin, preferably transparent, gel film after drying, which preferably hardens by baking / tempering. The term "sol-gel layer" in the present invention is intended to represent a layer prepared by a sol-gel method.

In this case, so-called nanosols can be used. The average particle diameter of such sols is in the range <800 nm, preferably <200 nm, particularly preferably <100 nm.

The sol-gel layer is based on one or more metal oxides and is preferably selected from at least one titanium, zirconium, silicon, aluminum, tin, boron or phosphorus oxide or mixtures thereof. Particular preference is given to containing silicon oxide, but it is also possible for other or further metal oxides to be present. In the context of the invention, the term "metal" also the semimetals, such as silicon and germanium, understood.

As "sol-gel solutions", for example, so-called classical sol-gel solutions are used according to the invention, in addition to a suitable amount of desired additives, a metal oxide precursor, a solvent, a minor amount of water for precondensation and a catalyst (acid or base ) or consist of. Furthermore, colloidal metal oxide solutions = solutions of nanoscale metal oxide powders in water or other solvents are used; In some cases, traditional sol-gel solutions are also mixed with nanoscale metal oxide powders. Solvents are usually water or an aqueous / organic solvent, such as, for example, ethanol or acetone. Long-term stable sol-gel solutions may also be stored in purely organic solvents. These sols are clear and stable solutions with solids contents typically in the range of about 1 to about 30 weight percent. The metal oxide contents can also be significantly higher. To produce a coating, a part of the solvent is evaporated, whereby the particles chemically or physically aggregate and a three-dimensional crosslinking (gelation) takes place. After complete evaporation of the solvent results in a solvent-free coating of a porous sol-gel layer, which under the influence of higher temperatures further networked and thereby hardened and compacted.

The sol-gel matrix can also be modified chemically in any manner by co-hydrolysis or co-condensation. These modifications are known to the person skilled in the art. Such organically modified sol-gel compounds are known, for example, under the brand ORMOCER® ^®.

In principle, the sol-gel coating can be carried out directly in structured form according to process variant (a) according to the invention using various printing techniques. In particular, the tampon and gravure are mentioned here, as they are particularly well suited for the processing of low-viscosity liquids.

In addition, a full surface coating of the article is possible, wherein the structuring of this coating in further operations is usually carried out using Abdecklacken according to the inventive process variants (b1) and (b2).

According to a first variant (a) according to the invention, in the case of the substrates the sol-gel solution which is converted to the sol-gel layer can be applied directly in structured form:

Structured liquid coatings can generally be applied to the substrate using known printing technologies, but so far this has not been known for sol-gel solutions used to make functional layers. Conventional sol-gel solutions dry very quickly, which can cause great difficulties in printing techniques. Without a modification of the solution, especially the solvents, many methods are unusable because the coating reacts on the transfer medium or in the printing nozzles. It is important that no / hardly any condensation reactions take place during the printing process. The present invention now provides ways in which - in contrast to the prior art - known printing technologies can be used, whereby the above problems are minimized or completely avoided.

The use of sol-gel solutions tailor-made for the special printing technology, which includes, for example, a modification of the viscosity of the solution and / or a suitable choice of the solvent, is the first to be used hitherto unavailable printing technologies accessible. For example, in pigment-filled systems, a highly viscous sol-gel solution can be used for screen printing.

Since sol-gel solutions generally have a comparatively low viscosity, tampon and intaglio printing in particular are suitable for the production of structured coated articles. The application of the sol-gel solution in already structured form according to the process (a) according to the invention is therefore carried out on the substrate, preferably with a low-viscosity sol-gel solution using a known printing process. By "low viscosity" is meant in the present invention, a viscosity in the range of about 0.1 to about 10 ⁴ mPa s.

If structured layers, in particular substrates with structured layers, for example decorative color layers, are to be prepared on a sol-gel basis, pigment-filled color formulations which contain a sol-gel solution, for example as a binder, are also preferably used. Depending on the choice of the ratio of pigment to binder content (including solvent) and optionally added thickening additives can then be set in the formulation, a very high viscosity. Such thickening additives are, for example, cellulose, cellulose ethers, starch, aerosils (pyrogenic silicas), bentones, hydrophobically modified polyoxyethylenes, acrylates, polyurethanes, polyamides, polyolefins, Castor oil and basic sulphonates.

If thickening additives are added and a highly viscous, sufficiently thixotropic sol-gel solution is obtained, the application of the structured coating is also possible by means of screen printing or other printing techniques, such as offset, pad and pad printing. A "high-viscosity", "sufficiently thixotropic" sol-gel solution is understood here to mean that the viscosity-in the absence of shear forces-is above a limit of about 10 ³ mPa s, in particular about 10 ⁴ to 10 ⁶ mPa s. Thixotropy refers to the property of a non-Newtonian fluid to exhibit a lower viscosity after shearing and to rebuild at rest.

Opposite the US Pat. No. 5,970,873 In the present invention (variant a) no "negative" image is generated, which then serves as the basis for the generation of a "positive" image, but a positive structure is produced directly. The substrate according to the invention, comprising a structure, is not an imaging element and there is also no imagewise application of a sol precursor. ie the use is not primarily for the production of lithographic printing plates. In addition, the ether or ester of the metal oxide used as the sol does not have to carry at least one "melanophilic" side group.

According to further variants (b1) and (b2) according to the invention, the sol-gel layer can be applied over the entire surface of the substrate and subsequently structured in further working steps:

The structuring of full-surface coatings usually succeeds by using Abdecklacken. These can be used in two different ways according to the two process variants (b1) and (b2) of the invention:

According to a variant of the invention, these can be applied directly to the substrate as positive coatings at the points of the layer to be structured (process variant (b1) according to the invention). Preferably, in this case (screen) printable Coating used. In this case, the application of the Abdecklacks can already be done preferably in a structured form.

Alternatively, a photoresist is used. In this case, the structuring can also take place after a full-area application of the photoresist in a second step with the aid of an exposure step and subsequent removal of the areas not to be lacquered. Subsequently, the full surface coating of the prepared substrate is carried out using the sol-gel solution. The use of (screen) printable paints is preferred over that of photo-resists because they are significantly less expensive and their application is associated with a significantly lower cost.

Any solvent or dispersant or solvent mixture suitable for such a process can be used as solvent or dispersant for the sol-gel solution of all processes according to the invention. Examples are water and alcohols, for example ethanol, or alcohol-water mixtures. For the preparation of sol-gel coatings based on silica, for example, alcohols, but also aprotic solvents, such as dioxane, or aqueous solvents can be used.

The sol-gel layers applied according to the invention, which are used in process variants (b1) and (b2) according to the invention, preferably have layer thicknesses in the range from 1 nm to 100 .mu.m, preferably 1 nm to 1 .mu.m, in particular 1 to 200 nm. Depending on the function, the (preferred) layer thicknesses vary greatly. If only a few monolayers are deposited on the substrate in the case of an easy-to-clean layer, ie the layer thickness moves here in the nm range, it may be preferred if pigment-filled, decorative sol-gel layers are opaque. This is achieved, for example, with layer thicknesses of at least 10 μm or significantly higher.

If a fully or partially coated layer is to be applied, it is preferably applied by a spraying or dipping method, wherein all other methods known to the person skilled in the art may also be used, e.g. a spin, roll coating (rolling), brushing, pouring or knife coating.

According to the invention, preference is given to sol-gel layers which fulfill very specific functions which can be used for commercial products. Drying according to process variant (b1) is preferably carried out in a temperature range from room temperature (25 ° C.) to 300 ° C. until essentially all the solvent has been removed, the solvent of the sol-gel solution being water, alcohol, all known to the person skilled in the art , in particular common, preferably halogen-free, low (boiling point: up to 120 ° C) and high boiling solvent (boiling point: 120 to 250 ° C) and mixtures thereof are preferred. The drying time is generally in the range of a few minutes to 1 or more days. In some applications, the quality of the layers thus formed is sufficient, so that no further production step for baking is required. -No preferred drying times can be specified, since these can be very different depending on the application.

After drying the sol-gel layer of Abdeckschicht is removed again. This can be done by mechanical means, such as stripping, wiping, brushing, chemical means, such as delamination with the aid of a solvent or water, acids or alkalis, or by using pyrolytic agents.

In most applications, the dried sol-gel layer is subsequently baked. A "burn-in" according to variant (b1) in the context of the invention means that the dried sol-gel layer is converted into its final form by chemical reaction, sintering and / or stimulation of diffusion processes. For this purpose, the substrate with the applied dried layer for a period of 10 minutes to 3 hours a temperature in the range between room temperature and 800 ° C, preferably between 250 and 800 ° C. exposed.

Coating lacquers generally can not be exposed to the temperatures necessary for curing the sol-gel layers, so that they are removed before stoving.

Baking has the advantage that the mechanical and chemical resistance of the layer increases drastically. In some cases, the layer only gets its actually desired function by the burn-in. The coated article in these cases can be used only after the baking step in the respective application.

Burning in can also specifically influence certain properties of the layer. For example, the optical antireflection effect of _{SiO2 TiO2} -Wechselschichtsystemen (anti-reflection) is critically dependent on the refractive indices of the respective, present in the layer packet individual layers. This in turn is structurally dependent. The chemical structure varies depending on the choice of baking conditions. Thus, the anti-reflection effect of such coating systems, inter alia, depends crucially on the conditions during the penetration of the layers.
As a result, the sol-gel layer is preferably already converted into its final form, so that further post-treatment steps are not necessary.

In contrast to the method according to the DE 100 19 822 A1 In the present invention, no microstructures are generated which can be used, for example, in semiconductor components, and become visible to the naked eye, for example, only under a microscope. On the other hand, according to the invention, macrostructured regions, for example coarse-structured, optionally large-area regions, are produced. This means that structures in the order of up to a minimum of about 50 to 100 microns (corresponding to about the width of a hair) can be made, so that always visible to the eye structures are produced. A transfer of such Microstructures on macrostructures would not be considered by a person skilled in the art due to the well-known special status of semiconductor technology.

According to a further variant of the invention, it is possible to apply the masking resist as a negative resist to a substrate which is already provided with the sol-gel layer over the whole area (process variant (b2) according to the invention).

The evaporation of the solvent or drying according to process variant (b2) is preferably carried out in a temperature range from room temperature to max. 200 ° C until essentially all the solvent has been removed, being used as the solvent of the sol-gel solution, water, alcohol, all known in the art, especially common, preferably halogen-free, low (boiling point: up to 120 ° C) and high boiling solvent (Boiling point: 120 to 250 ° C) and mixtures thereof are preferred. The drying time is generally in the range of a few minutes to 1 or more days. Because of the diversity of the layers to be produced, the above information is only an example.

Again, the patterning of the resist can advantageously be effected by means of suitable (screen) printing methods, i. Applying the resist in structured form, or photolithographically, i. after application, done. In a second method step, the sol-gel layer is then removed at the exposed locations, for example with a suitable chemical etching solution. Such an etching solution may be, for example, an aqueous NaOH solution or an aqueous HF solution. Finally, the covering is again mechanically, chemically or pyrolytically - as already described - removed.

Advantageously, the Abdecklack which is applied either in a structured form or structured after the order is not baked.

As a resist, in particular photoresist any known in the art paint can be used. Particularly preferred are paint classes, such as: topcoats, Peel-off lacquers, photostructurable lacquers (liquid resists, dry resists). Usable commercially available products are, for example: covering lacquer 80 2039 (from Ferro), Wepelan covering lacquer SD 2154 E (Peters), stripping lacquer SD 2962 P (Peters), liquid resist AZ 9260 (from Clariant), liquid resist AZ nLOF 2070 (Clariant), dry resist EtchMaster ES-102 (DuPont) and dry resist Riston 220 (DuPont).

The sol-gel solution used according to the invention preferably contains further constituents selected from the group consisting of inorganic and / or organic dyes, pigments and / or additives, such as thickener, dispersant, defoamer, anti-settling agent, surface tension modifier, processing aid, deaerator, lubricant and leveling agents, crosslinking additives, primers, and the like. Additives can be used, for example, for the specific introduction of specific functionalities. By the addition of organic and / or inorganic dyes or pigments, for example, additional color effects can be produced. In addition, pigments are able to introduce further functionalities, such as IR or UV reflection, into the layer.

• etwa 1 bis etwa 80 Gew.-% Metalloxid, Metalloxidprecursor oder Metalle, wie SiO₂. Alkoxysilane, Alkylalkoxysilane, fluorierte Alkylalkoxysilane, TiO₂, Titanalkoxide, kolloidales Silber bzw. kolloidale Silberverbindungen,
• etwa 20 bis etwa 99 Gew.-% Lösungsmittel, wie Wasser, Alkohole sowie alle dem Fachmann bekannten, insbesondere gängigen, vorzugsweise halogenfreien, niedrig- (Siedepunkt: bis 120 °C) und hochsiedenden Lösungsmittel (Siedepunkt: 120 bis 250 °C);
• 0 bis etwa 20 Gew.% Wasser zum Vorkondensieren;
• 0 bis etwa 5 Gew.-% Katalysator (Säure, wie konz. Salz-, Schwefel- oder Salpetersäure oder Lauge, wie Natron- oder Kalilauge);
• 0 Gew.-% bis etwa 50 Gew.-% farbgebender Komponente, wie organischen oder anorganischen Buntpigmenten bzw. organischen Farbstoffen und
• 0 Gew.-% bis etwa 10 Gew.-% Additive, wie Eindicker, Dispergiermittel, Verarbeitungshilfsmittel, Entschäumer, Entlüfter, Antiabsetzmittel, Oberflächenspannungsmodifizierer, Gleit- und Verlaufsmittel,

Vernetzungsadditive, Primer etc.Particular preference is given to using a sol-gel solution which comprises or consists of the following components:

• from about 1 to about 80 weight percent metal oxide, metal oxide precursors or metals such as SiO ₂ . Alkoxysilanes, alkylalkoxysilanes, fluorinated alkylalkoxysilanes, TiO ₂ , titanium alkoxides, colloidal silver or colloidal silver compounds,
• about 20 to about 99 wt .-% of solvents such as water, alcohols and all known in the art, especially common, preferably halogen-free, low (boiling point: up to 120 ° C) and high boiling solvent (boiling point: 120 to 250 ° C);
• 0 to about 20% by weight of water for precondensation;
• 0 to about 5% by weight of catalyst (acid such as concentrated hydrochloric, sulfuric or nitric acid or alkali such as sodium or potassium hydroxide);
• 0 wt .-% to about 50 wt .-% of coloring component, such as organic or inorganic colored pigments or organic dyes and
• From 0% to about 10% by weight of additives such as thickeners, dispersants, processing aids, defoamers, deaerators, anti-settling agents, surface tension modifiers, lubricants and leveling agents,

Crosslinking additives, primers etc.

The total amount of all components of the sol-gel solution naturally complements 100% by weight.

The substrate in the above method provided with one or more structures is not particularly limited in the present invention. Any type of material may be used, such as, for example, plastic, metal, wood, enamel, glass, ceramics, in particular glass-ceramic, preference being given to glass and glass-ceramic substrates. For example, alkali-containing float glasses, such as borosilicate glasses (eg Borofloat 33, Borofloat 40, Duran from Schott AG, Mainz), as well as alkali-free glasses (eg AF 37, AF 45 from Schott AG, Mainz), aluminosilicate glasses (eg Fiolax, IIIax from Schott AG, Mainz), alkaline earth glasses (eg B 270, BK 7 from Schott AG, Mainz), Li ₂ O-Al ₂ O ₃ -SiO ₂ float glass, discolored float glass with an iron concentration below 700 ppm, preferably below 200 ppm and, in a more specific application, soda-lime glasses, particularly the latter being preferred. Also preferred are display glasses, such as D263 from Schott-DESAG, Grünenplan. In principle, all known technical and optical glasses can be used.

Typical glass ceramics which are used as alkali-containing glass-ceramics are, for example lithium aluminosilicate (LAS) glass-ceramics, such as CERAN ^{®, ®} or ROBAX ZERODUR ^® (all brands of Schott AG, Mainz), but also alkali-free glass ceramics, such as magnesium aluminosilicates (MAS) can be used.

The substrate is not particularly limited in the invention not only in terms of the material but also in terms of shape, so that, for example, flat, round, rounded large and small objects can be used. Preference is given to objects made of or with glass and / or glass ceramics of any shape, such as glass tubes, glass lenses, ampoules, carpets, bottles, jugs. Slices, plates or any shaped parts.

Of course, it is also possible to use an optionally surface-treated substrate as well as a substrate already provided with a layer, for example a surface-treated or already coated glass. The substrate is provided at least on a part of its surface with a macrostructure according to the present invention. Of course, the entire surface may also be structured or the structure may be present on multiple parts of one or more surfaces. The structure can be applied, for example, on one or both sides, according to the shape of a substrate also on several sides.

The following are merely exemplary substrates: tiles, enamel parts, panes, in particular viewing panes, plates, panels, glazings of all kinds, shower enclosures, covers, work and cooking surfaces, as part of refrigerators or freezers, dining or drinking utensils, containers, Fire panels, chimney windows, oven panes as a glass cover for solar energy systems, medical glass, in particular a drug bottles, lenses or covers for displays, a component of hi-fi or computing or telecommunications equipment and the like.

It goes without saying that in addition to single layers and multi-layer systems can be used to produce a desired macrostructure.

The invention also relates to the partially or completely macro-structured layers produced according to the invention. These can be used, for example, in the form of functional layers, i. the partial or full-surface structured layer has one or more specific functions or properties. Examples of functional layers structured according to the invention are anti-reflection layers, color layers, decorative layers, photocatalytic layers, antimicrobial layers, anti-virus layers, anti-mold layers, anti-fungicidal layers, anti-algae layers, anti-fogging layers. Layers, cleaning layers, odor neutralizing layers, anti-fingerprint layers, air cleaning layers or combinations thereof.

• Fliesen, wie Keramik-, Emaille- oder Glasfliesen;
• Emailleteile, insbesondere bei Backofenmuffeln;
• Platten, wie Arbeitsplatten, zum Beispiel aus Glas oder Keramik, im Haushalt oder Labor;
• Verglasungen aller Art, insbesondere von Fenstern, beispielsweise Isolierglastüren für Schränke;
• Bilderrahmen;
• Architekturglas;
• Abdeckungen, beispielsweise für Displays;
• Beckenauskleidungen, wie Schwimmbadverkleidungen, Fischzuchtbecken;
• Spiegel, beispielsweise rückstrahlende Verkehrsspiegel;
• Wände, insbesondere Außenwände, beispielsweise von Zügen;
• Duschabtrennungen, beispielsweise aus Glas oder Kunststoff;
• Scheiben, wie Sichtscheiben, insbesondere Backofenscheiben, Kamin- und Mikrowellensichtscheiben;
• Schaufenster;
• Tafeln, wie Werbetafeln;
• Küchenutensilien, wie Schneidbrettchen, beispielsweise aus Glas, Keramik, Kunststoff oder Holz;
• Ablagen, beispielsweise aus Glas, Keramik, Kunststoff oder Metall;
• Kochflächen, beispielsweise Glaskeramikkochflächen;
• Behälter, wie Backschalen;
• Ess- oder Trinkutensilien, wie Trinkgläser, und
• Ausstattungen von Backöfen, Spülmaschinen oder Kühl- und Gefriermöbeln, beispielsweise Kühlschrankeinlegeböden, -fächer oder - schubladen.

The use of the substrates according to the invention, comprising a fully or partially macrostructured layer is very diverse. Examples include:

• Tiles, such as ceramic, enamel or glass tiles;
• Enamel parts, in particular with oven muffles;
• Plates, such as worktops, for example of glass or ceramic, in the household or laboratory;
• Glazing of all kinds, in particular of windows, for example insulating glass doors for cabinets;
• Picture Frame;
• Architectural glass;
• Covers, for example for displays;
• Pool linings, such as swimming pool coverings, fish breeding ponds;
• Mirrors, for example retro-reflective traffic mirrors;
• Walls, in particular outer walls, for example of trains;
• Shower enclosures, for example of glass or plastic;
• Discs, such as viewing windows, in particular oven panes, chimney and microwave viewing panes;
• Store window;
• Boards, such as billboards;
• Kitchen utensils, such as cutting boards, for example made of glass, ceramic, plastic or wood;
• Shelves, for example of glass, ceramic, plastic or metal;
• Cooking surfaces, for example glass ceramic cooking surfaces;
• Containers, such as baking cups;
• Eating or drinking utensils, such as drinking glasses, and
• Furnishings of ovens, dishwashers or refrigerators and freezers, such as refrigerator shelves, compartments or drawers.

Further possible applications are, for example, glass ceramic plates for a household appliance, a glass cover for solar energy systems, as a window of a dishwasher or cookware, such as a steamer, as a fire or medical glass, such as drug bottles, for containers or pipes, such as coated container or Pipe for dairy farming, as a window or cover for displays, component of hi-fi, computing or telecommunications equipment, for dining or drinking utensils, baby bottles, windows, optical lenses, laboratory glassware, in particular borosilicate glasses.

• Ein Beispiel sind kostengünstige Anti-Reflex-Schichten (low cost AR): Diese können beispielsweise aus einem kolloidalen SiO₂-So durch Tauchen gefertigt werden. Die Strukturierung der Schichten erfolgt vornehmlich in den Randbereichen der Substrate/Komponenten, um deren Einbau ins Gesamtsystem zu erleichtern oder gar zu ermöglichen.
• Anti-Reflex-Schichtsysteme können hergestellt werden: Bekannte Glasentspiegelungen für den sichtbaren Spektralbereich sind zum Beispiel AMIRAN- oder MIROGARD-Entspiegelungen der Schott AG: Es sind Interferenzfilter aus beispielsweise drei Schichten, wobei zunächst eine Schicht mit einem mittleren Brechungsindex, darauf eine Schicht mit hohem Brechungsindex, zumeist TiO₂, und darauf dann eine Schicht mit niedrigem Brechungsindex, meist SiO₂, abgeschieden wird. Bevorzugt ist daher in der vorliegenden Erfindung ein 3- oder 5-Schichtaufbau aus niedrigbrechenden SiO₂- und hochbrechenden TiO₂-Schichten im Wechsel. Gefertigt wird vorzugsweise aus Si- und Ti-haltigen Solen durch Tauchen. Flachglas mit diesen Beschichtungen wird beispielweise als Architekturglas oder als Verglasung in Bilderrahmen eingesetzt. Die Strukturierung des Schichtsystems dient vorzugsweise dekorativen Zwecken, wie z. B. dem Aufbringen eines Logos. Der gewünschte optische Effekt kann durch Strukturierung einer oder mehrerer Schichten des Systems, vorzugsweise der letzten Schicht des Systems oder durch Aufbringen einer zusätzlichen Schicht in strukturierter Form erfolgen.
• Ein weiteres Anwendungsbeispiel stellt eine farbige Unterseitenbeschichtung auf einer transparenten Glaskeramik dar: Es wird vorzugsweise ausgehend von einer pigmentgefüllten Sol-Gel-Farbe gefertigt. Die Farbe ist prinzipiell mit unterschiedlichen Viskositäten einstellbar, so dass neben den bereits beschriebenen Verfahren zum Auftrag von niederviskosen Sol-Gel-Lösungen, wie insbesondere Sprühen und Gießen, in geeigneten Fällen auch die Siebdrucktechnik zum Einsatz kommen kann. Unterseitenbeschichtete Glaskeramiken finden beispielsweise als Kochflächen Verwendung. Die Strukturierung der Schichten dient in diesem Fall der Displayfähigkeit sowie dekorativen Zwecken.
• Es können auch gefärbte, transparente Beschichtungen hergestellt werden: Hierzu wird vorzugsweise basierend auf einem Si-haltigen Sol, in dem organische Farbstoffe gelöst sind, gefertigt. Transparent gefärbte Beschichtungen dienen vor allem dekorativen Zwecken. Gleiches gilt für deren Strukturierung.
• Weiterhin sind auch photokatalytische Beschichtungen möglich: Beispiele sind TiO₂-Schichten (Anatas), gefertigt aus einem kolloidalen TiO₂-Sol durch Tauchen oder Schleudern. Die Schichten besitzen selbstreinigende Eigenschaften und haben aus diesem Grund einen sehr weiten Anwendungsbereich: Anti-Bakteriell, Anti-Virus, Anti-Schimmel, Anti-fungizid-, Anti-Algae, Anti-Fogging, Anti-Fingerprint-Schicht, Geruchsneutralisierung, Luftreinigung etc. Mit photokatalytischen Schichten versehen werden in diesem Zusammenhang beispielsweise Bodenfliesen, Fischzuchtbecken, rückstrahlende Verkehrsspiegel, Außenwände von Zügen, Architekturglas etc. Die Strukturierung der Schichten dient in diesen Zusammenhängen vornehmlich der Erleichterung der Einbaubarkeit der beschichteten Komponenten ins Gesamtsystem bzw. sie ist gar eine notwendige Voraussetzung hierfür.
• Erfindungsgemäß können auch anti-mikrobielle Beschichtungen bereitgestellt werden: Diese werden vorzugsweise aus einem Ag-haltigen, kolloidalen Sol durch Tauchen hergestellt. Derartig beschichtete Komponenten können in Kühlschränken Verwendung finden. Die Strukturierung erfolgt hier vornehmlich an den Rändern und kann die Einbaubarkeit der Komponenten ins System erleichtern bzw. eine notwendige Bedingung hierfür sein. Zusätzlich kann so die Menge der sehr teuren Beschichtung auf die relevanten Bereiche begrenzt werden.
• Weitere Beispiele sind easy-to-clean Beschichtungen: Hierzu werden Oberflächen von Gläsern und Glaskeramiken, beispielsweise in einer Silanisierungsreaktion mit längeren, perfluorierten Kohlenstoffketten modifiziert. Die Oberfläche erhält dadurch einen hydrophoben Charakter und wird durch die Absenkung der Oberflächenenergie sehr leicht reinigbar. Komponenten mit easy-to-clean-Schichten kommen vor allem im "White goods"-Bereich und dort vornehmlich bei "warm"-Anwendungen (Dauerbelastung bis 300°C) zum Einsatz. Konkrete Beispiele sind: Backofenscheiben, Backschalen, Kochflächen etc. Die Strukturierung der Schichten hat hier beispielsweise den Zweck, die Einbaubarkeit (zum Beispiel Kleben) des Substrats/der Komponenten ins Gesamtsystem zu erleichtern bzw. überhaupt erst zu ermöglichen.

The following are some examples of use of structured sol-gel layers or substrates provided herewith:

• An example are low-cost anti-reflex layers (low-cost AR): These can be made, for example, from a colloidal SiO ₂ -So by immersion. The structuring of the layers takes place primarily in the edge regions of the substrates / components in order to facilitate or even enable their incorporation into the overall system.
• Anti-reflective layer systems can be produced. Known glass reflections for the visible spectral range are, for example, AMIRAN or MIROGARD antireflective coatings from Schott AG. These are, for example, three layers of interference filters, with first a layer with a mean refractive index, then a layer with a high refractive index Refractive index, usually TiO ₂ , and then a layer of low refractive index, usually SiO ₂ , is deposited. Therefore, in the present invention, a 3- or 5-layer structure of low-refractive SiO ₂ and high-index TiO ₂ layers is preferably alternating. Is preferably prepared from Si and Ti-containing sols by dipping. Flat glass with these coatings is used, for example, as architectural glass or as glazing in picture frames. The structuring of the layer system is preferably used for decorative purposes, such. B. the application of a logo. The desired optical effect can be achieved by structuring one or more layers of the system, preferably the last layer of the system, or by applying an additional layer in structured form.
• Another application example is a colored underside coating on a transparent glass ceramic: it is preferably produced starting from a pigment-filled sol-gel color. The ink is in principle adjustable with different viscosities, so that in addition to the methods already described for the application of low-viscosity sol-gel solutions, in particular spraying and casting, the screen printing technique can also be used in suitable cases. Bottom-coated glass ceramics are used, for example, as cooking surfaces. The structuring of the layers in this case serves the display capability as well as decorative purposes.
• It is also possible to produce colored, transparent coatings. For this purpose, preference is given to using a sol containing Si in which organic dyes are dissolved, manufactured. Transparent colored coatings are used primarily for decorative purposes. The same applies to their structuring.
• Furthermore, photocatalytic coatings are also possible: Examples are TiO ₂ layers (anatase), made from a colloidal TiO ₂ sol by dipping or spinning. The layers have self-cleaning properties and therefore have a very wide range of applications: anti-bacterial, anti-virus, anti-mold, anti-fungicidal, anti-algae, anti-fogging, anti-fingerprint coating, odor neutralization, air cleaning, etc In this context, for example, floor tiles, fish tanks, retro-reflective traffic mirrors, outer walls of trains, architectural glass etc. are provided with photocatalytic layers. In these contexts, the structuring of the layers primarily serves to facilitate the installation of the coated components into the overall system or is even a necessary prerequisite therefor.
• Anti-microbial coatings can also be provided according to the invention: These are preferably prepared from an Ag-containing, colloidal sol by immersion. Such coated components can be used in refrigerators. The structuring takes place here primarily at the edges and can facilitate the installation of the components into the system or be a necessary condition for this. In addition, the amount of the very expensive coating can be limited to the relevant areas.
• Further examples are easy-to-clean coatings: For this purpose, surfaces of glasses and glass ceramics are modified, for example in a silanization reaction with longer, perfluorinated carbon chains. As a result, the surface acquires a hydrophobic character and is very easily cleaned by lowering the surface energy. Components with easy-to-clean coatings are mainly used in the "white goods" sector and are primarily used in "warm" applications (continuous load up to 300 ° C). Concrete examples are: oven panes, baking trays, cooktops, etc. The structuring of the layers has, for example, the purpose here of facilitating the installation (for example gluing) of the substrate (s) into the overall system or even making it possible in the first place.

The advantages of the present invention are many:
The present invention provides a substrate as well as methods for its production, wherein the advantages of the sol-gel technology can be used, ie it can be provided wet-chemically coated at low cost and low cost coated substrates. The substrates are not particularly limited, particularly preferred are glass and glass ceramics.

The sol-gel technology can be used in unexpected ways to produce almost arbitrarily structured substrates, although low-viscosity solutions can be used. Nevertheless, sharp and non-running structures are preserved. In addition, the viscosity of the sol-gel solution can be adjusted in the desired manner, so that it is possible to work with low-viscosity as well as highly viscous sol-gel solutions, whereby the best results are achieved for the respective application.

For structured application of the sol-gel solution can be made of known application and printing methods, so that no special equipment must be designed and designed.

The sol-gel method allows economic structuring of large areas, which can be used, inter alia, on aqueous systems, so that the applied structures release no toxic solvents, are completely inert and used safely indoors can be.

By the 3 variants of the method according to the invention a suitable variant can be selected, whereby a high degree of flexibility is possible.

The advantage of such sol-gel fabricated structures is also the frequently obtained good mechanical thermal and photochemical stability, room temperature capability and, if desired, high spectral transparency. Another advantage of such sol-gel layers is in most cases also that they are not a source of food for microorganisms, since they are completely toxicologically as well as biologically inert. The inorganic sol-gel structure to be produced in the cured state is a structure which is free of impurities. This is therefore also suitable for uses with food contact.

With the sol-gel method used according to the invention, it is possible to produce thin, glassy, optionally colored, functional layers in great variety and structure. It is possible to create tailor-made structures related to specific applications.

The following exemplary embodiments serve to illustrate the method according to the invention. They are to be understood merely as possible, exemplarily illustrated procedures, without restricting the invention to their content.

EXAMPLES Embodiment 1

Cooking surface made of a transparent glass ceramic with a displayable, colored underside coating

A displayable underside coating has recesses in those areas of the hob where electronic display panels and LEDs are located. The electronic display elements are thus better recognizable on the cooking surface. The structuring of the coating is realized by first masking the hob at the desired locations with a resist. As a rule, a sufficiently viscous and thixotropic lacquer (eg Wepelan Abdecklack SD 2154 E from Peters, Abziehlack SD 2962 P from Peters or Abziehlack 80 2039 from Ferro) is used for this purpose, which is applied by means of screen printing technology becomes. Depending on the type of paint used, it is particularly useful if it is baked before further operations (at temperatures of up to 200 ° C).

• Herstellung des Bindemittels:
  • 44,3 g Tetraethoxysilan (TEOS)
  • 25,7 g n-Propanol
  • 19,5 g destilliertes Wasser
  • 8,9 g Ethylenglykol
  • 1,8 g konzentrierte Salzsäure (37%)

An example of a sprayable pigment-filled sol-gel color (hue rose) is given below:

• Preparation of the binder:
  • 44.3 g of tetraethoxysilane (TEOS)
  • 25.7 g of n-propanol
  • 19.5 g of distilled water
  • 8.9 g of ethylene glycol
  • 1.8 g concentrated hydrochloric acid (37%)

• Herstellung der Farbe:
  • 100 g Bindemittel
  • 35,7 g Iriodin 103 Rutil Sterling Silver
  • 3,6 g Bayferrox 180
  • 7,1 g Aerosil 0X50

All ingredients are combined and the mixture stirred for 3 h.

• Production of the color:
  • 100 g of binder
  • 35.7 g Iriodin 103 Rutile Sterling Silver
  • 3.6 g Bayferrox 180
  • 7.1 g Aerosil 0X50

Pigments and fillers are stirred into the binder by means of a stirrer with dissolver disk. To adjust the sprayability, the color is mixed with a further 43.0 g of n-propanol as the solvent.

Following the pigment-filled sol-gel color is applied over the entire surface, for example by means of the spraying or casting process on the substrate and dried for sufficient time in the air.

Depending on the type of Abdecklacks used this is now removed by a suitable method. This is possible, for example, by treating the layer with an organic solvent (eg acetone) or mechanically by stripping off. The display fields are now free. Finally, the structured layer is baked under suitable conditions.

Reference example 2: Coated Mirogard glass with logo

In order to decorate an anti-reflective Mirogard glass with a logo, the anti-reflection effect of the AR 3-layer system is lifted at those points where the logo is to appear. The result is a so-called "contrast decoration" (or "indirect decoration"), where the last, ie low-refraction, SiO ₂ layer is recessed at the desired locations by applying the Si-containing sol realized by means of digital printing technique in the final coating step. the SiO ₂ layer is applied directly in a structured form, there is no more full-surface coating.

Claims (22)

1. A substrate, comprising at least one entire-surface or partial-surface macrostructured layer, obtainable by a method:

   - application of a sol-gel solution in a structured form onto a substrate, and

   - drying and/or baking by obtaining a sol-gel layer,

   with the application of the sol-gel solution being performed in an already structured form onto the substrate with a known printing method,
   and the printing method being chosen with a low-viscous sol-gel solution from tampon or gravure printing, or
   the application of the sol-gel solution being performed in structured form onto the substrate with a highly viscous, sufficiently thixotropic sol-gel solution with a printing method chosen from silk screen printing, tampon-offset or letterpress printing,
   with "low viscous" meaning a viscosity in the range of approximately 0.1 to approx. 10⁴ mPa s and "highly viscous", "sufficiently thixotropic" meaning a viscosity, in the absence of shearing forces, over a limit of approximately 10³ mPa s.
2. A substrate according to claim 1, characterized in that the solvent in the sol-gel solution is chosen from water, alcohol as well as known, especially common, preferably halogen-free, low-boiling (boiling point: up to 120°C) and high-boiling solvents (boiling point: 120 to 250°C) and mixtures thereof.
3. A substrate according to at least one of the preceding claims 1 to 2, characterized in that the sol-gel layer comprises further components, chosen from the group consisting of inorganic and/or organic dyestuffs, pigments and additives such as thickeners, dispersing agents, processing aids, antifoaming agents, de-aerators, antisettling agents, surface-tension modifiers, slip additives and flow-control agents, cross-linking additives, primers and the like.
4. A substrate according to at least one of the preceding claims 1 to 3, characterized in that the substrate is chosen from plastic, metal, especially special steel, wood, enamel, glass and ceramic material, especially glass ceramics, preferably glass and glass ceramics.
5. A substrate according to at least one of the preceding claims 1 to 4, characterized in that the substrate is transparent.
6. A substrate according to at least one of the preceding claims 1 to 5, characterized in that the sol-gel solution contains at least one titanium oxide, zirconium oxide, silicon oxide, aluminum oxide, tin oxide, boron oxide or phosphorus oxide, or mixtures thereof, preferably silicon oxide.
7. A method for producing a substrate, comprising an entire-surface or partial-surface macrostructured layer according to one of the claims 1 to 6, comprising the following steps:

   - application of a sol-gel solution in an already structured form onto a substrate;

   - drying and/or baking by obtaining a sol-gel layer,

   with the application of the sol-gel solution being performed in an already structured form onto the substrate with a known printing method,
   and the printing method being chosen with a low-viscous sol-gel solution from tampon or gravure printing, or
   the application of the sol-gel solution being performed in structured form onto the substrate with a highly viscous, sufficiently thixotropic sol-gel solution with a printing method chosen from silk screen printing, tampon-offset or letterpress printing,
   with "low viscous" meaning a viscosity in the range of approximately 0.1 to approx. 10⁴ mPa s and "highly viscous", "sufficiently thixotropic" meaning a viscosity, in the absence of shearing forces, over a limit of approximately 10³ mPa s.
8. A method for producing a substrate according to claim 7, characterized in that the method step of optional baking is omitted when the quality of the layer thus formed is sufficient.
9. A method according to at least one of the preceding claims 7 or 8, characterized in that the temperature for drying the sol-gel solution is set in the range of room temperature (25°C) to 300°C, preferably of room temperature (25°C) to 100°C.
10. A method according to at least one of the preceding claims 7 to 9, characterized in that the temperature for baking the sol-gel solution is set in the range of 200°C to 800°C, preferably 250° to 600°C.
11. A method according to at least one of the preceding claims 7 to 10, characterized in that the solvent of the sol-gel solution is chosen from water, alcohol as well as preferably halogen-free, low-boiling (boiling point: up to 120°C) and high-boiling solvents (boiling point: 120 to 250°C) and mixtures thereof, as known to the person skilled in the art.
12. A method according to at least one of the preceding claims 7 to 11, characterized in that further components are used in the sol-gel solution, chosen from the group consisting of organic and/or inorganic dyestuffs, pigments and additives such as thickeners, dispersing agents, processing aids, antifoaming agents, de-aerators, antisettling agents, surface-tension modifiers, slip additives and flow-control agents, cross-linking additives, primers and the like.
13. A method according to at least one of the preceding claims 7 to 12, characterized in that the substrate is chosen from plastic, metal, especially special steel, wood, enamel, glass and ceramic material, especially glass ceramics, preferably glass and glass ceramics.
14. A method according to at least one of the preceding claims 7 to 13, characterized in that a transparent substrate is chosen.
15. A method according to at least one of the preceding claims 7 to 14, characterized in that the substrate is structured on one side or both sides.
16. A method according to at least one of the preceding claims 7 to 15, characterized in that the sol-gel solution is produced with one or several inorganic metal oxides, chosen from titanium oxide, zirconium oxide, silicon oxide, aluminum oxide, tin oxide, boron oxide or phosphorus oxide, or mixtures thereof.
17. A method according to at least one of the preceding claims 7 to 16, characterized in that a sol-gel solution is used which comprises the following or consists of:

    approx. 1 to approx. 80 percent by weight of metal oxide, metal oxide precursor or metal(s);

    approx. 20 to approx. 99 percent by weight of solvent; 0 percent by weight to approx. 50 percent by weight of coloring component(s), and

    0 percent by weight to approx. 10 percent by weight of additive(s),

    with all components present adding up to 100 percent by weight.
18. Entire-surface or partial-surface macrostructured layer on a substrate, obtainable according to a method according to one of the preceding claim 7 to 17.
19. Entire-surface or partial-surface macrostructured layer according to claim 18, characterized in that the macrostructured layer is present in the inside regions of the substrate and is omitted in the boundary regions, or vice-versa.
20. The use of a partial-surface or entire-surface macrostructured layer on a substrate according to claim 18 or 19 in the form of a functional layer, chosen from an anti-reflex layer, color layer, decorative layer, photocatalytic layer, antimicrobial layer, anti-virus layer, anti-mold layer, fungicide layer, anti-algae layer, anti-fogging layer, anti-fingerprint layer, cleaning layer, odor-neutralization layer, air-cleaning layer, or combinations thereof.
21. The use of a partial-surface or entire-surface macrostructured layer according to claim 20, with the structuring of the layer having the purpose to facilitate the installation capability of the coated substrate into an overall system or to enable the same at all.
22. The use of a substrate, comprising at least a partial-surface or entire-surface macrostructured layer, according to one of the preceding claims 1 to 6, as a cooking surface, architectural glass, glazing, especially of windows, in picture frames, tiles, pool linings, mirrors, walls, panels, inspection glasses, baking trays, panes, equipment of baking ovens, dishwashers or refrigerator and freezer furniture, stowage places, covers, plates, containers, eating and drinking utensils, kitchen utensils, especially glass and glass ceramic objects.