Composition for coating substrate surfaces

Abstract

The invention relates to a composition obtained by reacting at least the components (S1) at least one compound of the general formula (SI) wherein R 1 and R 2 are each independently selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkyl aryl group; and R 3 and R 4 independently of each other, a branched or unbranched alkyl group with 1 to 6 carbon atoms or a group -C(O)-R 5 are, where R 5 each is a branched or unbranched alkyl group with 1 to 6 carbon atoms; (S2) a (3-glycidyloxypropyl)trialkoxysilane; and (S3) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof; is prepared.

Description

[0001] The invention relates to compositions particularly suitable for coating substrate surfaces. It further relates to an assembly comprising a first composition and a second composition. It also relates to uses of the compositions and methods for producing the compositions.

[0002] DE 10 2019 110 519 A1 [1] discloses a composition obtained by reacting a first composition with a second composition. The first composition contains an alkyltrialkoxysilane, a (3-glycidyloxypropyl)trialkoxysilane, water, and optionally an inorganic acid; the second composition contains an alkanol, a (3-glycidyloxypropyl)trialkoxysilane, and a crosslinker. The composition can be used to produce a sol-gel coating with which substrate surfaces can be coated.

[0003] Not every coating is equally suitable for every purpose. For example, anti-fouling coatings must have special properties. Fouling is generally understood as the formation of undesirable deposits on a surface. [2, 3] The total costs caused by fouling were estimated at 0.25% of the gross national product for developed countries in 2000. Fouling affects a wide variety of industries (e.g., food processing, wood processing, power generation).[4, 5] To reduce fouling, surfaces can be coated, other surface structures can be used, cleaning robots can be employed, or cleaning cycles can be adjusted. In practice, inorganic coatings and polymer coatings are often used for this purpose.

[0004] However, the production of inorganic coatings is energy-intensive, as they rely on electrochemical or gas-phase reactions. Organic polymer coatings are usually more flexible, but require a conversion layer for better adhesion of the organic layers, which sometimes requires carcinogenic chromium(VI) compounds. [6, 7]

[0005] Particularly in the marine sector, numerous traditional antifouling coatings based on the controlled release of biocides have been banned in recent decades due to their high environmental toxicity. [8] For example, the biocide tributyltin (TBT), widely used for this purpose, was banned by the International Maritime Organization through an international agreement that came into force in 2008. [9] As a result, copper, as well as other heavy metals and organic compounds, were used, which also have a high potential for bioaccumulation, which is why bans have already been issued in these cases, and further bans are to be expected. [10, 11]

[0006] Osborne reported on the application of sol-gel methods as an alternative for the corrosion protection of metals as early as 2001.

[12] His results showed that the produced sol-gel coatings exhibited promising adhesion and corrosion protection properties. Osborne used active coatings that continuously release active ingredients, but the incorporated reagents are constantly consumed. Many current publications incorporate catalytically or photocatalytically active substances, which also degrade over time.[13-15] Fluorinated alkyl chains or fluoropolymers are also frequently incorporated to reduce the surface energy of the coating.[13-15] An example of such a system is described in DE 10 2004 059 152 A1

[16] . However, such fluorine-containing substances are hazardous to the environment.Tetraethoxy- and alkyltriethoxysilanes are known to be strong hydrophobic agents and moderate fungicides.

[17] .

[0007] The object of the invention is to eliminate the disadvantages of the prior art. In particular, it is intended to provide a composition that can be used to form antifouling layers but does not contain fluorine-containing substances.

[0008] This object is achieved by the features of claims 1, 8, 13, 14, and 15. Advantageous embodiments of the inventions emerge from the features of the subclaims.

[0009] According to the invention, a composition is provided which is obtained by reacting at least the components (S1) at least one compound of the general formula (SI),wherein R 1 and R 2are each independently selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 3 and R 4 independently of one another, a branched or unbranched alkyl group having 1 to 6 carbon atoms or a group -C(O)-R 5 where R 5 each represents a branched or unbranched alkyl group having 1 to 6 carbon atoms; (S2) a (3-glycidyloxypropyl)trialkoxysilane; and (S3) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid, or a mixture thereof. This composition is referred to below as the first composition. It may be provided that the first composition does not contain any Q groups. It may be provided that the first composition does not contain any fluorine. Compounds of the general formula SI are also referred to below as "D-silanes" because they contain a D group.

[0010] It can be provided that the first composition is prepared by reacting at least the components (S1), (S2), (S3) and one component (S4), wherein component (S4) is a compound of the general formula S-II,wherein R 6is selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 7 , R 8 and R 9 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms.

[0011] It can be provided that the first composition is prepared by reacting at least the components (S 1A ), (S 1B ), (S2) and (S3) or by reacting at least the components (S 1A ), (S 1B ), (S2), (S3) and (S4), whereby component (S 1A ) is a compound of the general formula (S-IA),wherein R1 and R 2 have the meanings given in claim 1; and R 3A and R 4A are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (S 1B ) is a compound of the general formula (S-IB),wherein R 1 and R 2 have the meanings given in connection with the compound of the general formula SI; and R 3B and R 4B independently of each other a group -C(O)-R 5 where R 5 which has the meanings given in connection with the compound of the general formula SI.

[0012] The first composition can thus be obtained by reacting the component (S 1A ) and / or the component (S 1B) with the components (S2) and (S3) and optionally with the component (S4). The first composition can thus be obtained by reacting the components (S1), (S2) and (S3). The first composition can be obtained by reacting the components (S 1A ), (S2) and (S3) or by reacting the components (S 1B ), (S2) and (S3) or by implementing the components (S 1A ), (S 1B ), (S2) and (S3). Alternatively, the first composition can be obtained by reacting the components (S1), (S2), (S3) and (S4). The first composition can be obtained by reacting the components (S 1A ), (S2), (S3) and (S4) or by reacting the components (S 1B ), (S2), (S3) and (S4) or by converting the components (S 1A ), (S 1B), (S2), (S3), and (S4). It may be provided that no further components are used to prepare the first composition.

[0013] It can be provided that in component (S1) R 1 and R 2 are each independently a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 18 carbon atoms, preferably having 1 to 16 carbon atoms and particularly preferably having 1 to 10 carbon atoms. It can be provided that in component (S1) R 1 and R 2 are each independently a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 18 carbon atoms, preferably having 2 to 16 carbon atoms and particularly preferably having 2 to 10 carbon atoms. If R 1a substituted group, it may be substituted by one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen (except fluorine), haloalkyl (except fluoroalkyl), phenyl, cyano, nitro, nitrile, amino, monoalkylamino or dialkylamino. If R 2 a substituted group, it may be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen (except fluorine), haloalkyl (except fluoroalkyl), phenyl, cyano, nitro, nitrile, amino, monoalkylamino, or dialkylamino. The substituents are preferably hydrolysis-stable.

[0014] Preferably, R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, and phenyl. Preferably, R 1 and R2 each is methyl or phenyl, particularly preferably methyl. Preferably, R 1 and R 2 same alkyl groups.

[0015] The compound of the general formula S-IA is a compound of the general formula SI, in which R 3 and R 4 are each a branched or unbranched alkyl group having 1 to 6 carbon atoms. Preferably, R 3A and R 4A in the general formula S-IA are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Preferably, R 3A and R 4A each is methyl or ethyl, particularly preferably each is ethyl. Preferably, R 3A and R 4Aidentical alkyl groups. A preferred compound of general formula S-IA is dimethyldiethoxysilane (DMDEOS). Other preferred compounds of general formula S-IA are n-octylmethyldiethoxysilane and diphenyldiethoxysilane.

[0016] The compound of the general formula S-IB is a compound of the general formula SI, in which R 3 and R 4 independently of each other a group -C(O)-R 5 Preferably, R 5 independently at each occurrence is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl. Preferably, R 5 each is methyl or ethyl, particularly preferably each is ethyl. Preferably, both R 5 identical alkyl groups. A preferred compound of the general formula S-IB is diacetoxydimethylsilane (DMDAOS).

[0017] Component (S2) is a (3-glycidyloxypropyl)trialkoxysilane. Preferably, the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, and tert-butoxy. Particularly preferred is the (3-glycidyloxypropyl)trialkoxysilane (3-glycidyloxypropyl)triethoxysilane (GLYEO).

[0018] In a preferred embodiment, component (S1) is dimethyldiethoxysilane and component (S2) is (3-glycidyloxypropyl)triethoxysilane. In another preferred embodiment, component (S1) is diacetoxydimethylsilane and component (S2) is (3-glycidyloxypropyl)triethoxysilane. In another preferred embodiment, component (S 1A ) Dimethyldiethoxysilane, component (S 1B ) Diacetoxydimethylsilane and component (S2) (3-Glycidyloxypropyl)triethoxysilane.

[0019] It may be provided that in component (S4) R 6a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 18 carbon atoms, preferably having 1 to 16 carbon atoms and particularly preferably having 1 to 10 carbon atoms. It can be provided that in component (S4) R 6 a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 18 carbon atoms, preferably having 2 to 10 carbon atoms. If R 6 a substituted group, it may be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen (except fluorine), haloalkyl (except fluoroalkyl), phenyl, cyano, nitro, nitrile, amino, monoalkylamino, or dialkylamino. The substituents are preferably hydrolysis-stable.

[0020] Preferably, R 6selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and phenyl. Preferably, R 1 Methyl or phenyl, particularly preferably methyl.

[0021] It may be provided that in component (S4) R 7 , R 8 and R 9 are each independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl. Preferably, R 7 , R 8 and R 9 each is methyl or ethyl, particularly preferably each is ethyl. Preferably, R 7 , R 8 and R 9 identical alkyl groups. Component (S4) is preferably methyltriethoxysilane (MTEOS).

[0022] In a preferred embodiment, component (S1) is dimethyldiethoxysilane, component (S2) is (3-glycidyloxypropyl)triethoxysilane, and component (S4) is methyltriethoxysilane. In another preferred embodiment, component (S1) is diacetoxydimethylsilane, component (S2) is (3-glycidyloxypropyl)triethoxysilane, and component (S4) is methyltriethoxysilane. In another preferred embodiment, component (S 1A ) Dimethyldiethoxysilane, component (S 1B ) Diacetoxydimethylsilane, component (S2) (3-glycidyloxypropyl)triethoxysilane and component (S4) methyltriethoxysilane.

[0023] According to the invention, component (S3) is an aqueous solution of an acid. The acid can serve to catalyze the hydrolysis of the alkoxysilanes. The term "alkoxysilanes" refers to component (S1) of the first composition and, if provided, to component (S4) of the first composition. The acid can be a mixture of two or more acids. The mixture of two or more acids can be a mixture of a carboxylic acid and an inorganic acid, preferably a mixture of a carboxylic acid and a mineral acid.

[0024] Component (S3) may be an aqueous solution of a carboxylic acid or a mixture of two or more carboxylic acids. The carboxylic acid may be a monovalent, divalent, or trivalent carboxylic acid. A preferred carboxylic acid is a carboxylic acid of the general formula R 10 -COOH, where R 10is a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms. Preferred examples of a carboxylic acid are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, and caproic acid, with acetic acid being particularly preferred. The carboxylic acid can, for example, be present in the aqueous solution in a mass fraction of 1 to 50%, with a mass fraction of 2 to 20% being preferred. For example, the aqueous solution can be a 2%, 5%, 10%, or 20% aqueous solution of the carboxylic acid or carboxylic acid mixture. The "%" refers to the relative mass fraction of the carboxylic acid in the aqueous solution.

[0025] Component (S3) may be an aqueous solution of an inorganic acid or a mixture of inorganic acids. The inorganic acid may be, for example, a mineral acid such as hydrochloric acid (HCl), nitric acid, or sulfuric acid, with hydrochloric acid being preferred. The aqueous solution may, for example, contain 0.05 to 1 M of the inorganic acid or the mixture of inorganic acids, with 0.05 to 0.5 M being preferred and 0.1 M being particularly preferred. A 0.1 M aqueous hydrochloric acid solution is particularly preferred.

[0026] Component (S3) may be aqueous acetic acid or aqueous hydrochloric acid. Component (S3) may be an aqueous solution of an acid mixture, wherein the acid mixture is a mixture of acetic acid and hydrochloric acid.

[0027] It can be provided that the component (S1), the component (S2) and the component (S3) in a mass ratio m S1 : m S2 : m S3 of preferably 32 to 5 : 7 to 1 : 2, more preferably 25 to 12 : 5 to 1 : 2, even more preferably 19 to 17 : 3 to 1 : 2 and particularly preferably 19 : 1 : 2. Where m S1 the mass of component (S1), m S2 the mass of the component (S2) and m S3 the mass of the component (S3).

[0028] Is component (S1) component (S 1A ), it can be provided that the component (S 1A ), the component (S2) and the component (S3) in a mass ratio m S1A : m S2 : m S3 of preferably 32 to 5 : 7 to 1 : 2, more preferably 25 to 12 : 5 to 1 : 2, even more preferably 19 to 17 : 3 to 1 : 2 and particularly preferably 19 : 1 : 2. Where m S1A the mass of the component (S1A ), m S2 the mass of the component (S2) and m S3 the mass of component (S3). The following mass ratio is particularly preferred: (i) m S1A : m S2 : m S3 = 19 :1: 2 (see example D100)

[0029] Is component (S1) component (S 1B ), it can be provided that the component (S 1B ), the component (S2) and the component (S3) in a mass ratio m S1B : m S2 : m S3 of preferably 32 to 5 : 7 to 1 : 2, more preferably 25 to 12 : 5 to 1 : 2, even more preferably 19 to 17 : 3 to 1 : 2 and particularly preferably 19 : 1 : 2. Where m S1B the mass of the component (S 1B ), m S2 the mass of the component (S2) and m S3 the mass of the component (S3).

[0030] If component (S 1A ) and component (S 1B) is used to produce the first composition, it can be provided that the component (S 1A ), component (S 1B ), the component (S2) and the component (S3) in a mass ratio (m S1A + m S1B ) : m S2 : m S3 of preferably 32 to 5 : 7 to 1 : 2, more preferably 25 to 12 : 5 to 1 : 2, even more preferably 19 to 17 : 3 to 1 : 2 and particularly preferably 19 : 1 : 2. Where m S1A the mass of the component (S 1A ), m S1B the mass of the component (S 1B ), m S2 the mass of the component (S2) and m S3 the mass of component (S3). Component (S 1A ) and component (S 1B ) can be used in a mass ratio m S1A : m S1B from preferably 10:1 to 1:10, more preferably 5:1 to 1:5, even more preferably from 2:1 to 1:2 and particularly preferably from 1:1.

[0031] If component (S4) is used to produce the first composition, it can be provided that component (S1), component (S2), component (S3) and component (S4) are used in a mass ratio m S1 : m S2 : m S3 : m S4 of preferably 1 to 18.5 : 6 to 1 : 6 to 2 : 1 to 18, more preferably 2 to 15.5 : 4 to 1 : 4 to 2 : 2.5 to 16 and even more preferably 4 to 11.5 : 2 to 1 : 3 to 2 : 4.5 to 14. Where m S1 the mass of component (S1), m S2 the mass of the component (S2), m S3 the mass of the component (S3) and m S4 the mass of the component (S4). The following mass ratios are particularly preferred: (in the S1 : m S2 : m S3 : m S4 = 4:1: 2 : 14 (see example D25) (ii) m S1 : m S2 : m S3 : m S4 = 8:1: 2: 9.5 (see example D50) (iii) m S1 : m S2 : m S3 : m S4 = 11.5 : 1 : 2 : 4.5 (see example D75)

[0032] If component (S 1A ), component (S 1B ) and component (S4) is used to produce the first composition, it can be provided that the component (S 1A ), the component (S 1B ), the component (S2), the component (S3) and the component (S4), in a mass ratio m S1A : m S1B : m S2 : m S3 : m S4 of preferably 1 to 10 : 1 to 6 : 5 to 1 : 7 to 1 : 15 to 3, more preferably 2 to 8 : 1 to 5 : 3 to 1 : 5 to 1 : 12 to 7 and even more preferably 4 to 6 : 2 to 4 : 1 to 1 : 3 to 1 : 10 to 9. Where m S1A the mass of the component (S 1A ), m S1B the mass of the component (S 1B ), m S2 the mass of the component (S2), m S3 the mass of the component (S3) and mS4 the mass of the component (S4). The following mass ratios are particularly preferred: (in the S1A m S1B : m S2 m S3 : m S4= 4: 4 :1: 2: 9.5 (see example D50A) (ii) m S1A : m S1B : m S2 : m S3 : m S4 = 6: 2 :1: 2 : 9.5 (see example D50B)

[0033] It may be provided that the first composition contains, in addition to component (S1), component (S2), component (S3) and, if provided, component (S4), at least one solvent and / or a solubilizer. This may be particularly useful if one or both R 1 and R 2 of component (S1) are too large or too hydrophobic and / or if the residue R 6of component (S4) is too large or too hydrophobic. The term “too large” refers to the number of carbon atoms in the residue. For example, a residue can be “too large” if it has more than 8 or more than 10 carbon atoms. The use of the solvent and / or the solubilizer is then intended to ensure that the components can be provided as a homogeneous mixture. The solvent is preferably a non-polar, organic solvent. Preferred examples of such a solvent are n-pentane and n-hexane. The solubilizer is preferably a quaternary ammonium salt or phosphonium salt. Preferred examples of such a solubilizer are tetraalkylammonium halide or tetraalkylphosphonium halide. The proportion of the solvent and / or the solubilizer in the first mixture should not exceed 10 vol. %, based on the volume of the first mixture.

[0034] To produce the first composition, at least components (S1), (S2), (S3) and, if provided, (S4) are reacted with one another. For this purpose, component (S1) can be mixed with component (S2) and, if provided, component (S4) to obtain a first mixture. Component (S3) is then added to the first mixture to obtain a second mixture. Component (S3) can catalyze the conversion of components (S1), (S2) and, if provided, (S4) to form the first composition. It catalyzes the hydrolysis of components (S1), (S2) and, if provided, (S4), which are each silanes. Component (S3) serves as a catalyst in the production of the first composition. The first composition can thus be produced at least from components (S1), (S2) and, if provided, (S4) in the presence of component (S3).It may be provided that no further components other than components (S1), (S2), (S3) and, if provided, (S4) are used to produce the first composition.

[0035] The first composition can be produced at ambient pressure. It can be produced at ambient temperature, for example, room temperature.

[0036] The first composition can be used to form one or more layers. In particular, the first composition can be used to coat substrate surfaces. Curing can take place in air. The first composition can be cured at room temperature or elevated temperature. Curing at elevated temperature shortens the time required for curing. Curing at elevated temperature can, for example, take place at a temperature of 80 to 100°C. At such a temperature, curing can take place for a period of 30 minutes to 2 hours, for example. Curing at room temperature may require a longer period.

[0037] In addition to components (S1), (S2), (S3), and, if provided, (S4), the first composition may contain further components, for example one or more additives. An additive may, for example, be a filler. The filler(s) may impart color to a layer produced using the first composition, but may also perform other functions that may influence and / or determine the electrical, mechanical, magnetic, thermal, chemical, biological-medical, and / or other properties of the produced layer. However, it is not necessary for the first composition to be produced using a filler. Examples of fillers are zinc stearate and silicon dioxide. In another example, the additive may be a pigment.The pigment(s) can impart color to a layer produced using the third composition. The mass fraction of the filler(s) in the first composition is preferably no more than 35 wt.%, more preferably no more than 30 wt.%, and most preferably no more than 20 wt.%.

[0038] The first composition preferably does not contain any Q groups. For this reason, no component should be used to produce the first composition that can lead to the formation of Q groups and / or that contains Q groups. In particular, it can be provided that no tetraethylorthosilicate (TEOS) and no tetramethylorthosilicate (TMOS) is used to produce the first composition. The term "Q group" refers to a silicon atom tetrahedrally coordinated with four oxygen atoms. A Q group can, for example, be a Si(-O-Si)4 group. Since components (S1), (S2), and S4 do not contain any Q groups, it is ensured that the first composition also does not contain any Q groups.

[0039] The first composition can be used directly to coat substrate surfaces. Coating methods known from the prior art can be used for this purpose. For example, the first composition can be applied to a substrate surface by brushing, knife coating, dip coating, or spray coating. The substrate surface can be the surface of a substrate such as wood, natural fibers, plastic, synthetic fibers, glass, fiberglass panels, quartz glass, ceramic, metal, metal alloys, pressboard, paper, cardboard, paint layers, concrete, plaster, or stone. The flexibility of the fibers was not affected by the coating.

[0040] In addition to producing layers using the first composition, the third composition can also be used to produce molded articles. A molded article can be produced, for example, by infiltrating a porous material with the third composition or by casting the first composition and subsequent curing.

[0041] Layers produced from the first composition can be used, in particular, as antifouling coatings. They are swellable and flexible. They are also biocompatible and mechanically stable. The produced layers can be transparent.

[0042] According to the invention, the first composition is obtained by reacting components (S1), (S2), (S3), and, if provided, (S4). The first composition can be obtained as a sol component. The first composition can be reacted as a sol component with a hardener component. However, the first composition can also be used without the addition of a hardener component. In particular, the first composition can be used to produce layers without the addition of a hardener component. A second composition that can be used as a hardener component is described below.

[0043] According to the invention, a composition is further provided comprising a first composition and a second composition. The second composition may be a mixture of the following components: (h1) an alkanol; (h2) at least one silane, wherein the silane comprises a component (h 2A) and / or a component (h 2B ), where (h 2A ) is a (3-glycidyloxypropyl)trialkoxysilane; and (h 2B ) is a compound of the general formula (H-IB),wherein R 1 and R 2 are each independently selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 3B and R 4B independently of each other a group -C(O)-R 5 where R 5 has the meanings given in claim 1; and (h3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR13 )4, Zr(OR 14 )4, titanium acetylacetonate and mixtures thereof, wherein R 13 and R 14 a branched or unbranched alkyl group having 1 to 10 carbon atoms.

[0044] It may be provided that the second composition does not contain any Q groups, for example no Si(-O-Si)4 units.

[0045] Component (h1) can be a monohydric alcohol having 1 to 6 carbon atoms. Preferably, the alkanol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, and mixtures thereof. A preferred alkanol is ethanol. Methanol is not preferred due to its toxicity. Component (h1) serves as a solvent for components (h2) and (h3) in the second composition.

[0046] According to the invention, component (h2) is a silane. The silane can be component (h 2A ) and / or component (h 2B ). The second composition can therefore be either component (h 2A ) or component (h 2B ) or component (h 2A ) and component (h 2B ). The second composition can be used to cure a sol component. For example, it can be used to cure the first composition, but it can also be used to cure other sol components that contain at least one silane.

[0047] Component (h 2A ) is a (3-glycidyloxypropyl)trialkoxysilane. Preferably, the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, and tert-butoxy. Preferably, component (h 2A) is the same compound as component (S2). Particularly preferred is component (h 2A ) thus (3-Glycidyloxypropyl)triethoxysilane (GLYEO). It should be noted that component (h 2A ) may be included in addition to component (S2) in the composition described below.

[0048] Component (h 2B ) is a silane of the general formula H-IB. Preferably, R 1 and R 2 in the general formula H-IB, each independently represents a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 18 carbon atoms, preferably having 1 to 16 carbon atoms and particularly preferably having 1 to 10 carbon atoms. It can be provided that in component (S1) R 1 and R 2in the general formula H-IB are each independently a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 18 carbon atoms, preferably having 2 to 16 carbon atoms and particularly preferably having 2 to 10 carbon atoms. If R 1 a substituted group, it may be substituted by one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen (except fluorine), haloalkyl (except fluoroalkyl), phenyl, cyano, nitro, nitrile, amino, monoalkylamino or dialkylamino. If R 2a substituted group, it may be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen (except fluorine), haloalkyl (except fluoroalkyl), phenyl, cyano, nitro, nitrile, amino, monoalkylamino, or dialkylamino. The substituents are preferably hydrolysis-stable.

[0049] Preferably, R 5 in the general formula H-IB, independently at each occurrence, each is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl. Preferably, R 5 in the general formula H-IB each represents methyl or ethyl, particularly preferably ethyl. Preferably, both R 5 in the residues R 3B , R 4B of the general formula H-IB have identical alkyl groups. A preferred compound of the general formula H-IB is diacetoxydimethylsilane (DMDAOS).

[0050] Component (h3) is a crosslinker. The crosslinker can be a compound Ti(OR 13 )4, where R 13 has the meanings given above. The compound Ti(OR 13 )4 is a titanium(IV) alkoxide. Component (h3) is preferably selected from the group consisting of titanium(IV) alkoxide, n-propyl zirconate, titanium acetylacetonate, and mixtures thereof. A more preferred crosslinker is titanium(IV) butoxide, with titanium(IV) n-butoxide (TBOT) being particularly preferred. Titanium(IV) n-butoxide is a compound also known as titanium tetrabutoxide with empirical formula C 16 H 36 O4Ti.

[0051] In a preferred embodiment, the second composition comprises the following components: component (h1) is ethanol, component (h2) is (3-glycidyloxypropyl)triethoxysilane, and component (h3) is titanium(IV) butoxide. In a preferred embodiment, the second composition comprises the following components: component (h1) is ethanol, component (h2) is diacetoxydimethylsilane, and component (h3) is titanium(IV) butoxide. In a further preferred embodiment, the second composition comprises the following components: component (h1) is ethanol, component (h 2A ) is (3-glycidyloxypropyl)triethoxysilane, component (h 2B ) is diacetoxydimethylsilane, and component (h3) is titanium(IV) butoxide. The second composition may contain other components.

[0052] If the first composition contains a compound of the general formula S-IB, it can be provided that the second composition does not contain a compound of the general formula H-IB. If the second composition contains a compound of the general formula H-IB, it can be provided that the first composition does not contain a compound of the general formula S-IB. However, it can also be provided that both the first composition contains a compound of the general formula S-IB and the second composition contains a compound of the general formula H-IB. It is preferred that the compound of the general formula S-IB and the compound of the general formula H-IB are the same compound.

[0053] In one embodiment, the second composition consists only of components (h1), (h2) and (h3). In another embodiment, it consists only of components (h1), (h 2A) and (h3). In a further embodiment, it consists only of the components (h1), (h 2B ) and (h3). In yet another embodiment, it consists only of the components (h1), (h 2A ), (h 2B ) and (h3).

[0054] The second composition can be used as a curing component for the first composition, which represents the sol component. The second composition contains the crosslinker, so the first composition preferably does not contain a crosslinker.

[0055] In the second composition, the components (h1), (h2) and (h3) can be present in a mass ratio m h1 : m h2 : m h3 of preferably 0.5 to 4 : 0.5 to 4 : 0.1 to 2, more preferably 1 to 3 : 1 to 3 : 0.5 to 2, even more preferably 1.5 to 2.5 : 1.5 to 2.5 : 0.7 to 1.5 and particularly preferably 2 : 2 : 1. Where m h1 the mass of component (h1), m h2the mass of component (h2) and m h3 the mass of component (h3). Components (h2) can be component (h 2A ), component (h 2B ) or both components.

[0056] If the component (h 2B ), the components (h1), (h 2A ), (h 2B ) and (h3) in a mass ratio m h1 : m h2A : m h3 : m h2B of preferably 0.25 to 6 : 0.25 to 5.5 : 0.25 to 6 : 0.1 to 2, more preferably 0.5 to 4 : 0.5 to 3.5 : 0.5 to 4 : 0.15 to 2, even more preferably 1 to 3 : 1 to 2.5 : 1 to 2 : 0.25 to 1.5 and particularly preferably 2 : 1.5 : 1 : 0.5. Where m h1 the mass of component (h1), m h2A the mass of the component (h 2A ), m h3 the mass of component (h3) and m h2B the mass of the component (h 2B ).

[0057] In a preferred embodiment, the second composition is a mixture whose component (h1) is ethanol, whose component (h 2A ) (3-Glycidyloxypropyl)triethoxysilane (GLYEO) and its component (h3) titanium(IV) butoxide (TBOT). The components (h1), (h 2A ) and (h3) in a mass ratio m h1 : m h2 : m h3 = 2 : 2 : 1 in the second composition. In another preferred embodiment, the second composition is a mixture whose component (h1) is ethanol, whose component (h 2A ) (3-Glycidyloxypropyl)triethoxysilane (GLYEO), whose component (h3) is titanium(IV) butoxide (TBOT) and whose component (h 2B ) Diacetoxydimethylsilane (DMDAOS). The components (h1), (h 2A ), (h3) and (h 2B ) in a mass ratio m h1 : m h2A : m h3 : m h2B= 2 : 1.5 : 1 : 0.5 must be included in the second composition.

[0058] To produce the second composition, components (h1), (h2), and (h3) are mixed together. In contrast to the production of the first composition, the production of the second composition does not necessarily involve a chemical reaction. This is reflected in the high long-term stability of the second composition. To produce the second composition, component (h3) can be introduced into component (h1) or a first portion of component (h1) and mixed with it to obtain a first mixture. Component (h2) is then introduced into the first mixture to obtain a second mixture. If only a first portion of component (h1) was previously used, the remaining second portion of component (h1) can be used to absorb any residues of component (h3) and to add both together to the second mixture.Given the high viscosity of component (h3)—this applies particularly when titanium(IV) butoxide is used as component (h3)—vigorous stirring of the first and second mixtures is advantageous to achieve a homogeneous distribution of components (h2) and (h3) in component (h1). Even if the preparation of the second composition is not necessarily associated with a chemical reaction, reactions between the components of the mixture cannot be completely ruled out. For example, a reaction between OR can occur. 13 -groups of the crosslinker Ti(OR 13 )4 with ethanol molecules cannot be completely ruled out.

[0059] The second composition can be produced at ambient pressure. It can be produced at ambient temperature, for example, room temperature.

[0060] The volume ratio of the first composition to the second composition may be 0.5 to 2:2 to 0.5, with a volume ratio of 1:1 being preferred.

[0061] The first composition and the second composition are preferably provided separately from one another to avoid premature and undesired curing. By combining the first composition and the second composition, a third composition is obtained. This third composition can be used particularly advantageously for forming layers, in particular for forming layers on substrate surfaces. In one embodiment, the composition according to the invention can consist of a sol component obtained by reacting only components (S1), (S2), (S3) and, if provided, (S4), and a hardener component consisting only of components (h1), (h2) and (h3). However, it can additionally contain one or more additives.

[0062] According to the invention, a composition is thus provided which is produced from the composition according to the invention by reacting the first composition with the second composition. This composition is referred to in the present invention as the third composition. To produce the third composition, the first composition and the second composition are mixed with one another. The volume ratio of the first composition to the second composition can be 0.5 to 2:2 to 0.5, with a volume ratio of 1:1 being preferred. The third composition cures under the action of the crosslinker contained in the second composition, i.e. component (h3). Curing can take place at ambient pressure and ambient temperature, for example room temperature.

[0063] The third composition preferably does not contain any Q groups. For this reason, no component should be used to produce the third composition that can lead to the formation of Q groups and / or that contains Q groups. In particular, the first composition and the second composition should not contain any component that can lead to the formation of Q groups and / or that contains Q groups. In particular, it can be provided that the first, second, and third compositions do not contain tetraethylorthosilicate (TEOS) or tetramethylorthosilicate (TMOS), or that these compounds are used to produce the first, second, or third composition. Since components (S1), (S2), (S4), and (h2) do not contain any Q groups, it is ensured that the third composition does not contain any Q groups either. It can thus be provided that the third composition does not contain any Si(-O-Si)4 units.

[0064] Preferably, the third composition does not contain fluorine. For this reason, no component containing fluorine should be used to prepare the third composition. In particular, the first composition and the second composition should not contain fluorine. The layers obtained using the third composition are preferably fluorine-free.

[0065] The third composition may contain one or more additives. An additive may, for example, be a filler. The filler(s) may impart color to a layer produced using the first composition, but may also perform other functions that may influence and / or determine the electrical, mechanical, magnetic, thermal, chemical, biological-medical and / or other properties of the produced layer. However, it is not necessary for the third composition to be produced using a filler. A filler may, for example, be zinc stearate or silicon dioxide. In another example, the additive may be a pigment. The pigment(s) may impart color to a layer produced using the third composition.The mass fraction of the filler(s) in the third composition is preferably not more than 35 wt.%, more preferably not more than 30 wt.% and particularly preferably not more than 20 wt.%.

[0066] The third composition can be prepared in one embodiment by reacting the reaction product of only components (S1), (S2), (S3) and, if provided, (S4) with the mixture of only components (h1), (h2), (h3) and, if provided, (h4). In another embodiment, it can be prepared by reacting the reaction product of only components (S1), (S2), (S3) and, if provided, (S4) with the mixture of only components (h1), (h2), (h3) and, if provided, (h4) and subsequently adding one or more additives. Component (h2) can be component (h 2A ), component (h 2B ) or both components.

[0067] The third composition can be used to form one or more layers. A layer produced using the third composition is a hybrid material layer based on siloxanes. This layer can cure at room temperature. It is biocompatible and mechanically stable. It is also swellable and flexible. Layers produced from the third composition can be used, in particular, as antifouling coatings. The first composition and the composition according to the invention are also storage-stable.

[0068] The third composition obtained by mixing the first and second compositions can be used directly to coat substrate surfaces. Coating methods known from the prior art can be used for this purpose. For example, the third composition can be applied to a substrate surface by brushing, knife coating, dip coating, or spray coating. The substrate surface can be the surface of a substrate such as wood, natural fibers, plastic, synthetic fibers, glass, fiberglass panels, quartz glass, ceramic, metal, metal alloys, pressboard, paper, cardboard, paint layers, concrete, plaster, or stone. The flexibility of the fibers was not affected by the coating.

[0069] In addition to producing layers using the third composition, the third composition can also be used to produce molded articles. A molded article can be produced, for example, by infiltrating a porous material with the third composition or by casting the third composition and subsequent curing.

[0070] Layers produced from the first composition can be used in particular as antifouling coatings.

[0071] The invention enables the production of a two-component sol-gel coating using silanes containing D groups. These silanes are component (S1), for example, alkoxysilanes containing D groups. The layers produced using the third composition according to the invention are preferably free of Q groups and fluorine.

[0072] The layers obtained using the third composition differ from the layers known from DE 10 2019 110 519 A1 in that they are more flexible. The use of component (S 1B ), which is preferably a diacetoxydialkylsilane, enables the production of layers that exhibit increased adhesion. Die-sol components, for the production of which component (S 1B ) can be synthesized at room temperature and are stable at room temperature for several months.

[0073] The present invention provides a two-component layer system based on a sol-hardener mixture for producing hybrid materials. The composition according to the invention is a two-component system, with the first component being the sol component and the second component being the hardener component. A mixture of the sol component and the hardener component can be used to produce layers that can be considered hybrid materials.

[0074] In a preferred embodiment, the first composition, which is the sol component, is composed of at least the components MTEOS (methyltriethoxysilane, C7H 18 O3Si), DMDEOS (dimethyldiethoxysilane, C6H 16 O2Si), GLYEO ((3-glycidyloxypropyl)triethoxysilane, C 12 H 26 O5Si), 0.1 M HCl and optionally diacetoxydimethylsilane (C6H 12O4Si). The hydrolysis of the silanes is catalyzed by 0.1 M HCl. A preferred hardener component consists of ethanol (C2H5OH), GLYEO and TBOT (titanium(IV) butoxide, C 16 H 26 O4Ti). The hardener component can be added to the sol component to allow the layers to cure at room temperature. However, it is also possible to use the first composition alone, i.e., without adding a hardener component. For this purpose, it may be advantageous to allow the first composition to post-cure thermally.

[0075] Layers of the first composition and layers of the third composition are biocompatible due to the advantageous conditions during synthesis and application of the compositions. The advantageous conditions during synthesis include the ability to produce the first, second, and third compositions at ambient temperature, for example, room temperature, and ambient pressure, and the ability to cure the layers of the first composition and the layers of the third composition at ambient temperature, for example, room temperature, and ambient pressure.

[0076] The first composition and the second composition are suitable for a wide variety of substrates. Replacing just 10 mol% of the methyltriethoxysilane from the sol described in DE 10 2019 110 519 A1 with diethoxydimethylsilane results in a first composition with an increased shelf life of at least 11 months, although a longer period has not yet been tested. The first and the third compositions can be used particularly advantageously for the production of flexible and swellable coatings. They are therefore suitable as antifouling coatings. Using the first composition and the third composition, swellable, flexible, biocompatible, and mechanically stable silicon-based coatings can be produced. The coatings can be considered hybrid coatings. Furthermore, the first composition is storable.

[0077] The layers produced using the first composition and the layers produced using the third composition are characterized by advantageous properties. It is possible to produce the layers free of Q groups. This is due to 29Si-CP / MAS-NMR spectra of the layers demonstrated this. The layers can cure at room temperature. This is generally not the case for many state-of-the-art sol-gel systems. The resulting layers are mechanically very stable and adhere well. According to DIN EN ISO 2409, the layers achieve the highest stability on stainless steel and plates made of the copper alloy CU3. Thermogravimetric measurements (TG measurements) demonstrated that the layers only undergo significant thermal decomposition above 200 °C. Both the sol component, i.e. the first composition, and the hardener component, i.e. the second composition, are storage-stable for months, i.e. at least 11 months, at room temperature. The first composition and the second composition can be applied to create layers using all conventional application methods, for example, doctor blade coating, brushing, dipping, and spraying.The first and second compositions can be used to coat a wide variety of substrates. The resulting layers are very flexible and well-suited to swelling. Furthermore, the first and second compositions can be used to produce molded articles, for example, by infiltration into porous materials or by casting and subsequent curing.

[0078] The term "alkyl," unless otherwise stated, refers in particular to a saturated aliphatic hydrocarbon group having a branched or unbranched carbon chain with 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl group may optionally be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, amino, monoalkylamino, or dialkylamino, unless specifically stated otherwise.

[0079] The term "alkenyl," unless otherwise stated, refers in particular to an unsaturated aliphatic hydrocarbon group having a branched or unbranched carbon chain of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and most preferably 2 to 6 carbon atoms, which has at least one olefinic double bond and more preferably a single double bond. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, methylallyl, 1,1-dimethylallyl, propenyl, butenyl, pentadienyl, hexenyl, octenyl, and the like. An allyl group is preferred. The alkenyl group may optionally be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, amino, monoalkylamino, or dialkylamino, unless specifically stated otherwise.

[0080] The term "aryl," unless otherwise stated, refers in particular to a monovalent cyclic aromatic hydrocarbon group, which may comprise a mono-, bi-, or tricyclic aromatic ring. Examples of aryl groups are optionally substituted phenyl, naphthyl, phenanthryl, fluorenyl, indenyl, azulenyl, oxydiphenyl, biphenyl, methylenediphenyl, aminodiphenyl, diphenyl sulfidyl, diphenylsulfonyl, diphenylisopropylidenyl, benzodioxanyl, benzodioxylyl, benzoxazinyl, benzoxazinonyl, benzopiperadinyl, benzopiperazinyl, benzopyrrolidinyl, benzomorpholinyl, methylenedioxyphenyl, ethylenedioxyphenyl, and the like, although this list is not exhaustive. Aryl preferably includes optionally substituted phenyl and optionally substituted naphthyl, with phenyl being particularly preferred.The aryl group may optionally be substituted with one or more substituents, each substituent independently being hydroxy, alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, amino, monoalkylamino or dialkylamino, unless specifically stated otherwise.

[0081] The term "alkylaryl," unless otherwise stated, refers in particular to a monovalent aryl group bearing one or more alkyl groups, where the aryl group and the alkyl group are as defined above. Preferably, the aryl group is a phenyl group, where the alkyl group can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. Preferably, the aryl group bears only one alkyl group.

[0082] The term “halogen” refers, unless otherwise stated, to chlorine, bromine or iodine.

[0083] The term Q group refers, unless otherwise stated, to a structural unit of a poly(organo)siloxane. Poly(organo)siloxanes, also known as silicones, are polymeric compounds in which silicon atoms are linked via oxygen atoms to form a chain-like or network-like framework. Four structural units, also known as siloxane units, are distinguished: Monofunctional units are referred to as M groups or "M", where M stands for (R Z )3SiO 1 / 2 An M group forms a chain end. Difunctional units are called D groups or "D", where D stands for (R 2 )2SiO 2 / 2 A D group forms an unbranched section of the backbone. Trifunctional units are referred to as T groups or "T", where T stands for R z SiO 3 / 2A T group forms a branch of the framework. Tetrafunctional units that form a cross-link are called Q groups or "Q", where Q stands for SiO 4 / 2 stands. R z stands for a substituted or unsubstituted hydrocarbon residue.

[0084] The invention will be explained in more detail below using exemplary embodiments, which are not intended to limit the invention, with reference to the drawings. Fig. 1 photographic images of substrates to which a layer of a third composition according to the invention is applied; Fig. 2 29 Si-CP / MAS spectra of layers obtained from compositions according to the invention and a comparison composition; Fig. 3 more 29 Si-CP / MAS spectra of layers obtained from compositions according to the invention; Fig.4 a diagram of thermogravimetric measurements of layers obtained from composition 3Z50 under air and under nitrogen; Fig. 5 is another diagram of thermogravimetric measurements of layers obtained from composition 3Z50 under air and under nitrogen; Fig. 6 a diagram of thermogravimetric measurements of layers obtained from the compositions 3Z50-2 and 3Z50-3; Fig. 7 microscopic images of coated bronze plates after immersion tests in brackish water for two months; Fig. 8 images of coated CU3 plates after immersion tests in brackish water for two months; Fig. 9 images of coated slides after seven days in saline solution; Fig. 10 a photograph of air bubbles on a coated surface in a water-filled sample chamber; Fig.11 is a diagram showing bubble contact angles on coated substrate surfaces using a box plot; Fig. 12 another diagram showing bubble contact angles on coated substrate surfaces using a box plot; Fig. 13A a photograph of coated stainless steel plates after the cross-cut test; Fig. 13B is a photograph of a coated copper alloy plate after undergoing the cross-cut test; Fig. 14 a photograph of coated plates after the mandrel bending test; Fig. 15 photographs of coated copper alloy plates after adhesion tests; Fig. 16 additional photographs of coated copper alloy plates after conducting adhesion tests; Fig.17 photographs of coated panels after the mandrel bending test; Fig. 18 enlarged photographs of coated plates after the mandrel bending test; Fig. 19 digital microscopic images of coated plates after the cross-cut test; and Fig. 20 enlarged photographs of coated fabrics.

[0085] In the following, the term "vigorous stirring" refers to the maximum possible stirring speed at which the stirring tool used, for example, a magnetic stir bar, still rotates steadily, but at least 600 revolutions per minute (rpm). The stirring speed should not be changed until the end of the reaction. Example 1: Preparation of the sol component D25

[0086] Methyltriethoxysilane (MTEOS, component (S4)), dimethyldiethoxysilane (DMDEOS, component (S1A )), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m MTEOS : m DMDEOS : m GLYEO : m0, 1M HCl = 14:4:1:2. Methyltriethoxysilane, dimethyldiethoxysilane, and (3-glycidyloxypropyl)triethoxysilane were weighed into a vessel and homogenized by stirring to obtain a mixture. With vigorous stirring, 0.1 M HCl was slowly added dropwise to the mixture. The synthesis was carried out with or without ice cooling. During the HCl addition, a temperature rise of approximately 10 °C was observed. After HCl, which serves as a catalyst, was completely added, stirring was continued until a clear sol was obtained. The clear sol is sol component D25. Example 1A: Preparation of the sol component D50

[0087] The sol component D50 was prepared as described in Example 1, except that methyltriethoxysilane (MTEOS, component (S4)), dimethyldiethoxysilane (DMDEOS, component (S 1A )), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m MTEOS : m DMDEOS : m GLYEO : m0, 1 M Hc1 = 9.5 : 8 : 1 : 2 were mixed together. A clear sol was obtained as sol component D50.

[0088] The sol component D50 was storable for at least four months at room temperature. A longer-term study has not yet been conducted. Example 1B: Preparation of the sol component D75

[0089] The sol component D75 was prepared as described in Example 1, except that methyltriethoxysilane (MTEOS, component (S4)), dimethyldiethoxysilane (DMDEOS, component (S 1A)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m MTEOS : m DMDEOS : m GLYEO : m 0,1 M HC1 = 4.5 : 11.5 : 1 : 2 were mixed together. A clear sol was obtained as sol component D75.

[0090] The sol component D75 was storable for at least four months at room temperature. A longer-term study has not yet been conducted. Example 1C: Preparation of the sol component D100

[0091] Dimethyldiethoxysilane (DMDEOS, component (S 1A )), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m DMDEOS : m GLYEO : m0, 1 M HC1 = 19 : 1 : 2. The sol component D100 did not contain methyltriethoxysilane (MTEOS, component (S4)).

[0092] Dimethyldiethoxysilane and (3-glycidyloxypropyl)triethoxysilane were weighed into a vessel and homogenized by stirring to obtain a mixture. With vigorous stirring, 0.1 M HCl was slowly added dropwise to the mixture. The synthesis was carried out with or without ice cooling. A temperature increase of approximately 10 °C was observed during the HCl addition. After HCl, which serves as a catalyst, was completely added, stirring was continued until a clear sol was obtained. The clear sol is sol component D100. Example 1D: Preparation of the sol component D50A

[0093] Methyltriethoxysilane (MTEOS, component (S4)), dimethyldiethoxysilane (DMDEOS, component (S 1A )), Diacetoxydimethylsilane (DMDAOS, component (S 1B ), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m MTEOS : m DMDEOS: m DMDAOS : mGLYEO : m0, 1 M HCl = 9.5:4:4:1:2. Methyltriethoxysilane, dimethyldiethoxysilane, diacetoxydimethylsilane, and (3-glycidyloxypropyl)triethoxysilane were weighed into a vessel and homogenized by stirring to obtain a mixture. With vigorous stirring, 0.1 M HCl was slowly added dropwise to the mixture. The synthesis was carried out with or without ice cooling. During the HCl addition, a temperature rise of approximately 10°C was observed. After HCl, which serves as a catalyst, was completely added, stirring was continued until a clear sol was obtained. The clear sol is sol component D50A. Example 1E: Preparation of the sol component D50B

[0094] The sol component D50B was prepared as described in Example 1D, except that methyltriethoxysilane (MTEOS, component (S4)), dimethyldiethoxysilane (DMDEOS, component (S 1A )), Diacetoxydimethylsilane (DMDAOS, component (S 1B) (3-Glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) in a mass ratio m MTEOS : m DMDEOS m DMDAOS : m GLYEO : m0, 1 M HCl = 9.5 : 6 : 2 : 1 : 2. A clear sol was obtained as sol component D50B. Comparative Example 1: Preparation of the sol component VB-DO

[0095] Methyltriethoxysilane (MTEOS, component (S4)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (S2)) and aqueous 0.1 M hydrochloric acid (0.1 M HCl, component (S3)) were mixed in a mass ratio m MTEOS : m GLYEO : m0, 1 M HCl = 19 : 1 : 2. The sol component VB-DO did not contain dimethyldiethoxysilane (component (S1). The formulation of the sol component VB-DO corresponds to the formulation known from DE 10 2019 110 519 A1.

[0096] Methyltriethoxysilane and (3-glycidyloxypropyl)triethoxysilane were weighed into a vessel and homogenized by stirring to obtain a mixture. With vigorous stirring, 0.1 M HCl was slowly added dropwise to the mixture. The synthesis was carried out with or without ice cooling. A temperature increase of approximately 10 °C was observed during the HCl addition. After HCl, which serves as a catalyst, was completely added, stirring was continued until a clear sol was obtained. The stirring time was 0.5 h. The clear sol is the sol component VB-DO. Example 2: Production of the hardener component H1

[0097] Ethanol (component (h1)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (h2)) and titanium(IV) butoxide (TBOT, component (h3)) were used in a mass ratio of m Ethanol : m GLYEO : m TBOT= 2:2:1. 90% of the ethanol was placed in a beaker. GLYEO was added. This mixture was homogenized by stirring. TBOT was weighed and added with continuous stirring via a dropping funnel or slowly using a beaker. The remaining ethanol was used to completely transfer the TBOT into the dropping funnel and then rinse the dropping funnel or beaker. The mixture was stirred for a further two hours at room temperature. Examples 2A and 2B: Production of additional hardener components

[0098] Additional hardener components were prepared as described in Example 2, except that the ratio m Ethanol : m GLYEO : m TBOT in the range of m Etha- nol : m GLYEO : m TBOT = 2 : 1 - 3.5 : 1. In Example 2A, the ratio m was Ethanol : m GLYEO : m TBOT2: 1.5: 1, resulting in hardener component H2. In Example 4B, the ratio m was Ethanol : m GLYEO : m TBOT 2 : 3.5 : 1, which resulted in hardener component H3.

[0099] The other hardener components were used to cure the sol components prepared in Examples 1 to 1E, producing homogeneous, clear layers in each case. Example 3: Preparation of a composition 3Z25 from sol component D25 and hardener component H1

[0100] The sol component D25 prepared according to Example 1 and the hardener component H1 prepared according to Example 2 were added to a beaker in a mass ratio of 1:1 and then stirred using a magnetic stirrer until a clear, suspended matter-free solution was formed. This solution is an example of a third composition and is referred to below as Composition 3Z25.

[0101] Composition 3Z25 was then used directly for coating. Composition 3Z25 was stable for several weeks in closed containers. Examples 3A to 3G: Preparation of further compositions from a sol component and hardener component H1

[0102] The compositions given in Table 1 were prepared in the same manner as described in Example 3, except that the sol components and hardener components given in Table 3 were used. Table 1 Sol component Hardener component Description of the composition Example 3A D50 (Example 1A) H1 3Z50 Example 3B D75 (Example 1B) H1 3Z75 Example 3C D100 (Example 1C) H1 3Z100 Example 3D D50A (Example 1D) H1 3Z50A Example 3E D50B (Example 1E) H1 3Z50B Example 3F D50 (Example 1A) H2 (Example 2A) 3Z50-2 Example 3G D50 (Example 1A) H3 (Example 2B) 3Z50-3 Comparative example 3: Composition of sol component VB-3Z0 and hardener component H1

[0103] The composition VB-3Z0 was prepared as described in Example 3, except that the sol component VB-DO prepared according to Comparative Example 1 was used instead of the sol component D25. Example 4: Application of compositions 3Z25, 3Z50, 3Z75, 3Z100, 3Z50A and 3Z50B

[0104] The compositions 3Z25, 3Z50, 3Z75, 3Z100, 3Z50A, and 3Z50B were applied to the surfaces of the following substrates: copper alloy (CU3), stainless steel plates (X6Cr17), fiberglass plates, quartz glass, and natural fibers. The resulting coatings were examined.

[0105] The Fig. The substrates shown in Figure 1 have a surface on which a layer of a composition according to the invention or a comparative composition is formed (left: cotton and linen coated with 3Z50; center: glasses coated with - from left to right - 3Z100, 3Z75, 3Z50, 3Z25, and VB-3Z0; right: copper alloy coated with 3Z50). The flexibility of the fibers was not affected by the coating. Example 5: Investigation of the layersa) Characterization of the layers

[0106] The layers prepared according to Example 4 were 29Si solid-state NMR spectroscopy was used to examine the layers. The analysis revealed that the layers did not contain any Q groups.

[0107] Fig. 2 shows the 29 Si-CP / MAS spectrum of powdered coatings obtained using compositions 3Z25, 3Z50, and a reference composition VB-3Z0. The presence of the D groups was detected by the chemical shift. These groups are not present in the reference composition VB-3Z0. Fig. 3 shows that with increasing dimethyldiethoxysilane content of the sol component, the proportion of D groups increases. The T groups in composition 3Z100 are caused by the presence of GLYEO in the sol component and the curing agent component. Q groups would be indicated by signals with a chemical shift in the range of -78 ppm to -120 ppm

[18] .

[0108] Table 2 shows the percentage molar fractions of the D and T groups, which were determined by spectrum deconvolution. Table 2 Chemical shift group VB-3Z0 3Z25 3Z50 3Z75 3Z100 -7.1 ppm D1 - 0,4 % 0,7 % 0,9 % 1,3 % -12.6 ppm D1 - 2,1 % 3,5 % 3,1 % 4,9 % -18.6 ppm D2 - 3,9 % 13,9 % 14,2 % 14,7 % -20.7 ppm D2 - 12,3 % 18,6 % 31,8 % 51,2 % -48.6 ppm T1 0,5 % 2,3 % 0,9 % 0,3 % 0,2 % -57.1 ppm T2 27,8 % 24,0 % 15,4 % 12,8 % 5,9% -66.1 ppm T3 71,7 % 55,0 % 47,0 % 36,9 % 21,8 % b) Thermal resistance of the coatings based on TG measurements

[0109] Coatings produced according to Example 4 were tested using thermogravimetric (TG) measurements. For this purpose, the coatings were dried and pulverized. The test showed that the coatings were resistant to temperatures exceeding 200 °C.

[0110] The Fig. 4 and Fig. Figure 5 shows diagrams of thermogravimetric measurements of coatings obtained using the composition 3Z50. The measurements were carried out either under air or nitrogen. The thermal stability up to over 200 °C is Fig.4. The decomposition of the layer depends on whether the measurement is carried out under inert conditions, e.g., nitrogen, or air. Fig. Figure 5 shows that, depending on the atmosphere used, the maximum reaction rate occurs between 290 °C and 369 °C. The abbreviation "DTG" stands for differentiated thermogravimetry.

[0111] Fig. Figure 6 shows a diagram of thermogravimetric measurements of a coating obtained using composition 3Z50-2 and a coating obtained using composition 3Z50-3, each under a nitrogen atmosphere. The diagram shows that, depending on the composition of the hardener component used, the maximum reaction conversion occurs between 360 °C and 382 °C. The hardener components H2 and H3 differ in their GLYEO content. c) Swelling capacity and layers

[0112] The swelling capacity of coatings obtained using compositions according to the invention was investigated. The coatings adhered consistently to the substrate surface during swelling in freshwater as well as in salt water, and during subsequent drying. Tests were conducted in brackish water and in a saline solution considered to be artificial seawater. Starting with a replacement of 50 mol% of MTEOS with DMDEOS—relative to a reference composition prepared using a sol component that did not contain D-silane but did contain MTEOS, such as VB-3Z0—cracking during swelling and subsequent drying was completely prevented (see Fig.7). The resulting smooth surface has already been proven to limit corrosion and fouling during a two-month immersion test in brackish water. The inventors suspect that the layers are not completely infiltrated by the surrounding medium.

[0113] Fig. Figure 7 shows on the left a microscopic image of a bronze plate containing a layer of the reference composition VB-3Z0 and on the right a microscopic image of a bronze plate containing a layer of 3Z50, each after immersion tests in brackish water for two months. Fig.Figure 8 shows images of cleaned CU3 plates after a 2-month immersion test in brackish water. The uncoated CU3 plate (left) shows a rough surface and traces of corrosion. The middle plate was coated with a layer of the reference composition VB-3Z0, which was produced using the sol component VB-DO, i.e., a sol component without D groups. The layer cracked after swelling. The right plate was coated with a layer of 3Z50, which was produced using the sol component D50, i.e., a sol component with D groups. The 3Z50 layer is stable even during swelling and does not crack. d) Generation of hydrophobic layers

[0114] The surface wettability of the 3Z50 layer has already been analyzed using contact angle and bubble contact angle measurements. The contact angles formed by the water droplets and air bubbles can be used to determine the wettability (hydrophobic or hydrophilic) of the coated samples. This, in turn, influences the growth of organisms on the substrates. The coated slides used for the measurement method allow the same conclusions to be drawn as the tested CU3 plates. Starting at a replacement of 50 mol% of the MTEOS with DMDEOS – based on Comparative Example 1, with the proviso that the mass fraction of MTEOS stated there is considered to be 100 mol% – no cracks appeared in the coating after swelling and drying (see Fig. 9).

[0115] Fig.Figure 9 shows coated slides after seven days in saline solution (artificial seawater): left: layer of VB-3Z0, middle: layer of 3Z25, right: layer of 3Z50. Fig. Figure 10 shows an image of air bubbles in the water-filled sample chamber on a surface coated with a layer of 3Z50. The air bubbles were approximately 8 µL in size.

[0116] The determination of the bubble contact angles showed that by adding DMDEOS, hydrophobization could be achieved starting from an exchange of 25 mol% of the MTEOS with DMDEOS – based on Comparative Example 1, with the proviso that the mass fraction of MTEOS stated therein is considered to be 100 mol% – which was reflected in a reduction of the bubble contact angle. A higher D-group content did not significantly change this bubble contact angle (see Fig. 11 and Fig.12). The inventors suspect that the methyl groups of DMDEOS preferentially accumulate at the surface, so that an increase in the DMDEOS content no longer has a strong influence on surface wettability.

[0117] Fig. Figure 11 shows bubble contact angles on glass slides using a box plot. The slides were soaked in distilled water for 3 days prior to measurement. The left and right bubble contact angles were averaged. At least 20 measurement points were recorded for all coated slides, and 40 measurement points each for 3Z25 and 3Z50 coatings.

[0118] Fig.Figure 12 shows bubble contact angles on glass slides using a box plot. The slides were soaked in distilled water for 3 days prior to measurement. The left (L) and right (R) bubble contact angles are plotted separately to visualize any possible slide tilt. At least 20 measurement points were recorded for all coated slides. e) Determination of the element distribution using CHNS analysis

[0119] The coatings produced according to Example 4 were analyzed using CHNS analysis. CHNS analysis is an elemental analysis used to determine the mass percentage ω% of the elements C, H, N, and S. The results are shown in Table 3. It can be seen that the proportion of carbon and hydrogen in the coating increases due to the increase in the proportion of methyl groups, which, unlike the ethoxy groups, are not cleaved off during the hydrolysis reaction.

[0120] Table 3 shows the elemental distribution determined by CHNS analysis. The determination was carried out on powdered coatings. It was shown that with increasing proportions of D groups (from VB-3Z0 to 3Z100), the mass fraction of carbon and hydrogen in the formulation increases. Table 3 Name / Element content N in ω% C in ω% H in ω% S in ω% VB-3Z0 0,00 29,8 5,6 0,00 3Z50 0,00 32,0 5,9 0,00 3Z75 0,00 33,4 6,8 0,00 3Z100 0,00 34,3 7,1 0,00 f) Determination of the solid content of the layers after drying

[0121] The solids content of the layers prepared according to Example 4 was investigated. The solids content describes the mass fraction ω present after drying the layer for 24 h at 60 °C compared to the initial mass of the third composition used for its preparation and prepared according to one of Examples 3, 3A-3G: ω=EW layer after 24 h drying at 60°CEW third composition before drying⋅100%

[0122] The term "EW" refers to the sample weight. The results are shown in Table 4. Table 4 Designation / Element contents Solid content in ω% VB-3Z0 43,1 3Z25 37,9 3Z50 37,1 3Z75 39,1 3Z100 36,2 g) Determination of the mechanical stability of the layers

[0123] The mechanical stability of the coatings produced according to Example 4 was determined. The determination was carried out by cross-cut testing, also known as the "cross-cut test," according to DIN EN ISO 2409:2020-12

[19] . The coatings were applied to plates made of stainless steel X6Cr17 and copper alloy CU3. The best cross-cut characteristic value of 0 (smooth cut edges, no chipping) was achieved on both substrates.

[0124] Fig.13A shows on the left a plate made of stainless steel X6Cr17 on which a layer of 3Z25 was formed, in the middle a plate made of stainless steel X6Cr17 on which a layer of 3Z50 was formed, and on the right a plate made of stainless steel X6Cr17 on which a layer of 3Z100 was formed, after carrying out the cross-cut test. Fig. Figure 13B shows a plate made of copper alloy CU3 on which a layer of 3Z50 was formed after performing the cross-cut test. h) Elasticity test of the layers

[0125] The elasticity of the layers produced according to Example 4 was tested. The test was carried out according to DIN EN ISO 1519:2011-04

[20] using a mandrel bending test. The layers exhibited a high degree of flexibility using this method. The elasticity and resistance of the layers increased with increasing D-group content (see Table 5).

[0126] Fig.Figure 14 shows, on the left, a plate made of stainless steel X6Cr17 on which a layer of VB-3Z0 was formed, after conducting the mandrel bending test with a mandrel having a mandrel diameter of 32 mm. The mandrel bending tests show, on the right, a plate made of stainless steel X6Cr17 on which a layer of 3Z100 was formed, using a mandrel with a mandrel diameter of 10 mm. The mandrel bending tests confirmed the high flexibility of the layers made of compositions according to the invention, which increases with increasing D-group content.

[0127] Table 5 shows an overview of mandrel bending tests performed. The mandrel bending tests provide information about flexibility. Table 5 Composition used Mandrel diameter in mm Test passed? VB-3Z0 32 No - cracks and flaking observed 3Z25 32 Yes 25 No - cracks and flaking observed 3Z50 32 Yes 25 Yes 16 No - cracks observed 3Z75 32 Yes 25 Yes 16 Yes 10 No - cracks and flaking observed 3Z100 25 Yes 16 Yes 10 Yes 8 No - a few fine cracks on the bending point, but no chipping 6 No - a few fine cracks on the bending point, but no chipping (i) Determination of layer thickness

[0128] The layer thicknesses of the coatings produced according to Example 4 were determined using the PosiTector 6000 GP coating thickness gauge from De-Felsko. Layer thicknesses of 5 to 13 µm were determined for the coatings produced using the compositions 3Z25, 3Z50, 3Z75, and 3Z100. The deviations can be explained by the manual application. Due to the different proportions of D groups, no significant change in the dry film thickness was observed. (j) Determination of adhesion strength

[0129] The adhesion strength of the coatings produced according to Example 4 was determined according to DIN EN ISO 4624:2016-08

[21] . The determined adhesion strength values ​​were highly dependent on the substrate used. Plates made of stainless steel X6Cr17 have a smooth, mirror-like surface, which reduces adhesion. The CU3 plates have a rougher surface, which increases the adhesion of the coating to the substrate. However, the sanding pattern and the grit of the sandpaper influenced the results. Different drying times of the samples also led to differing results. The results are shown in Table 6. The maximum adhesive strength determinable with the device used is 24.0 MPa. No additional primer was used.

[0130] Table 6 does not reveal a direct trend regarding how adhesion is modified by the addition of D groups. On stainless steel, a decrease in adhesion was observed, but this cannot be confirmed for the copper alloy. The surface condition of the Cu3 alloy has a stronger influence here. Table 6 Composition used stainless steel (X6Cr17) Copper alloy (CU3) Adhesion minimum in MPa Adhesion maximum in MPa Adhesion minimum in MPa Adhesion maximum in MPa VB-3Z0 0,6 2,4 4,2 10,5 3Z50 0,6 1,5 3,0 12,2 3Z75 0,5 1,8 - - 3Z100 0,3 2,1 6,6 12,1

[0131] Fig. Figure 15 shows images of adhesion tests performed on a CU3 plate coated with a layer of 3Z100 (left) and on a CU3 plate coated with a layer of 3Z50 (right). Example 6(a) Influence of the residues R 5 and R 6 of component (S 1A ) in the Sol component

[0132] In addition to experiments in which the sol component dimethyldiethoxysilane (DMDEOS, component (S 1A)), further experiments were carried out in which dimethyldiethoxysilane was completely or partially replaced by diphenyldiethoxysilane and n-octylmethyldiethoxysilane. This is intended to determine the influence of the alkyl groups, ie the radicals R 1 and R 2 in the compound of the general formula SI.

[0133] By adding or replacing DMDEOS, further hydrophobization of the substrate surface was sought. n-Octylmethyldiethoxysilane and diphenyldiethoxysilane were incorporated into the sol component both in combination with DMDEOS and without DMDEOS. The following data refer to Comparative Example 1, with the proviso that the mass fraction of MTEOS stated therein is considered to be 100 mol%. The sum of the stated molar fractions of the D-silane(s) each results in 100 mol%, which in turn refers to the molar fraction of MTEOS being replaced. With reference to experiment (i), this means that the two D-silanes DMDEOS and diphenyldiethoxysilane together replace 75 mol% of the MTEOS contained in Comparative Example 1, with 95 mol% of the replaced MTEOS being replaced by DMDEOS and 5 mol% of the replaced MTEOS being replaced by diphenyldiethoxysilane.

[0134] The following sol components were carried out using diphenyldiethoxysilane: (i) 75 mol% of the MTEOS was replaced by D-silanes (95 mol% DMDEOS, 5 mol% diphenyldiethoxysilane). (ii) 25 mol% of the MTEOS was replaced by D-silanes (75 mol% DMDEOS, 25 mol% diphenyldiethoxysilane). (ii) 25 mol% of the MTEOS was replaced by D-silanes (100 mol% diphenyldiethoxysilane). (iv) 100 mol% of the MTEOS was replaced by D-silanes (100 mol% diphenyldiethoxysilane).

[0135] All tests, except test (iv), in which a complete replacement of the MTEOS was carried out - based on Comparative Example 1 - resulted in sols that were miscible with the hardener component H1 in a ratio of 1:1 and could be applied. By adding diphenyldiethoxysilane, the bond strength could be increased to 18 MPa on CU3 plates according to DIN EN ISO 4624:2016-08

[21] .

[0136] The following sol components were prepared using n-octylmethyldiethoxysilane. The following data refer to Comparative Example 1, with the proviso that the mass fraction of MTEOS stated therein is considered to be 100 mol%. The sum of the stated molar fractions of the D-silane(s) each equals 100 mol%, which in turn refers to the molar fraction of the MTEOS being replaced. With reference to experiment (v), this means that the two D-silanes DMDEOS and n-octylmethyldiethoxysilane together replace 25 mol% of the MTEOS contained in Comparative Example 1, with 75 mol% of the replaced MTEOS being replaced by DMDEOS and 25 mol% of the replaced MTEOS being replaced by n-octylmethyldiethoxysilane. (v) 25 mol% of the MTEOS was replaced by D-silanes (75 mol% DMDEOS, 25 mol% n-octylmethyldiethoxysilane). (vi) 25 mol% of the MTEOS was replaced by D-silanes (100 mol% n-octylmethyldiethoxysilane) (vii) 100 mol% of the MTEOS was replaced by D-silanes (100 mol% n-octylmethyldiethoxysilane).

[0137] All experiments, except experiment (vii), in which a complete replacement of the MTEOS was carried out - based on comparative example 1 - led to application-ready sols which can be mixed with the hardener component H1 in a ratio of 1:1. (b) Influence of component (S 1B ) in the Sol component

[0138] In addition to experiments in which the sol component dimethyldiethoxysilane (DMDEOS, component (S 1A )), further sol components were prepared in which dimethyldiethoxysilane was completely or partially replaced by diacetoxydimethylsilane (DMDAOS, component (S 1B)). DMDAOS differs from DMDEOS in the hydrolyzable group on the silicon-bonded oxygen atom, i.e., instead of an ethoxy group, DMDAOS contains an acetoxy group. The hydrolyzable group determines the reaction rate at the inorganic component of the silane of the general formula (S-IB), where: acetoxy > methoxy > ethoxy.

[22]

[0139] The following data refers to Comparative Example 1, with the proviso that the mass fraction of MTEOS stated therein is considered to be 100 mol%. The sum of the stated molar fractions of the D-silane(s) each equals 100 mol%, which in turn refers to the molar fraction of MTEOS being replaced. With reference to Experiment (viii), this means that the two D-silanes DMDEOS and diacetoxydimethylsilane together replace 50 mol% of the MTEOS contained in Comparative Example 1, with 80 mol% of the replaced MTEOS being replaced by DMDEOS and 20 mol% of the replaced MTEOS being replaced by diacetoxydimethylsilane. The following sol components were prepared: (viii) 50 mol% of the MTEOS was replaced by D-silanes (80 mol% DMDEOS, 20 mol% diacetoxydimethylsilane). This sol component corresponds to sol component D50B (Example 1E). (ix) 50 mol% of the MTEOS was replaced by D-silanes (50 mol% DMDEOS, 50 mol% diacetoxydimethylsilane). This sol component corresponds to sol component D50A (Example 1D). (x) 100 mol% of the MTEOS was replaced by D-silanes (100 mol% diacetoxydimethylsilane).

[0140] These sol components could all be mixed 1:1 with the hardener component H1 (see Example 3). The resulting mixtures of sol component and hardener component were stable for several weeks. Mixtures obtained with sol components (viii) and (ix) were stable for at least 5 months, with only a slight increase in viscosity. The sol components (viii) and (ix) were stable for at least 5 months. For sol component (x), in which the DMDEOS was completely replaced, the viscosity increased significantly after 3 months, rendering this sol component no longer miscible with the hardener component. This is due to the higher hydrolysis rate.

[0141] The third composition obtained with sol component (viii) and hardener component H1 is composition 3Z50B, the third composition obtained with sol component (ix) and hardener component H1 is composition 3Z50A. (c) Influence of component (h 2B ) in the hardener component

[0142] Experiments were carried out to use diacetoxydimethylsilane (component (h 2B )) into the hardener component, since the hardener component does not yet contain any water and hydrolysis only begins when the sol component and hardener component are mixed. For this purpose, tests were carried out in which GLYEO (component (h 2A )) was completely or partially replaced by diacetoxydimethylsilane. The data refer to hardener component H1 (Example 2), with the proviso that the mass fraction of GLYEO stated therein is considered to be 100 mol%.

[0143] The following tests were carried out: (xi) 25 mol% of the GLYEO is replaced by diacetoxydimethylsilane. (xii) 100 mol% of the GLYEO is replaced by diacetoxydimethylsilane. (xii) 25 mol% of diacetoxymethylsilane in addition to GLYEO.

[0144] Usable hardener components were obtained in all experiments. These hardener components were reacted with sol components described in Examples 1 to 1E. However, the hardener component (xii) was only reacted with sol components that did not contain diacetoxydimethylsilane in the sol component. d) Examination of the adhesive strength

[0145] The adhesion strength of coatings made of 3Z50B and 3Z50A was determined according to DIN EN ISO 4624:2016-08

[21] . Compared to the compositions according to the invention that did not contain diacetoxydimethylsilane, the best results were obtained for coatings made of 3Z50B and 3Z50A. The addition of diacetoxydimethylsilane increased the adhesion strength. The adhesion strength of these coatings was so high that the coatings on the CU3 copper alloy remained completely intact during the DIN standard test and did not peel off. In the coating made of 3Z50B, 20 mol% of DMDEOS was replaced by diacetoxydimethylsilane, compared to composition 3Z50. In the coating made of 3Z50A, 50 mol% of DMDEOS was replaced by diacetoxydimethylsilane, compared to composition 3Z50.

[0146] Fig.Figure 16 shows images of adhesion tests performed on a CU3 plate coated with a layer of 3Z50B (left) and on a CU3 plate coated with a layer of 3Z50A (right). The layers are completely intact after the adhesion test.

[0147] Table 7 shows the bond strengths of 3Z50B and 3Z50A coatings on a copper alloy, determined according to DIN EN ISO 4624:2016-08. The maximum bond strength determined with the device used is 24.0 MPa. No additional primer was used. Table 7 Composition used Copper alloy (CU3) Adhesion minimum in MPa Adhesion maximum in MPa 3Z50B 8,04 13,8 3Z50A 17,9 21,3 e) Elasticity test of the layers

[0148] The elasticity of the 3Z50B and 3Z50A layers was tested. The test was conducted according to DIN EN ISO 1519:2011-04

[20] using a mandrel bending test. The layers achieved comparable values ​​in the elasticity test to those of 3Z50 layers. The elasticity and resistance of the layers increased with increasing D-group content (see Table 8). Due to the increased adhesion to the substrate, the 3Z50B and 3Z50A layers flaked only slightly, and the higher the DMDAOS content, the less flaking was visible at the bending point.

[0149] Table 8 shows the results of mandrel bending tests carried out with layers of 3Z50B and 3Z50A, which allow a statement about the flexibility of the layers. Table 8 Composition of the coating Mandrel diameter in mm Test passed? 3Z50B 20 Yes 16 No - a few fine cracks on the bending point, but no chipping 10 No - a few fine cracks on the bending point, but no chipping 3Z50A 20 Yes 16 No - a few fine cracks on the bending point, but no chipping 10 No - a few fine cracks on the bending point, but no chipping

[0150] Fig.Figure 17 shows (top left and top center) plates made of stainless steel X6Cr17, on which a layer of 3Z50B or a layer of 3Z50A was formed, after conducting the mandrel bending test with a 20 mm mandrel; top right, a plate made of stainless steel X6Cr17, on which a layer of VB-3Z0 was formed, after conducting the mandrel bending test with a 32 mm mandrel; below, plates made of stainless steel X6Cr17, on which layers of 3Z50A were formed, each after conducting the mandrel bending test with a 20 mm mandrel (left), 16 mm mandrel (center), and 12 mm mandrel (right). These DIN standard tests confirmed the high flexibility of the layers.

[0151] Fig. Figure 18 shows enlarged photographs of the bending edge of the mandrel bending test. The higher the DMDAOS content in the composition used to produce the layer, the smaller the defect areas (left: layer of 3Z50B; right: layer of 3Z50A). f) Determination of the mechanical stability of the layers

[0152] The mechanical stability of the coatings obtained from 3Z50B and 3Z50A was determined using a cross-cut test according to DIN EN ISO 2409:2020-12

[19] . The coatings were applied to X6Cr17 stainless steel plates. The best cross-cut value of 0 (smooth cut edges, no chipping) was achieved on these plates.

[0153] Fig. 19 shows on the left and right in different magnifications a plate made of stainless steel X6Cr17, on which a layer of 3Z50A was formed, after the cross-cut test. Example 7Coating of fabrics

[0154] Layers of 3Z100 (top) and 3Z50 (bottom) were applied to different fabric samples (left column: linen, right column: cotton). After drying, a moderate water-repellent effect was observed, which is due to the hydrophobic treatment of the surface. The repellent effect is particularly good on linen. These layers can thus be used to create water-repellent fabrics. Example 8 Durability of the sol components

[0155] By adding DMDEOS to the sol component, a significantly longer shelf life is achieved compared to the coating known from DE 10 2019 110 519 A1. To date, a shelf life of 11 months has been confirmed for the sol components containing DMDEOS. Sol components without the addition of DMDEOS flocculated after approximately 2 months when the sol component and hardener component were mixed. To investigate the shelf life of the sol components, sol components D10, D25, and D50 were stored for 11 months at 7 °C and mixed with the hardener component H1 in a mass ratio of 1:1 for the mixing test. Example 9: Comparison with systems known from DE 10 2019 110 519 A1

[0156] The invention provides a first composition that can be used as a sol component. The first composition can be prepared without ice cooling. The inventors investigated the preparation of the first composition in batch sizes of 500 ml and found that ice cooling was not required. It has further been found that the shelf life of the first composition can be increased by several months if DMDEOS is a component of the first composition.

[0157] The coatings according to the invention obtained using the third composition exhibit higher coating elasticity according to DIN EN ISO 1519:2011-04

[20] . A minimum mandrel diameter of 10 mm could be used for a layer made of 3Z100. D100 is used as the sol component to produce a layer made of 3Z100. In contrast, the sol-hardener mixture described in DE 10 2019 110 519 A1 already showed severe cracking at a mandrel diameter of 32 mm.

[0158] The coatings according to the invention are crack-resistant when swelled in distilled water, artificial seawater (saline solution), and brackish water. This applies particularly to coatings produced using a sol component, for which DMDEOS was used. Determination of the bubble contact angle confirms hydrophobicity of the surfaces coated with such coatings. Crosslinking of the DMDEOS in the coating is confirmed by solid-state NMR analysis and CHNS analysis (increased C and H content).

[0159] By partially or completely replacing DMDEOS with DMDAOS, the adhesion strength of the layers could be increased. literature [1] E. Kroke, K. Kraushaar, F. Gellrich, DE 102019 110 519 A1, 2020 [2] TK Tuoc, miner. Scales Deposits, 2015, 20, 533-556 [3] DL Tijing, YC Woo, J.-S. Choi, S. Lee, S.-H. Kim, H.-K. Shon, J. Membr. Sci. 2015, 475, 215-244 [4] P. Stephan, S. Kabelac, M. Kind, D. Mewes, K. Schaber, T. Wetzel, VDI Heat Atlas - Technical Supporter VDI Society for Process and Chemical Engineering; Springer-Verlag GmbH, Berlin, Heidelberg, 2019. [5] H. Müller-Steinhagen, Handbook [of] heat exchanger fouling: Mitigation and cleaning technologies; Publico Publications, Essen; 2000. [6] S. Langenfeld, G. Jonschker, H. Schmidt, Mat.-wiss. u. Werkstofftech. 1998, 29, 23-29 [7] JH Osborne, Prog. Org. Coat. 2001, 41, 280-286 [8] E. Almeida, TC Diamantino, O. Sousa, Prog. Org. Coat. 2007, 59, 2-20 [9] International Convention on the Control of Harmful Anti-Fouling Systems on Ships, 2001, 2001.

[10] Federal Environment Agency Antifouling Agents, https: / / www.umweltbundesamt.de / themen / chemikalien / biozide / biozidprodukte / antifoulingmittel, 2023, Accessed: 21 February 2023

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[16] J. Harenburg, A. Kuhrt, F. Meier, DE 10 2004 059 152 A1, 2004

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[18] G. Engelhardt, H. Jancke, D. Hoebbel, W. Wieker, Z. Chem. 1974, 14, 109-110

[19] DIN Deutsches Institut für Normung eV, Beschichtungsstoffe - Gitterschnittprüfung, 2020, Beuth Verlag GmbH, Berlin.

[20] DIN German Institute for Standardization, Coating materials - Mandrel bending tests (cylindrical mandrel), 2019, Beuth Verlag GmbH, Berlin.

[21] DIN German Institute for Standardization, Coating materials - Tear-off test for determining adhesion strength, 2016, Beuth Verlag GmbH, Berlin.

[22] G. Jonschker, Sol-Gel Technology in Practice; Vincentz Network, Hanover; 2014. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] DE 10 2019 110 519 A1 [0002, 0072, 0076, 0095, 0155, 0157] DE 10 2004 059 152 A1

[0006] Cited non-patent literature

[0000] DIN EN ISO 2409

[0077] DIN EN ISO 2409:2020-12

[0123] DIN EN ISO 1519:2011-04

[0125] DIN EN ISO 4624:2016-08 [0129, 0135, 0145, 0147] DIN EN ISO 1519:2011-04 [20

[0148] DIN EN ISO 2409:2020-12 [19

[0152] ISO 1519:2011-04 [20

[0157] E. Kroke, K. Kraushaar, F. Gellrich, DE 102019 110 519 A1, 2020

[0159] TK Tuoc, miner. Scales Deposits, 2015, 20, 533-556

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[0159] P. Stephan, S. Kabelac, M. Kind, D. Mewes, K. Schaber, T. Wetzel, VDI Heat Atlas - Technical Supporter: VDI Society for Process and Chemical Engineering; Springer-Verlag GmbH, Berlin, Heidelberg, 2019

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[0159]

Claims

[1] Composition prepared by reacting at least the components (S1) at least one compound of the general formula (SI),wherein R 1 and R 2 are each independently selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 3 and R 4 independently of one another, a branched or unbranched alkyl group having 1 to 6 carbon atoms or a group -C(O)-R 5 where R 5 each represents a branched or unbranched alkyl group having 1 to 6 carbon atoms; (S2) a (3-glycidyloxypropyl)trialkoxysilane; and (S3) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof. [2] Composition according to claim 1, characterized by that it is produced by reacting at least the components (S1), (S2), (S3) and one component (S4), wherein component (S4) is a compound of the general formula S-II,wherein R 6 is selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 7 , R 8 and R 9are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms. [3] Composition according to claim 1 or claim 2, characterized by that they can be achieved by implementing at least the components (S 1A ), (S 1B ), (S2) and (S3) or by reacting at least the components (S 1A ), (S 1B ), (S2), (S3) and (S4), whereby component (S 1A ) is a compound of the general formula (S-IA) in which R 1 and R 2 have the meanings given in claim 1; and R 3A and R 4A are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (S 1B ) is a compound of the general formula (S-IB),wherein R 1 and R 2 have the meanings given in claim 1; and R 3Band R 4B independently of each other a group -C(O)-R 5 where R 5 has the meanings given in claim 1. [4] Composition according to any one of the preceding claims, characterized by that the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy. [5] Composition according to any one of the preceding claims, characterized by that component (S1) is dimethyldiethoxysilane or diacetoxydimethylsilane and that component (S2) is (3-glycidyloxypropyl)triethoxysilane. [6] Composition according to any one of the preceding claims, characterized by that R 1 , R 2 , R 3 , R 4 and R 5 are each selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and phenyl. [7] Composition according to any one of the preceding claims, characterized by that component (S3) is aqueous acetic acid or aqueous hydrochloric acid. [8] A composition comprising a first composition and a second composition, wherein the first composition is a composition according to any one of claims 1 to 7 and the second composition is a mixture of at least the components (h1) an alkanol; (h2) at least one silane, wherein the silane comprises a component (h 2A ) and / or a component (h 2B ), where (h 2A ) is a (3-glycidyloxypropyl)trialkoxysilane; and (h 2B ) is a compound of the general formula (H-IB),wherein R 1 and R 2are each independently selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; and R 3B and R 4B independently of each other a group -C(O)-R 5 where R 5 has the meanings given in claim 1; and (h3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR 13 )4, Zr(OR 14 )4, titanium acetylacetonate and mixtures thereof, wherein R 13 and R 14 a branched or unbranched alkyl group having 1 to 10 carbon atoms; [9] The assembly according to claim 8, characterized by that component (h 2A ) 3-Glycidyloxypropyl)triethoxysilane is. [10] A composition according to claim 8 or claim 9, characterized by that the alkanol is selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, sec-butanol, tert-butanol and mixtures thereof. [11] Assembly according to one of claims 8 to 10, characterized by that component (h1) is ethanol, component (h2) is (3-glycidyloxypropyl)triethoxysilane and component (h3) is titanium(IV) butoxide. [12] The assembly according to claim 11, characterized by that the mass ratio of the first composition to the second composition is 0.5 to 5 : 5 to 0.

5. [13] A composition prepared from a composition according to any one of claims 8 to 12 by reacting the first composition with the second composition. [14] Use of a composition according to any one of claims 1 to 7 or claim 13 for coating a substrate surface or forming a shaped body. [15] A process for preparing a composition according to claim 13, characterized by that the first composition is mixed with the second composition.

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