DE102019006134A1 - Process for modifying the surface properties of mineral substrates, glass and glazed substrates - Google Patents

Abstract

Method for modifying the surface properties of mineral substrates, glass and glazed substrates, in which a precursor material is applied to the surface of the substrate to be modified and the surface is subsequently either dried or cleaned or cleaned and dried.

Description

The present invention relates to a method for modifying the surface properties of mineral substrates, glass and glazed substrates.

Nowadays, materials with mineral surfaces or generally mineral substrates are used in a wide variety of areas. They serve as building and construction materials, countertops, wall and floor tiles and much more. These materials include, in particular, natural stone, artificial stone, ceramics and concrete. Glass is also used in many ways, for example as window glass, for shower cubicles and for furniture.

All of these materials have in common that their surface properties are usually in need of improvement or at least alternatives to previous methods for producing such materials are desirable. The improvements sought relate in particular to the surface hardness, but also to the dirt resistance and / or the possibility of easy cleaning of such surfaces, their hydrophobic or hydrophilic properties and their behavior towards microbial germs, in particular bacteria, viruses, algae and fungi. In addition, there is a need for technically simple and economical processes.

Methods are already known from the prior art with which surface properties of mineral substrates are modified and, in general, improved. Worth mentioning in this context are the DE10346018 , the DE102011087060 as well as the DE102016114000 . In general, these materials still have a surface hardness that is in need of improvement, for example.

Despite various efforts in the present field, there is still a need for the simplest and most economical method possible, and it is therefore the object of the present invention to specify at least one further method for hardening mineral surfaces which overcomes at least one of the disadvantages known from the prior art.

The present object is achieved by a method according to the attached claim 1 and the independent claims 4 and 9. Advantageous refinements are each the subject matter of the directly or indirectly referenced claims.

In its simplest embodiment, the present invention relates to a method for modifying the surface properties of mineral substrates, glass and glazed substrates, in which a precursor material is applied to the surface of the substrate to be hardened and the surface is subsequently either dried or cleaned or cleaned and dried becomes.

The mineral surfaces include in particular those made of natural stone, artificial stone, ceramic and concrete, but all mineral surfaces can be processed with the method according to the invention, for example also of plaster of paris or gypsum fiber boards.

During the investigations into the present invention it has surprisingly been found that even the application of a precursor material which, starting from one or more members of the trivalent and tetravalent metal alkoxides, colloidal silica sol, alkali water glass and tetraethylorthosilicate hydrolyzate, methyltriethylorthosilicate hydrolyzate and three- or group comprising tetravalent metal halides, the precursor material from the aforementioned group not being selected exclusively on the basis of colloidal silica sol, alkali water glass or a combination of these two, leading to an increase in the surface hardness of the treated substrate. It was particularly surprising that even the application of a precursor material which comprises a single member of the aforementioned group, as long as this is not silica sol or alkali water glass, and simple drying after application can bring about such an increase in the surface hardness of the treated substrate.

When selecting several compounds for the production of the precursor material, the combinations of metal alkoxide and tetraethyl orthosilicate hydrolyzate and / or methyl triethyl orthosilicate hydrolyzate are; Metal alkoxide, silica sol and / or alkali water glass; Metal alkoxide, tetraethyl orthosilicate hydrolyzate and / or methyl triethyl orthosilicate hydrolyzate and silica sol and / or water glass are particularly preferred. These combinations as the starting point for the precursor material already lead to excellent results in terms of the hardness of the treated substrates, without the need for further functionalization.

Regardless of the selected combination of the starting compounds mentioned for the production of the precursor material, the trivalent and / or tetravalent metal alkoxides are made from the metal alkoxides of B, Al, Si, Ti and Zr and the metal halides are made from tetrachlorosilane, trichlorosilane, titanium tetrachloride, titanium trichloride, aluminum trichloride, Zirconium tetrachloride and boron trichloride are preferably selected. The metal alkoxides are particularly preferred here because they are easier to handle.

An advantageous development of the method according to the invention, which is independent of the number of components selected for producing the precursor material, provides that the substrate is further functionalized, with functionalization in the context of the present invention in particular providing the substrate surface with further advantageous and therefore, desirable properties are understood. This further functionalization can be a further increase in surface hardness, imparting antimicrobial properties, coloring, deepening of color, increasing the degree of gloss, improving chemical resistance, improving scratch resistance or a combination of two or more of these properties.

To achieve this, in a particular embodiment of the invention, a functionalizing agent imparting or promoting the corresponding property is simply added to the precursor material or, in another embodiment, such a functionalizing agent, alone or in combination of several of these, is used to produce a functionalizing agent in Used in the form of a solution or suspension. Both are fundamentally familiar to the person skilled in the art, since in each case it is only a matter of bringing one or more functionalizing agents into solution or suspending them so that they are present in an administrable form.

If functionalizing agent is not already added to the precursor material, in this embodiment of the invention, after drying or cleaning or cleaning and drying, the further functionalization of the substrate surface by applying a functionalizing agent made from one or more functionalizing agents, followed by further drying or cleaning or Cleaning and drying, carried out.

An alternative embodiment of the present invention relates to a method for modifying surfaces of resin-bonded artificial stones, in which a mixture of water, one or more organic solvents and one or more acids is applied to the surface of the substrate to be modified and the surface is then either dried or cleaned or cleaned and dried. In this embodiment of the method according to the invention, too, a functionalizing agent can already be introduced directly into the mixture described above.

In a modification of this method, it is also possible not to incorporate the functionalizing agent directly into the mixture, but to apply a functionalizing agent after drying or cleaning or cleaning and drying in order to give the surface one or more of the aforementioned properties obtainable by functionalizing.

Regardless of whether it is further functionalized, this is particularly advantageous with resin-bonded artificial stone, because it can save polishing processes or at least have to be carried out with significantly less effort, whereby it is assumed that the advantageous effect is based on the combination of solvent and acid, which causes a softening or partial dissolution of the resin part of the artificial stone and thus facilitates its plasticization and at least leads to a smoother substrate surface.

When modifying artificial stone, however, the embodiment of the method according to the invention in which at least one trivalent or tetravalent metal cation is contained in the precursor material is more preferred, since here metal oxide crystals crystallize out in a very fine and uniform distribution during the plasticization of the resin component close packing ensure particular stability and thus hardness of the treated substrate.

In general, the colloidal silica sols used according to the invention are available, for example, inexpensively under the trade names LEVASIL® and KÖSTROSOL® and can usually be used in the present process without further pretreatment. The also inexpensive Li, Na and K water glasses, which are available as a solution and can be used directly, or are dissolved in a corresponding amount of water before use, can also be used as alkali water glasses.

After the precursor material has been applied, the treated mineral surface is briefly cleaned to remove any excess material or dirt. This can be done in a simple way and, in the simplest case, by blowing off the surface with compressed air or a blower, possibly also by polishing with one or more polishing heads, polishing plates or a combination of blowing and polishing, in which case the surface is first blown off and then is easily polished off with the polishing heads or polishing plates.

The alkoxide radicals are generally of any nature, but C ₁ -C ₄ alkoxides are generally preferred solely because of their comparatively favorable availability. In particular, the methoxides, ethoxides, iso- and n-propoxides and the n-, iso- and tert-butoxides are to be emphasized. The propoxides are particularly preferred.

It has also been shown, surprisingly, that it has an advantageous effect on the crystallization taking place if the precursor material contains, in addition to at least one metal alkoxide, tetraethyl orthosilicate hydrolyzate and / or methyl triethyl orthosilicate hydrolyzate, a combination of at least one metal alkoxide, tetraethyl orthosilicate hydrolyzate and / or methyltriethylorthosilicate hydrolyzate as well as silica sol and / or alkali water glass is a precursor material which leads to particularly hard surfaces and is therefore also particularly preferred.

Regardless of the embodiment of the method according to the invention selected, the aforementioned drying is preferably carried out by means of a fan device and / or a heating device, such as for example IR radiators, or a combination of both, in particular by means of a heated fan device.

Also regardless of the chosen embodiment of the method according to the invention, cleaning is preferably carried out in the simplest case by blowing off with compressed air, a blower or by light polishing with polishing devices with low contact pressure customary in the field of ceramics and artificial stone processing.

The step of functionalization, which is independent in a simple embodiment of the invention and, with the exception of the exclusive selection of silica sol and / or alkali water glass from the group mentioned at the beginning for producing the precursor material, surprisingly leads to an even greater increase in the hardness of the surface of the treated Substrate and gives the substrate surface further, advantageous functional properties. First of all, hydrophobization and hydrophilization of the substrate surface should be mentioned here, which make it difficult for dirt to adhere or enable easy cleaning. An improved chemical resistance of the surface can also be obtained in this way. Also has antimicrobial properties. The color, depth of color or the degree of gloss of the substrates can also be modified in this way.

It is preferred that the functionalizing agent is selected from the group comprising hydrophobicizing agents, hydrophilicizing agents and agents imparting antimicrobial properties, in particular glycolsilanes, polyether-functional trimethoxysilane, amino- and diamino-functional silanes, preferably 3-aminopropylmethyldiethoxysilane (AMMO), 3- Aminopropyltriethoxysilane (AMEO), bis (3-triethoxysilyl-propyl) amine, bis (3-trimethoxysilyl-propyl) amine and 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO), epoxysilanes, such as 3-glycidyloxypropyltrimethoxysilane (3- glycidyloxypropyltrimethoxysilane), glycidyloxypropyltriethoxysilane (GLYEO), ureido silanes, especially 3-ureidopropyltriethoxysilane, polyether Polydimethoxysilan, fumed silica, Polyfluoropolyether, polyurethane with Polyfluoropolyether skeleton PFPE Tetraurethanacrylat, PFPE urethane methacrylate, fluoroacrylate and fluoroacrylate polymers, such as methyl fluoroacrylate 2, alkylsilanes, arylsilanes, Cyclosiloxanes, linear siloxanes, compounds ungen of Zn, Sn, Cu, Fe, Ni and / or Pt, TiO ₂ , titanates, titanium silicates, dichloro-2-n-octyl-4-isothiazolin-3-one, 2,3-dichlorophenylpiperazine, 2-phenylphenol, benzoic acid , Polyhexanide, isothiazolines and quaternary ammonium compounds.

In general, glycolsilanes, for example, can be used for hydrophilization, but compounds such as polyether-functional trimethoxysilane, amino- and diamino-functional silanes such as 3-aminopropylmethyldiethoxysilane (AMMO), 3-aminopropyltriethoxysilane (AMEO), bis (3-triethoxysilylpropysilyl) amine, bis (3-triethoxysilylpropysilyl) amine propyl) amine, 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO), epoxysilanes, such as, for example, 3-glycidyloxypropyltrimethoxysilane (GLYMO), 3-glycidyloxypropyltriethoxysilane (GLYEmodifiedO), ureidimethylsilanes, such as 3-ureido-propyl-propylsilane, ureidimethylsilanes such as 3-ureidyloxy-propylsilane, kiesydimethyl-propylsilane, kiesydimethyl-propylsylsilanes such as 3-ureido-propyl-propylsilanes, kiesydimethyl-propylsilanes such as 3-ureido-propylsiloxysilane (DAMO), epoxysilanes

For hydrophobization, silicone oils, polyfluoropolyethers (available as Fluorolink® P54), polyurethane with a polyfluoropolyether structure (Fluorolink® P 56), PFPE tetraurethane acrylate (Fluorolink® AD 1700), PFPE urethane methacrylate (Fluorolink® MD 700), fluoroacrylate or Fluoroacrylate polymers such as methyl 2-fluoroacrylate can be used.

In addition, the compounds listed below can be used, for example, as water repellants. All of the listed silanes are hydrolyzed in water and are in solution as silanol or polymerized as siloxane.

The silanes can have methoxy, ethoxy or chloro groups as functional leaving groups.

Alkylsilanes: hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, octyltrichlorosilane, methyltrimethoxysilane

Methyltriethoxysilane, isobutyltrimethoxysilane and (2,4,4-trimethylpentyl) triethoxysilane.

Arylsilanes: phenyltrimethoxysilane and phenyltriethoxysilane.

Cyclosiloxanes: dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, and octamethylcyclotetrasiloxane.

Linear siloxanes: polydimethylsiloxanes, hexamethyldisiloxane, amino-functional polydimethylsiloxane, polydimethylsiloxane (OH terminated).

The surfaces of the substrates mentioned can also be given an antimicrobial finish. In particular, antibacterial, fungicidal, algicidal and antiviral surface properties are obtained by incorporating appropriate metals or metal cations, such as silver, platinum, copper, zinc, tin, nickel and iron as functionalizing agents in the precursor material or in the functionalizing agent.

_{Ti in the form of TiO 2} , in particular anatase, titanates, such as alkali and alkaline earth titanates, metal titanates, in particular barium titanate, strontium titanate, aluminum titanate are particularly suitable for a corresponding anti-microbial functionality, and thus can be used without restriction as a functionalization agent within the scope of the present invention , Cobalt titanate, certitant, manganese titanate, iron titanate, nickel titanate, the silicates of the aforementioned metal cations and titanium silicates.

Antibacterial and fungicidal organic substances such as dichloro-2-n-octyl-4-isothiazolin-3-one, 2,3-dichlorophenylpiperazine, 2-phenylphenol, benzoic acid, polyhexanide, isothiazolines, in particular methylisothiazolinone, chloromethylisothiazolinone, benzisothiazolinone, octylisothiazolinone and Dichloroctylisothiazolinone, quaternary ammonium compounds, for example didecyldimethylammonium chloride; C12-16-benzylalkyldimethylammonium chloride, cetyltrimethylammonium bromide, C12-14-alkyl [(ethylphenyl) methyl] dimethylammonium chloride, tetrabutylammonium hydroxide, cetylpyridinium chloride and imidazole) are likewise provided as part of the functionalizing agent.

In addition, there is also the possibility of modifying and improving the color, the depth of color and / or the degree of gloss of the substrates by using colorants and / or color bodies known to the person skilled in the art, for example carbon black for blackening or deepening, as a functionalizing agent. This is particularly important in the case of artificial stones and is therefore preferred for the same.

Regardless of the chosen embodiment of the method according to the invention, it is preferred if the precursor material and / or the functionalizing agent are each present as a solution or suspension, since these are easy to handle and dose. Although the solution and / or suspension can in principle be applied in any way, for example by dipping, flooding, pouring, dripping, brushing and printing, application by spraying or printing, for example using the technology of inkjet printing or digital printing, is preferred. in particular spraying with a spray mist with a fine to very fine droplet size. This has an advantageous effect on the homogeneity of the surface of the treated substrate.

It is more preferred if the application of the precursor material and the application of the functionalizing agent take place simultaneously and / or from a mixture thereof, because in this way only one step is carried out and only has to be dried or cleaned or dried and cleaned once .

The present invention further relates to a modified mineral substrate, glass or glazed substrate, obtained according to one of the method embodiments described above in the form of a plate, tile, slabs, a 3-D molded part and in particular in the form of a kitchen worktop, floor tile, a washing machine or sink, a shower tray, a wall or facade element, an insulating element or a drywall element.

• 1 eine Oberfläche eines mit dem Precursor-Material nach Beispiel 1 behandelten Kunststeins;
• 2 eine Oberfläche eines entsprechenden Kunststeins wie in 1, jedoch ohne Oberflächenmodifikation;
• 3 eine Oberfläche eines Kunststeins wie in 1 in größerer Auflösung;
• 4 eine Oberfläche eines Kunststeins wie in 2 in größerer Auflösung;
• 5 eine Oberfläche einer Keramik, die mit einem Precursor-Material behandelt wurde, das ausgehend von Zr-n-Propoxid und kolloidalem Kieselsol hergestellt wurde;
• 6 eine Oberfläche einer unbehandelten Keramik bei gleicher Auflösung wie in 5;
• 7 eine Oberfläche einer Keramik wie in 5 bei größerer Auflösung;
• 8 eine Pore in einer Keramik wie in den 5 und 7 bei noch größerer Auflösung,
• 9 eine Oberfläche einer Keramik, die mit einem erfindungsgemäßen Precursor-Material und nachfolgend mit einem Hydrophobierungsmittel behandelt wurde, und
• 10 eine Oberfläche einer Keramik mit Kristallabscheidungen in Poren wie in 9 bei größerer Auflösung.

The present invention is explained in more detail below on the basis of exemplary embodiments and with reference to the accompanying figures. The figures show scanning electron microscope images of the different substrates in different resolutions. Show it:

• 1 a surface of an artificial stone treated with the precursor material according to Example 1;
• 2 a surface of a corresponding artificial stone as in 1 but without surface modification;
• 3rd a surface of an artificial stone as in 1 in larger resolution;
• 4th a surface of an artificial stone as in 2 in larger resolution;
• 5 a surface of a ceramic which has been treated with a precursor material made from Zr-n-propoxide and colloidal silica sol;
• 6th a surface of an untreated ceramic with the same resolution as in 5 ;
• 7th a surface of a ceramic as in 5 at higher resolution;
• 8th a pore in a ceramic like in the 5 and 7th with even higher resolution,
• 9 a surface of a ceramic which has been treated with a precursor material according to the invention and subsequently with a hydrophobing agent, and
• 10 a surface of a ceramic with crystal deposits in pores as in 9 at a higher resolution.

As already mentioned herein, the starting substances for the precursor material are carefully added to an appropriate amount of water and stirred for 2 to 48 hours, the solution, at least as long as no silica sol and / or alkali water glass is added, becoming slightly cloudy to the maximum. This precursor material can be used in this way or stored for a longer period of time.

The precursor material produced in this way is then applied to a corresponding substrate. Although in principle any type of application that ensures uniform wetting of the substrate surface can be used, according to the invention it is preferred to effect application by spraying with a fine spray mist or by printing, because in this way a particularly uniform, continuous material application can be achieved. In addition, the application quantity can be regulated very easily and well. In general, it is sufficient if the surface is just completely wetted.

Depending on the composition of the precursor material, in particular depending on the proportion of volatile constituents, in particular alcohols or other organic solvents, the partially hydrolyzed or hydrolyzed metal compounds of the precursor material crystallize out in the form of their oxides or mixed oxides within a very short time, so that For example, an artificial stone or a ceramic has a surface with greater hardness than the untreated substrate after a simple drying process. Drying can be carried out more easily under ambient conditions, accelerated by blowing off with compressed air or by means of a blower. The drying process can be accelerated further by means of heated pressurized or blown air or, for example, by means of IR radiation.

Since only small amounts of material are required to achieve a surprisingly large effect of improving the surface hardness, the process generally does not require any further aftertreatment, since at best small or very small amounts of excess material are present. At the same time, easy cleaning, which is common in the field, can be done, as with common polishing devices, so that even the last material residues are removed. An elaborate polishing under high pressure and material use Polishing aid is not absolutely necessary. At the same time, more intensive, in particular longer-lasting, light polishing of ceramic and natural stone substrates leads to better pore filling and consequently at least to greater surface hardness and, in the case of artificial stones, to deeper modification of the substrate and more visually appealing surfaces. The use of high pressure and / or high temperature should be avoided, at least until the pores are completely filled, because the surface would be immediately vitrified.

1 shows the result of the method according to the invention, in which a composition of a precursor material was treated according to Example 1 given below. In the figure, the deposition of zirconium oxide crystals can be clearly seen in the right part of the picture, in particular filling the space between mineral components, of which only one can be seen in the left third of the picture as an almost completely smooth surface, the smoothness by filling the originally existing pores was caused with the precursor material and subsequent crystallization.

In comparison, the illustration in 2 , which shows an untreated artificial stone, a significantly larger presence of pore-like spaces can be recognized.

3rd shows a surface of an artificial stone as in 1 in greater resolution, whereby a deposition of zirconium oxide crystals can be seen not only in the pores, but also on the surface of the mineral component of the artificial stone. The formation of a practically continuous layer of hard zirconium oxide crystals is seen as an essential reason for the greater hardness of the treated substrate and is unexpected, especially with regard to the small amount of precursor material used.

4th shows an untreated artificial stone in the same resolution as 3rd for comparison. The significantly larger and deeper pores or gaps can also be seen here.

In a further example, a ceramic was treated with a precursor material according to Example 13. The result is in 5 shown. The silicon oxide and zirconium oxide crystals are clearly visible here, they are probably mixed crystals or mixtures of the crystals, on the surface and in the pores of the substrate. The difference to the in 6th The surface of a corresponding, untreated ceramic shown in the picture can be seen very clearly.

This becomes clearer in 7th who have a ceramic like in 5 shows in larger resolution. Here, too, the crystal deposits can be clearly seen, as well as a small depth of the pores after the treatment by the method according to the invention. This fact can be seen even better in 8th which shows a deposition in a pore of the ceramic after the application of the precursor material described above according to Example 13 and thus a filling of the same. In this context, it is assumed that it is precisely the filling and stabilization of the pores, in addition to the formation of a practically continuous layer, that makes a considerable contribution to the surprising improvement in the surface hardness of the substrate. A fact that is considered to be independent of the substrate treated.

In another embodiment of the method according to the invention, a precursor material is first applied to a substrate surface, dried and / or lightly cleaned and then a hydrophobizing agent and then simply dried. The result is in 11 shown. This figure shows how a completely continuous layer was formed on a ceramic substrate by this treatment, filling up all the pores, so that instead of the original pores, only slight depressions can be seen.

In 10 is a pore of the in 11 shown, treated ceramic substrate shown in full format. It is not only noticeable that the pore is completely filled, it is also very smooth.

Based on 9 and 10 the completely unexpected finding of a further increased hardness compared to a ceramic treated exclusively with precursor material due to the greater smoothing of the surface and very homogeneous layer formation can be illustrated very well.

In a further independent embodiment of the method according to the invention, surfaces of resin-bonded artificial stones have succeeded by treatment with a mixture of water, one or more organic solvents and one or more acids by spraying and subsequent drying and, if necessary, light cleaning by prolonged, light polishing with at least slight loosening and softening of the resin part of the artificial stone as well as subsequent Functionalizing to improve their hardness and to give a greater depth of color. For this purpose, one or more solvents such as acetone, acetylacetonate, isopropanol and ethyl acetate in combination with one or more of hydrochloric acid, nitric acid, sulfuric acid and acetic acid can be used and are sufficient. The increase in surface hardness is not as great as when using the precursor material described at the outset, but at least it leads to a noticeable improvement in scratch resistance, with the deepening of the color already being excellent.

These improvements in properties are attributed to the already described easy dissolving and facilitating or promoting plasticizing and the associated improvement in smoothness.

The percentages in the following examples are all in percent by weight.

Individual components of the compositions in the examples are each mixed and stirred for a period of between 2 and 48 hours. Examples 1 to 16 are examples of compositions for the precursor material.

Example 1: demi. water 64.9% Isopropanol 27.3% Zr-n-propoxide 5.5% Hydrochloric acid 37% 1.3% Nitric acid 64.9% 1.0%

Example 2: demi. water 61.5% Isopropanol 23.7% Zr-n-propoxide 12.5% Hydrochloric acid 37% 1.3% Nitric acid 64.9% 1.0%

Example 3: demi. water 90.0% Al isopropoxide 5.0% Nitric acid 64.9% 5.0%

Example 4: demi. water 90.5% Al isopropoxide 7.5% Nitric acid 64.9% 2.0%

Example 5: demi. water 87.5% Al isopropoxide 7.5% Nitric acid 64.9% 5.0%

Example 6: demi. water 88.0% Al isopropoxide 10.0% Nitric acid 64.9% 2.0%

Example 7: demi. water 85.0% Al isopropoxide 10.0% Nitric acid 64.9% 5.0%

Example 8: demi. water 83.0% Al isopropoxide 15.0% Nitric acid 64.9% 2.0%

Example 9: demi. water 65.0% Al isopropoxide 25.0% Nitric acid 64.9% 10.0%

Example 10: Zr-n-propoxide 5.0% Triethoxy (2,4,4trimethylpentyl) silane 13.2% Decamethylcyclopentasiloxane 6.2% demi. water 65.6% Polyfluoropolyether 7.6% (Fluorolink® P54) Pt complex in silicone polymer 1.1% (Wacker® catalyst C 05) Nitric acid 64.9% 1.3%

Example 11: Al-iso-propoxide 5.2% Octyltriethoxysilane 15.2% Hexadecyltriethoxysilane 7.6% Triethoxy (2,4,4trimethylpentyl) silane 7.6% demi. water 50.8% PFPE tetra-urethane acrylate 7.6% (Fluorolink® AD 1700) Pt complex in silicone polymer 1.1% (Wacker® catalyst C 05) Nitric acid 64.9% 4.9%

Example 12: Silica sol (7 nm) 5.6% (Levasil® CC 301) Silica sol (12 nm) 7.4% (Levasil® CC 401) demi water 57.0% Isopropanol 10.9% Zr-n-propoxide 2.2% Hydrochloric acid 37% 0.5% Nitric acid 64.9% 0.4% Formic acid 85% 8.0% Tetraethyl orthosilicate 8.0% (Dynasylan® A)

Example 13: Silica sol (5 nm) 14.0% Silica sol (22 nm) 18.5% demi. water 49.8% Isopropanol 13.7% Zr-n-propoxide 2.8% Hydrochloric acid 37% 0.7% Nitric acid 64.9% 0.5%

Example 14 demi. water 45.1% Isopropanol 11.9% Zr-n-propoxide 6.3% Hydrochloric acid 37% 0.6% Nitric acid 64.9% 0.5% Formic acid 85% 14.3% Tetraethyl orthosilicate 14.3% (Wacker TES 28) Ethanol 7.0%

Example 15 Silica sol (55 nm) 6.0% Silica sol (9 nm) 10.2% Silica sol (5-100 nm) 1.6% demi. water 51.1% Acetic acid 60% 12.5% Formic acid 85% 6.1% Tetraethyl orthosilicate 8.8% Isopropanol 3.7%

Example 16 demi. water 73.7% Isopropanol 17.7% Zr-n-propoxide 3.6% Hydrochloric acid 37% 0.8% Nitric acid 64.9% 0.7% LWG 3.5%

A hydrophilic functionalization is possible with the compositions of Examples 17 and 18: Example 17: 3-aminopropyltriethoxysilane (AMEO) 2.5% Polyether-functional trimethoxysilane 6.1% Silica sol (5 nm) 1.5% Silica sol (9 nm) 4.5% demi. Water 89.5% Acetic acid 60% 4.0% Isopropanol 0.9%

Example 18: Bis (3-triethoxysilyl-propyl) amine 5.8 3-glycidyloxypropyltrimethoxysilane (GLYMO) 2.7% polyether modified polydimethylsiloxane 19.1% demi. water 62.4% Fumed silica 10%

A hydrophobic functionalization is possible by using a functionalization agent with a composition according to Examples 19 and 20.

Example 19: Triethoxy (2,4,4trimethylpentyl) silane 17.1% Methyltrimethoxysilane 2.2% demi. water 75.3% nitric acid 1.2% Fluoroacrylate 4.2%

Example 20: Octyltriethoxysilane 4.2% Hexadecyltriethoxysilane 2.5% Phenyltriethoxysilane 5.6% amino-functional polysiloxane 1.2% demi. water 83.9% Acetic acid 60% 2.1% Titanium tetrabutanolate 0.5%

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• DE 10346018 [0004]
• DE 102011087060 [0004]
• DE 102016114000 [0004]

Claims (9)

Method for modifying the surface properties of mineral substrates, glass and glazed substrates, in which a precursor material is applied to the surface of the substrate to be modified and the surface is subsequently either dried or cleaned or cleaned and dried. Procedure according to Claim 1 , characterized in that the precursor material is made from one or more members of the trivalent and tetravalent metal alkoxides, colloidal silica sol, alkali water glass, tetraethylorthosilicate hydrolyzate, methyltriethylorthosilicate hydrolyzate and trivalent or tetravalent metal halides group, the precursor material is not made exclusively from colloidal silica sol, alkali water glass or a combination of these two. Method according to one of the Claim 2 , characterized in that the trivalent and / or tetravalent metal alkoxides are selected from the metal alkoxides of B, Al, Si, Ti and Zr and the metal halides from tetrachlorosilane, trichlorosilane, titanium tetrachloride, titanium trichloride, aluminum trichloride, zirconium tetrachloride and boron trichloride. Method for modifying surfaces of resin-bonded artificial stones, in which a mixture of water, one or more organic solvents and one or more acids is applied to the surface of the substrate to be modified and the surface is subsequently either dried or cleaned or cleaned and dried. Method according to one of the Claims 1 to 4th , characterized in that further functionalization of the substrate surface is carried out by introducing a functionalization agent into the precursor material or, after drying or cleaning or cleaning and drying, applying a functionalizing agent, followed by further drying or cleaning or cleaning and drying. Method according to one of the Claim 5 , characterized in that the functionalizing agent is selected from the group comprising water repellants, water repellants, colorants and color bodies and agents imparting antimicrobial properties, in particular glycolsilanes, polyether-functional trimethoxysilane, amino- and diamino-functional silanes, preferably 3-aminopropylmethyldiethoxysilane (AMMO ), 3-aminopropyltriethoxysilane (AMEO), bis (3-triethoxysilyl-propyl) amine, bis (3-trimethoxysilyl-propyl) amine and 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO), epoxysilanes, such as 3-glycidyloxypropyltrimethoxOysil ), 3-glycidyloxypropyltriethoxysilane (GLYEO), ureido silanes, especially 3-ureidopropyltriethoxysilane, polyether Polydimethoxysilan, fumed silica, Polyfluoropolyether, polyurethane with Polyfluoropolyether skeleton PFPE Tetraurethanacrylat, PFPE urethane methacrylate, fluoroacrylate and fluoroacrylate polymers, such as methyl-fluoroacrylate 2- , Alkylsilanes, arylsilanes, cyclosilos xanes, linear siloxanes, compounds of Zn, Sn, Cu, Fe, Ni and / or Pt, TiO ₂ , titanates, titanium silicates, dichloro-2-n-octyl-4-isothiazolin-3-one, 2,3-dichlorophenylpiperazine, 2-phenylphenol, benzoic acid, polyhexanide, isothiazolines and quaternary ammonium compounds, with functionalizing agents being obtainable from one or more of the functionalizing agents as a solution or suspension. Method according to one of the preceding claims, characterized in that the precursor material and / or the functionalizing agent is in each case present as a solution or suspension and is applied by means of spraying or printing. Method according to one of the Claims 5 to 6th , characterized in that the application of the precursor material and the application of the functionalizing agent take place simultaneously or from a mixture thereof. Modified mineral substrate obtained according to one of the preceding claims in the form of a plate, tile, slab, a 3-D molded part and in particular in the form of a kitchen worktop, floor tile, a washbasin or sink, a shower tray, a wall or facade element, an insulating element or a drywall element.

Images