Composition for coating substrate surfaces

Abstract

The invention relates to a composition, produced by reacting a first mixture with a second mixture, wherein (a) the first mixture is a mixture of at least the components (a1) a chitosan; and (a2) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof; and (b) the second mixture is a mixture of at least the components (b1) of a compound of the general formula (I) wherein R1 is 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 R2, R3 and R4 independently of one another are each a branched or unbranched alkyl group with 1 to 6 carbon atoms; and (b2) a (3-glycidyloxypropyl)trialkoxysilane.

Description

Description Composition for coating substrate surfaces

[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 on a substrate surface is desirable. To prevent damage to the substrate by paint applied to a substrate surface, for example, to create graffiti, a barrier layer can be applied to the substrate surface [5]. Such a barrier layer is intended to prevent the graffiti paint from penetrating the substrate and to facilitate its removal [6]. These barrier layers are applied, for example, to monuments, houses, trains, and substrates located in public spaces.Although the barrier layers do not prevent the application of graffiti to a substrate surface, the easier removal of the graffiti prevents the use of chemicals for this purpose, which themselves or their by-products pose environmental and health risks as well as high financial costs [3, 4]. The barrier layers mentioned are called anti-graffiti coatings (AGCs) when they contain a dye.

[0004] Graffiti is created using paints with a wide variety of chemical bases. For example, graffiti paints based on alkyd resins and acrylates, spray paints based on polyurethanes, chalk, ballpoint pen inks, marker inks (which can be permanent or water-soluble), lipstick inks, and wax and oil pastels are used [3, 7]. Adhesive labels and posters are also applied [3, 7]. It is a challenge to find a barrier layer that allows for the easy removal of chemically different paints, adhesive labels, and posters [8, 9]. At the same time, the barrier layer is expected to maintain the appearance of the substrate surface unchanged [9]. Furthermore, the barrier layer should be easy to apply to the substrate surfaces.In other words, the barrier layer should adhere to the substrate surface, but at the same time, it should possess a non-stick effect to discourage the application of graffiti. Finally, the barrier layer should be resistant to certain cleaning methods and environmental influences [8, 9].

[0005] Most of the single-layer systems currently in use are based on hydrophobic and oleophobic products such as fluorinated siloxanes [10, 11], These are intended to reduce the surface energy of the coating and improve the oxidative, chemical and thermal stability [8, 12], One such system is described in DE 10 2004 059 152 A1 as an anti-stick layer

[0013] , However, the use of these fluorinated compounds is restricted on large surfaces due to their high cost and their environmentally hazardous effect [5], Tetraethoxy- and alkyltriethoxysilanes, on the other hand, have been described as strong hydrophobing agents and moderate fungicides

[0014] , Anti-graffiti coatings based on per- or polyfluorinated alkyl compounds (PF AS) are also known

[0029] , However, for the reasons mentioned, it is desirable that such coatings are fluorine-free.Approaches to producing fluorine-free anti-graffiti coatings include, for example, polyester-siloxane-based layers

[0030] .

[0006] Antifouling and anticorrosive coatings are also known. Currently known systems rely partly on modification of the surface properties, which is also often achieved by the addition of fluorinated alkyl chains or fluorine polymers [15-17], Active coatings are also used which continuously release active substances, e.g. catalytically or photocatalytically active substances, but thereby the introduced reagents are constantly consumed [18-20],

[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 enables the production of a layer with a non-stick effect. Furthermore, it is intended to provide a composition comprising a first and a second composition, a third composition produced from the composition, uses of the third composition, and a process for producing the compositions.

[0008] This object is achieved by the features of claims 1, 11, 13, 14, 15, and 16. Advantageous embodiments of the inventions emerge from the features of the subclaims.

[0009] According to the invention, a composition is provided which is prepared by reacting a first mixture with a second mixture, wherein (a) the first mixture is a mixture of at least the components (ai) a chitosan; and (a2) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof; and (b) the second mixture is a mixture of at least the components (bi) a compound of general formula I, (Formula I) where R 1 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 2 , R 3 and R 4 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (b2) a (3-glycidyloxypropyl)trialkoxysilane; 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.

[0010] It can be provided that the second mixture is a mixture of at least component (bi), component (b2) and one component (bs), wherein component (b) is a compound of the general formula (II) (Formula II) where R 5 and R 6are 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 7 and R 8 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms. First mixture

[0011] The first mixture contains chitosan as component (ai). The first mixture is therefore referred to as the chitosan component.

[0012] The first mixture comprises at least components (ai) and (a2). It may comprise additional components. However, it may also be provided that the first mixture consists only of components (ai) and (a2).

[0013] According to the invention, component (ai) is a chitosan. A chitosan is a biopolymer. This biopolymer is used, for example, in medicine [2]. The chitosan provided according to the invention can contain a repeating unit of the general formula III Chitosan can be produced by deacetylation of chitin, which is why chitosan can contain acetylated amino groups. The number of acetylated amino groups in chitosan can be expressed as the degree of deacetylation. The degree of deacetylation can be defined by the following formula: where QDA is the percentage degree of deacetylation. The degree of deacetylation can be at least 60%, preferably at least 70%, more preferably at least 75%, even more preferably at least 80%, and particularly preferably at least 90%. The chitosan preferably has a molecular weight of 80,000 to 500,000 Da, preferably of 100,000 to 300,000 Daltons. The molecular weight can be determined, for example, by means of gel permeation chromatography (see, for example, BP Andrews: Estimation of the molecular weights of proteins by Sephadex gel filtration. In: Biochem J. (1964), Vol. 91(2), pp. 222-33) or mass spectroscopic methods.

[0014] According to the invention, component (a2) is an aqueous solution of an acid. The higher the concentration of the acid in the aqueous solution, the faster the chitosan is homogenized. However, the stability of the produced sol component decreases with increasing acid concentration. The acid can serve to catalyze the hydrolysis of the alkoxysilanes in a sol-gel system. Such a sol-gel system is described below in connection with the third composition according to the invention. The term "alkoxysilanes" refers to component (bi) of the second mixture and, if provided, component (bs) of the second mixture. 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.

[0015] Component (a2) 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 n -COOH, where R 11 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 a mass fraction of 1 to 50% in the aqueous solution, 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. In order to achieve the fastest possible homogenization of the chitosan on the one hand and the longest possible shelf life of the sol component on the other, 10% aqueous acetic acid is best suited for the production of the sol component.

[0016] Component (a2) 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.

[0017] It can be provided that component (a2) is an aqueous solution of an acid mixture, wherein the acid mixture is a mixture of acetic acid and hydrochloric acid.

[0018] In a preferred embodiment, component (ai) is chitosan and component (a2) is aqueous acetic acid. The use of aqueous acetic acid instead of aqueous hydrochloric acid is advantageous because chloride ions could promote the corrosion of metallic substrates.

[0019] It can be provided that the component (ai) and the component (a2) in a mass ratio m ai : m a 2 of preferably 1 : 30 to 130, more preferably 1 : 50 to 110, even more preferably 1 : 70 to 90 and particularly preferably 1 : 80 to obtain the first mixture. Where m ai the mass of the component (ai) and m a 2 the mass of component (a2).

[0020] It can be provided that the first mixture contains at least one solvent and / or a solubilizer in addition to component (ai) and component (a2). This can be particularly useful when the carboxylic acid has more than 10 carbon atoms. The use of the solvent and / or the solubilizer is then intended to ensure that the first mixture can be provided as a homogeneous mixture. The solvent is preferably a non-polar, organic solvent. Preferred examples of such a solvent are α-pentane and α-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 be 10 vol.-%, based on the volume of the first mixture. Second mixture

[0021] The second mixture contains at least one alkoxysilane as component (bi). The second mixture is therefore referred to as the alkoxysilane component.

[0022] The second mixture comprises at least components (b1) and (b2). It may additionally comprise component (b2). The second mixture may comprise further components. However, it may also be provided that the second mixture consists only of components (b1) and (b2) or that the second mixture consists only of components (b1), (b2), and (b2).

[0023] It may be provided that in component (bi) R 1is 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 (bi) R 1 a substituted or unsubstituted, branched or unbranched alkenyl group with 2 to 18 carbon atoms, preferably with 1 to 10 carbon atoms. If R 1 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 substituents. A preferred substituent is nitrile.

[0024] Preferably, R 1selected from the group consisting of methyl, ethyl, n-propyl, t-propyl, n-butyl, iso-butyl, iso-butyl, tert-butyl, and phenyl. Preferably, R 1 Methyl or phenyl, particularly preferably methyl.

[0025] It may be provided that in component (bi) R 2 , R 3 and R 4 are each independently selected from the group consisting of methyl, ethyl, n-propyl, t-propyl, n-butyl, ziso-butyl, ts-butyl and tert-butyl. Preferably, R 2 , R 3 and R 4 each is methyl or ethyl, particularly preferably each is ethyl. Preferably, R 2 , R 3 and R 4 same alkyl groups.

[0026] Preferably, component (bi) is a methyltriethoxysilane (MTEOS).

[0027] Component (b2) is a (3-glycidyloxypropyl)trialkoxysilane. Preferably, the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, propoxy, and butoxy. Particularly preferred is the (3-glycidyloxypropyl)trialkoxysilane (3-glycidyloxypropyl)triethoxysilane. (GLYEO).

[0028] It may be provided that in component (bs) R 5 and R 6 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 (bi) R 5 and R 6 independently of one another, each represent a substituted or unsubstituted, branched or unbranched alkenyl group having 2 to 18 carbon atoms, preferably having 1 to 16 carbon atoms and especially preferably having 1 to 10 carbon atoms. If R 5 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. A preferred substituent is nitrile. 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. A preferred substituent is nitrile. The substituents are preferably hydrolysis-stable substituents.

[0029] Preferably, R 5 and R 6are each independently selected from the group consisting of methyl, ethyl, n-propyl, w-propyl, n-butyl, iso-butyl, iso-butyl, tert-butyl, vinyl, and phenyl. Preferably, R 5 and R 6 each is methyl or phenyl, particularly preferably methyl. Preferably, R 5 and R 6 same alkyl groups.

[0030] It may be provided that in component (bs) R 7 and R 8 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-butyl, n-butyl, and n-butyl. Preferably, R 7 and R 8 each is methyl or ethyl, particularly preferably each is ethyl. Preferably, R 7 and R 8 same alkyl groups.

[0031] Preferably, component (bs) is a dimethyldiethoxysilane (DMDEOS).

[0032] In a preferred embodiment, component (b1) is methyltriethoxysilane and component (b2) is (3-glycidyloxypropyl)triethoxysilane. In another preferred embodiment, component (b1) is methyltriethoxysilane, component (b2) is (3-glycidyloxypropyl)triethoxysilane, and component (b) is dimethyldiethoxysilane.

[0033] It can be provided that the component (bi) and the component (b2) in a mass ratio mt,i : mt,2 of preferably 10 to 30 : 1, more preferably 15 to 25:1, even more preferably 18 to 22:1, and particularly preferably 19:1, to obtain the second mixture. Where mbi is the mass of component (b1) and mt,2 is the mass of component (b2).

[0034] It can be provided that component (bi), component (bs) and component (b2) are mixed in a mass ratio mbi:mb3:mb2 of preferably 10 to 20:3 to 13:1, more preferably 12 to 18:3 to 10:1, even more preferably 13 to 15:3 to 5:1 and particularly preferably 14:4:1. Here, mbi is the mass of component (bi), mb2 is the mass of component (b2) and mb3 is the mass of component (bs).

[0035] It may be provided that the second mixture contains, in addition to component (b1), component (b2) and, if provided, component (b3), at least one solvent and / or a solubilizer. This may be particularly useful if the residue R 1 component (bi) is too large or too hydrophobic and / or if one or both residues R 5 , R 6of component (b2) are 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 second mixture can be provided as a homogeneous mixture. The solvent is preferably a non-polar, organic solvent. Preferred examples of such a solvent are λ-pentane and λ-hexane. The solubilizer is preferably a quaternary ammonium salt or a 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. First composition

[0036] According to the invention, the first composition is obtained by reacting the first mixture with the second mixture. The first composition can be obtained as a sol component.

[0037] In a preferred embodiment, the first composition is obtained by reacting a first mixture, whose component (ai) is chitosan and whose component (a2) is aqueous acetic acid, with a second mixture, whose component (bi) is methyltriethoxysilane and whose component (b2) is (3-glycidyloxypropyl)triethoxysilane. In another preferred embodiment, the first composition is obtained by reacting a first mixture, whose component (ai) is chitosan and whose component (a2) is aqueous acetic acid, with a second mixture, whose component (bi) is methyltriethoxysilane, whose component (b2) is (3-glycidyloxypropyl)triethoxysilane and whose component (bi) is dimethyldiethoxysilane.

[0038] To produce the first composition, at least the first mixture and the second mixture are reacted with one another. For this purpose, provision can be made for the second mixture to be admixed with the first mixture to obtain the first composition. To produce the first composition, the first mixture and the second mixture can be reacted in a mass ratio m i : m 2 of preferably 1 : 0.5 to 4, more preferably 1 : 1 to 3, even more preferably 1 : 1.5 to 2.5, and particularly preferably 1 : 2. Here, m i is the mass of the first mixture and m 2 is the mass of the second mixture.

[0039] 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. Second composition

[0040] A second composition may be provided which comprises a mixture of at least the components (ci) an alkanol; (C2) a (3-glycidyloxypropyl)trialkoxysilane; and (C3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR 9 )4, Zr(OR 10 )4, titanium acetylacetonate and mixtures thereof, wherein R 9 and R 10 a branched or unbranched alkyl group having 1 to 10 carbon atoms;

[0041] It may be provided that the second composition does not contain any Q groups, for example no Si(-O-Si)4 units.

[0042] Component (ci) 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, w-propanol, n-butanol, n-butanol, sec-butanol, c-butanol, and mixtures thereof. A preferred alkanol is ethanol. Methanol is not preferred due to its toxicity. Component (ci) serves as a solvent for components (ci) and (C3) in the second composition.

[0043] Component (C2) is a (3-glycidyloxypropyl)trialkoxysilane. Preferably, the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, α-propoxy, α-propoxy, α-butoxy, α-butoxy, α-butoxy, sec-butoxy, and α-butoxy. Preferably, component (C2) is the same compound as component (b2). Thus, component (C2) is particularly preferably (3-glycidyloxypropyl)triethoxysilane (GLYEO). It should be noted that component (C2) is included in addition to component (b2) in the composition described below.

[0044] Component (C3) is a crosslinker. The crosslinker can be a compound Ti(OR 9 )4, where R 9 has the meanings given above. The compound Ti(OR 9)4 is a titanium(IV) alkoxide. Component (C3) is preferably selected from the group consisting of titanium(IV) alkoxide, propylzirconate, titanium acetylacetonate, and mixtures thereof. A more preferred crosslinker is titanium(IV) butoxide, with titanium(IV) butoxide (TBOT) being particularly preferred. Titanium(IV) butoxide is a compound also known as titanium tetrabutoxide with the molecular formula CieHaeCUTi.

[0045] In a preferred embodiment, the second composition comprises the following components: Component (C1) is ethanol, component (C2) is (3-glycidyloxypropyl)triethoxysilane, and component (C3) is titanium(IV) butoxide. The second composition may contain additional components. In one embodiment, it consists only of components (C1), (C2), and (C3).

[0046] 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.

[0047] In the second composition, the components (C1), (C2) and (C3) can be present in a mass ratio m ci : m C 2 : m C 3 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 ci the mass of the component (ci), m C 2 is the mass of component (C2) and m C 3 the mass of component (C3).

[0048] In a preferred embodiment, the second composition is a mixture whose component (C1) is ethanol, whose component (C2) is (3-glycidyloxypropyl)triethoxysilane (GLYEO), and whose component (C3) is titanium(IV) butoxide (TBOT). Components (C1), (C2), and (C3) can be present in a mass ratio m ci : m C 2 : m C 3 = 2 : 2 : 1 must be included in the second composition.

[0049] To produce the second composition, components (C1), (C2), and (C3) 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 (C3) can be introduced into component (C1) or a first portion of component (C1) and mixed with it to obtain a first mixture. Component (C2) is then introduced into the first mixture to obtain a second mixture. If only a first portion of component (C1) was previously used, the remaining second portion of component (C1) can be used to absorb any residues of component (C3) and to add both together to the second mixture.Given the high viscosity of component (C3)—this applies particularly when titanium(IV) butoxide is used as component (C3)—vigorous stirring of the first and second mixtures is advantageous to achieve a homogeneous distribution of components (C2) and (C3) in component (C1). 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. 9 -groups of the crosslinker Ti(OR 9 )4 with ethanol molecules cannot be completely ruled out. Compilation

[0050] According to the invention, a composition is further provided which comprises the first composition and the second composition. In this case, a mass ratio of the first composition to the second composition can be preferably 1:0.5 to 4, more preferably 1:0.5 to 2, even more preferably 1:0.5 to 2 2 1 and particularly preferably 1 : -. A mass ratio of 1 : - corresponds to a mass ratio of the first composition to the second composition of 2 : 3.

[0051] The first composition and the second composition are preferably provided separately from one another in order 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 only of the components (ai), (a2), (bi), (b2), (ci), (C2) and (C3). In another embodiment, it can consist only of the components (ai), (a2), (bi), (b2), (bs), (ci), (C2) and (C3). The composition according to the invention can contain one or more additives in addition to the components (ai), (a2), (bi), (b2), (ci), (C2) and (C3).The composition according to the invention may contain one or more additives in addition to the components (ai), (a2), (bi), (b2), (bs), (ci), (C2) and (C3). Third composition

[0052] According to the invention, a composition is thus provided which is produced from the inventive composition by reacting the first composition with the second composition. This composition is referred to in the present invention as the third composition. The third component can be a sol component of a sol-gel system that can be cured using a hardener. The third composition is also referred to below as the sol component.

[0053] To prepare the third composition, the first composition and the second composition are mixed together. The mass ratio of the first composition to the second composition can preferably be 1:0.5 to 4, more preferably 1:0.5 to 2, even more preferably 1:0.5 to 1 and 2 particularly preferably 1 : -. Under the action of the crosslinker contained in the second composition, ie component (C3), the third composition cures. The third composition can be prepared at ambient temperature. It can be prepared at room temperature. It can be prepared without Ice cooling. The latter applies, as the inventors determined, particularly when the third composition has a volume of 500 ml or less.

[0054] 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 tetraethyl orthosilicate (TEOS) or tetramethyl orthosilicate (TMOS) and / or that none of these compounds is used to produce the first, second or third composition. Because neither the first mixture nor the second mixture nor the second composition contain any Q groups, it is ensured that the third composition also does not contain any Q groups.It can thus be provided that the second and third compositions do not contain any Si(-O-Si)4 units.

[0055] 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.

[0056] The third composition may contain one or more additives, but this is not mandatory. An additive may, for example, be a filler. The filler(s) may have functions that can influence and / or determine the electrical, mechanical, magnetic, thermal, chemical, biological-medical and / or other properties of the produced layer. A filler may, for example, be zinc stearate or silicon dioxide. In another example, the additive may be a pigment. The pigment(s) may be added to a layer that produced using the third composition. However, it is not necessary for the third composition to be produced using an additive. The mass fraction of the additive(s) in the third composition is preferably no more than 35 wt.%, more preferably no more than 30 wt.%, and particularly preferably no more than 20 wt.%.

[0057] In one embodiment, the third composition can be prepared by reacting the reaction product of only components (ai), (a2), (bi) and (b2) with the mixture of only components (ci), (C2) and (C3). In another embodiment, it can be prepared by reacting the reaction product of only components (ai), (a2), (bi) and (b2) with the mixture of only components (ci), (C2) and (C3) and then adding one or more additives. In a further embodiment, the third composition can be prepared by reacting the reaction product of only components (ai), (a2), (bi), (b2) and (bs) with the mixture of only components (ci), (C2) and (C3).In another embodiment, it can be prepared by reacting the reaction product of only components (ai), (a2), (bi) (b2) and (bs) with the mixture of only components (ci), (C2) and (C3) and then adding one or more additives.

[0058] 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 cures at room temperature, is biocompatible, and mechanically stable.

[0059] The third composition can be used to coat substrate surfaces. The third composition can be cured in air. The third composition can be cured at room temperature. Curing at elevated temperatures is not required, but is possible. Curing at elevated temperatures reduces the time required to achieve complete curing.

[0060] A preferred third composition is prepared by reacting (A) a first composition serving as a sol component, which is prepared from a first mixture of (ai) chitosan; and (a2) aqueous acetic acid; and a second mixture of (bi) Methyltriethoxysilane (MTEOS); and (b2) (3-Glycidyloxypropyl)triethoxysilane (GLYEO); (B) with a second composition serving as a hardener component, which is a mixture of (ci) ethanol; (C2)(3-Glycidyloxypropyl)triethoxysilane (GLYEO); and (C3) Titanium(IV) butoxide (TBOT). One or more additives may be added to this third composition.

[0061] A preferred third composition is prepared by reacting (A) a first composition serving as a sol component, which is prepared from a first mixture of (ai) chitosan; and (a2) aqueous acetic acid; and a second mixture of (bi) methyltriethoxysilane (MTEOS); (b2) (3-Glycidyloxypropyl)triethoxysilane (GLYEO); and (bs) dimethyldiethoxysilane (DMDEOS); (B) with a second composition serving as a hardener component, which is a mixture of (ci) ethanol; (C2)(3-Glycidyloxypropyl)triethoxysilane (GLYEO); and (C3) Titanium(IV) butoxide (TBOT). One or more additives may be added to this third composition. Process for preparing the third composition

[0062] According to the invention, a process for producing a third composition is further provided, wherein the first composition is mixed with the second composition. It may be provided that one or more additives are added to the resulting third composition immediately after mixing the first composition with the second composition.

[0063] Further details of the process according to the invention have already been described above in connection with the third composition. Reference is made to these details. Use of the third composition

[0064] The third composition can be used to produce layers. The produced layers can be transparent layers. 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 third composition is preferably used to coat plaster or stone.The flexibility of the fibers was not affected by the coating. The coating gave the paper a water-repellent effect. Glass, for example, could be used in glass windows.

[0065] Apart from the production of 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 infiltration of a porous material with the third composition or by casting the third composition and subsequent curing.

[0066] The layers obtained using the third composition according to the invention have a number of advantageous properties. It is possible to produce layers that are free of Q groups. This is particularly true in 29Si-CP / MAS NMR spectra of the layers are evident. The absence of Q groups is advantageous because the resulting layers exhibit greater flexibility, as no rigid framework, especially a rigid framework of Si(-O-Si)4 units, is formed, thus avoiding stresses and cracks.

[0067] The third composition according to the invention cures at room temperature. This is not the case, in particular, with many sol-gel systems known from the prior art. The layers produced using the third composition according to the invention are mechanically very stable and adhere well. Testing of such layers according to DIN EN ISO 2409:2013-06 showed extremely high stability on steel plates, e.g., stainless steel plates, and plates made of a copper alloy.

[0068] The layers produced using the third composition according to the invention are thermally stable up to temperatures of 250 °C. Only above 250 °C do the layers begin to decompose significantly, as demonstrated by thermogravimetric measurements.

[0069] Advantageously, the first composition and the second composition, i.e. both the sol component and the hardener component, are stable for several months at room temperature. An even longer storage stability can be achieved if the first mixture and the second mixture are stored separately. In this case, the composition can comprise or consist of three separate components, namely the first mixture, the second mixture, and the second composition. Such a composition can also be referred to as a 3-component system or 3K system. The sol component, i.e. the first composition, is preferably prepared immediately before reaction with the second composition, ie the hardener component.

[0070] To create layers from the third composition, all conventional application methods can be used, such as brushing, squeegeeing, pipetting, painting, dipping, and spraying, although this list is not exhaustive. Spraying includes manual spraying, spraying with a paint gun, and robot-assisted spraying. Dipping includes dip coating. Additional layers can be applied to dried layers, for example, using a brush.

[0071] The layer made from the third composition can cure at ambient temperature, for example, at room temperature. It can cure at ambient pressure.

[0072] Layers created from the third composition exhibit a non-stick effect. This non-stick effect allows such a layer to be used as an antifouling and anti-corrosion layer. Layers created from the third composition also exhibit an anti-graffiti effect. Graffiti can be easily removed from the layer, as experimental results have confirmed. Furthermore, layers created from the third composition are highly transparent layers. The appearance of the surface of the substrate coated with such a layer is not altered by the layer.

[0073] Layers produced from the third composition exhibit high mechanical stability. They are resistant to acidic to basic conditions. They also possess a water-repellent effect. For this reason, such a layer can be used to coat packaging materials such as paper. This enables the use of environmentally friendly packaging materials based on renewable raw materials.

[0074] Layers produced from the third composition contain nitrogen. This nitrogen originates from the chitosan provided according to the invention. The nitrogen in the coatings is detectable by elemental analysis. Coatings produced from the third composition are preferably free of the element fluorine. This is particularly advantageous if the coatings are to be used as anti-graffiti coatings.

[0075] Layers created from the third composition are biocompatible, mechanically stable, viscous layers. They can be considered biopolymer hybrid layers. They possess non-stick and anti-graffiti properties.

[0076] Compared to the system known from DE 10 2019 110 519, the third compositions exhibit a higher viscosity, which significantly simplifies industrial application. Furthermore, the layers obtained from the third composition according to the invention exhibit a non-stick effect, increased adhesion to various substrates, and are stable at room temperature for several months. The third composition can be prepared at room temperature. Three-component system

[0077] According to the invention, a three-component system is further provided, which comprises: (a) a first mixture of at least the components (ai) a chitosan; and (a2) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof; (b) a second mixture of at least the components (bi) a compound of general formula I, (Formula I) where R 1 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 2 , R 3 and R 4 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (b2) a (3-glycidyloxypropyl)trialkoxysilane; and (c) a third mixture of at least the components (ci) an alkanol; (C2) a (3-glycidyloxypropyl)trialkoxysilane; and (C3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR 9 )4, Zr(OR 10 )4, titanium acetylacetonate and mixtures thereof, wherein R 9 and R 10 a branched or unbranched alkyl group having 1 to 10 carbon atoms.

[0078] Details of the first mixture have been described above, in particular in the section “First mixture”. Details of the second mixture have been described above, in particular in the section “Second mixture”. Details of the third mixture have been described above, in particular in the section “Second composition”. If the first mixture is mixed with the second If the mixture is reacted, the above-described "First Composition" is obtained, which is described in more detail in particular in the section "First Composition." If the thus-obtained first composition is reacted with the third mixture, the above-described "Third Composition" is obtained, which is described in more detail in particular in the sections "Third Composition," "Process for Preparing the Third Composition," and "Use of the Third Composition." Reference is made to these explanations. Definitions of chemical terms

[0079] 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.

[0080] 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.

[0081] 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. Preferably, aryl 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 being independently hydroxy, alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, amino, monoalkylamino or dialkylamino, unless specifically stated otherwise.

[0082] 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, n-propyl, n-butyl, n-isobutyl, n-butyl, or n-butyl. Preferably, the aryl group bears only one alkyl group.

[0083] The term “halogen” refers, unless otherwise stated, to chlorine, bromine or iodine.

[0084] 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 )3SiOi / 2. An M group forms one chain end. Difunctional units are referred to as D groups or “D”, where D stands for (R z )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 zSiO2 / 2. A T group forms a branch of the framework. Tetrafunctional units that form a crosslink are called Q groups or "Q," where Q stands for SiO4 / 2. R z stands for a substituted or unsubstituted hydrocarbon residue.

[0085] 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 a 29 Si-CP / MAS spectrum of a layer according to the invention obtained from composition 3Z25; Fig. 2 is a diagram of thermogravimetric measurements of layers according to the invention obtained from composition 3Z25-A and 3Z25-B; Fig. 3 is another diagram of thermogravimetric measurements of layers according to the invention obtained from composition 3Z25-A and 3Z25-B; Fig.4A a photograph of a coated stainless steel plate after the cross-cut test; Fig. 4B is a photograph of a coated copper alloy plate after cross-cut testing; Fig. 5 a photograph of coated plates after the mandrel bending test; Fig. 6A is a photograph of a layer peeled from a copper alloy; Fig. 6B is a photographic image of a layer peeled from a stainless steel plate; Fig. 7A photographs of a coated plate during the scraping of a lacquer from the coating; Fig. 7B photographs of a coated plate before and after removing a lacquer from the coating; Fig. 8 photographs of coated fabric samples; Fig. 9 is a diagram showing the time-dependent viscosity change of third compositions according to the invention; and Fig. 10 shows another photograph of coated plates after the dome bending test.

[0086] 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 chitosan component

[0087] Chitosan (component (ai)) and 10% aqueous acetic acid (component (a2)) were used in a ratio of macetic acid : mchitosan = 80 : 1. The two components were then homogenized with vigorous stirring.

[0088] Chitosans from different manufacturers with different properties were tested to ensure their suitability for sol-gel systems. All three commercially available products tested produced homogeneous, clear layers. Table 1 lists the commercially available chitosans used. Table 1 : Chitosan used for the sol-gel mixture Example lA to ID: Production of further chitosan components

[0089] Additional chitosan components were prepared as described in Example 1, except that instead of 10% aqueous acetic acid in Example 1A, 2% aqueous acetic acid was used, in Example 1B 5% aqueous acetic acid, in Example IC 20% aqueous acetic acid, and in Example ID 0.1 M aqueous hydrochloric acid was used. Example 2: Preparation of the alkoxysilane component DO

[0090] Methyltriethoxysilane (MTEOS, component (bi)) and (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (b2)) were mixed in a ratio of mMTEOS : mGLYEO = 19 : 1. MTEOS and GLYEO were weighed into a vessel and homogenized by stirring. Example 2A: Preparation of the alkoxysilane component D25

[0091] Methyltriethoxysilane (MTEOS, component (bi)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (b2)) and dimethyldiethoxysilane (DMDEOS, component (b )) were used in a ratio of MTEOS : MDEOS : GLYEO = 14:4:1. MTEOS, DMDEOS, and GLYEO were weighed into a container and homogenized by stirring. Example 2B: Preparation of the alkoxysilane component D50

[0092] Methyltriethoxysilane (MTEOS, component (b1)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (b2)), and dimethyldiethoxysilane (DMDEOS, component (b)) were mixed together in a ratio of 9:8:1. MTEOS, DMDEOS, and GLYEO were weighed into a vessel and homogenized by stirring. Example 3: Preparation of the sol component SoO

[0093] The chitosan component prepared according to Example 1 was mixed with the alkoxysilane component D0 prepared according to Example 2 in a ratio of 1:2. With vigorous stirring, the chitosan component was slowly added dropwise to the silane component. Two phases formed. After complete addition of the chitosan component, stirring was continued until a clear sol was formed, which is the sol component SoO.

[0094] The produced sol component SoO could be stored at room temperature for 6 months. Example 3A: Preparation of the sol component So25

[0095] The sol component So25 was prepared as described in Example 3, except that the alkoxysilane component D25 prepared according to Example 2A was used instead of the alkoxysilane component D0.

[0096] The produced sol component So25 could be stored at room temperature for 6 months. Example 3B: Preparation of the sol component So50

[0097] The sol component So50 was prepared as described in Example 3, except that the alkoxysilane component D50 prepared according to Example 2C was used instead of the alkoxysilane component D0.

[0098] The prepared sol component So50 could be stored at room temperature for 2 months. Example 4: Production of the hardener component

[0099] Ethanol (component (C1)), (3-glycidyloxypropyl)triethoxysilane (GLYEO, component (C2)), and titanium(IV) butoxide (TBOT, component (C3)) were used in a ratio of mEthanoi: GLYEO: mTBOT = 2:2:1. The reaction was carried out with vigorous stirring. 90 vol.% 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 to rinse the dropping funnel or beaker. Stirring was continued for 2 hours at room temperature. Examples 4 A and 4B: Preparation of additional hardener components

[0100] Additional hardener components were prepared as described in Example 4, except that the ratio of mEthanoi:mGLYEO:mTBOT was varied within the range of mEthanoi:mGLYEO:mTBOT = 2:1-3:1. In Example 4A, the ratio of mEthanoi:mGLYEO:mTBOT was 2:1:1, and in Example 4B, it was 2:3:1.

[0101] The other hardener components were used to cure the sol component SoO prepared in Example 3, producing homogeneous, clear layers in each case. Example 5: Preparation of a composition 3Z0 from sol component SoO and hardener component

[0102] The sol component SoO prepared according to Example 3 and the hardener component prepared according to Example 4 were added to a beaker in a mass ratio of 3:2 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 3ZO.

[0103] The composition 3Z0 was then used directly for coating. Example 5A: Preparation of a composition 3Z25 from sol component So25 and hardener component

[0104] Composition 3Z25 was prepared as described in Example 5, except that sol component So25 prepared according to Example 3A was used instead of sol component SoO. Composition 3Z25 was then used directly for coating. Example 5B: Preparation of a composition 3Z50 from sol component So50 and hardener component

[0105] Composition 3Z50 was prepared as described in Example 5, except that sol component So25 prepared according to Example 3B was used instead of sol component So25. Composition 3Z50 was then used directly for coating. Example 5C: Preparation of a composition 3Z25-A from sol component So25 and hardener component

[0106] Composition 3Z25 was prepared as described in Example 5, except that instead of sol component SoO, the sol component So25 prepared according to Example 3A was used and that instead of the hardener component prepared according to Example 4, The hardener component prepared according to Example 4A was used. The composition 3Z25-A was then used directly for coating. Example 5D: Preparation of a composition 3Z25-B from sol component So25 and hardener component

[0107] Composition 3Z25 was prepared as described in Example 5, except that the sol component So25 prepared according to Example 3A was used instead of the sol component SoO, and the hardener component prepared according to Example 4B was used instead of the hardener component prepared according to Example 4. Composition 3Z25-B was then used directly for coating. Example 6: Application of compositions 3Z0, 3Z25, 3Z25-A, 3Z25-B, and 3Z50

[0108] The compositions 3Z0, 3Z25, 3Z25-A, 3Z25-B, and 3Z50 were applied to the surfaces of the following substrates: copper alloy (CU3), stainless steel plates (X6Crl7), fiberglass plates, quartz glass, paper, synthetic and natural fibers. The resulting coatings were examined. Example 7: Miscibility of compositions 3Z0, 3Z25, 3Z25-A, 3Z25-B, and 3Z50 with additives

[0109] The miscibility of compositions 3Z0, 3Z25, 3Z25-A, 3Z25-B, and 3Z50 with additives was investigated. For this purpose, the compositions were mixed with one of the pigments lamp black, titanium oxide, zinc white, alizarin madder lake, Solvent Black 29, or with one of the fillers zinc stearate, talc, or carbon nanotubes (CNTs). Solvent Black 29 is a liquid pigment dissolved in ethanol. Carbon nanotubes are a nanofiller that influences the surface topography and wettability of the produced layers.

[0021]

[0110] The mixtures obtained by mixing the compositions 3Z0, 3Z25, 3Z25, 3Z25-A, 3Z25-B and 3Z50 with an additive were applied to substrate surfaces and the formed layers were examined. Example 8: Investigation of the layers a) Characterization of the layers

[0111] The layers prepared according to Examples 6 and 7 were 29 Si solid-state NMR spectroscopy was used to examine the layers. The investigation revealed that the layers did not contain any Q groups.

[0112] Fig. 1 shows the 29 Si-CP / MAS spectrum of a powdered layer obtained using composition 3Z25. The distribution of the T groups is evident. The absence of Q groups was confirmed by the absence of signals with a chemical shift in the range from -78 ppm to -120 ppm

[0022] . Table 2 shows the molar percentages of the D and T groups determined by spectral deconvolution of this layer. Table 2 b) Thermal resistance of the coatings based on TG measurements

[0113] The coatings produced according to Examples 6 and 7 were tested using thermogravimetric (TG) measurements. For this purpose, the coatings were dried and pulverized. The test showed that the coatings were resistant up to 250 °C.

[0114] Fig. 2 shows a diagram of thermogravimetric measurements of a layer obtained using composition 3Z25-A and a layer obtained using composition 3Z25-B. The composition Settlements 3Z25-A and 3Z25-B differ in the mass fraction of ITIGLYEO. The diagram shows that the coatings were resistant up to 250 °C.

[0115] Fig. 3 shows a diagram of thermogravimetric measurements of a coating obtained using composition 3Z25-A and a coating obtained using composition 3Z25-B. The diagram shows that, depending on the composition of the hardener, the maximum reaction conversion occurs between 345 °C and 400 °C. The abbreviation "DTG" stands for differentiated thermogravimetry. c) Determination of the element distribution using CHNS analysis

[0116] The layers produced according to Examples 6 and 7 were analyzed using CHNS analysis. CHNS analysis is an elemental analysis used to determine the mass percentage of the elements C, H, N, and S. The results are shown in Table 3. It can be seen that with increasing proportion of D groups originating from the alkoxysilane component, from D0 to D50, the mass fraction of carbon and hydrogen in the formulation increases, and the chitosan, which is evident in the nitrogen content, is incorporated into the layer. The term "hardener" in Table 3 refers to the hardener component produced according to Example 4. Table 3 d) Determine the solid content of the layers after drying

[0117] The solids content of the layers produced according to Examples 6 and 7 was investigated. The solids content describes the mass fraction of CD present after drying the layer for 24 hours at 60 °C compared to the initial mass of the third composition used for its production and produced according to one of Examples 5 to 5D: The term "EW" refers to the initial weight. The results are shown in Table 4. The term "hardener" in Table 4 refers to the hardener component prepared according to Example 4. Table 4 e) Determination of the mechanical stability of the layers

[0118] The mechanical stability of the coatings produced according to Examples 6 and 7 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

[0023] . The coatings were applied to plates made of stainless steel X6Crl7 and copper alloy CU3. The best cross-cut characteristic value of 0 (smooth cut edges, no chipping) was achieved on both substrates.

[0119] Fig. 4A shows a plate made of stainless steel X6Crl7 on the left, on which a layer of 3Z50 was formed, and a plate made of stainless steel X6Crl7 on the right, on which a layer of 3Z0 was formed, after the cross-cut test. Fig. 4B shows a plate made of copper alloy CU3 on which a layer of 3Z0 was formed, after the cross-cut test. f) Elasticity testing of the layers

[0120] The elasticity of the layers produced according to Examples 6 and 7 was tested. The test was carried out according to DIN EN ISO 1519:2011-04

[0024] using a mandrel bending test. The layers exhibited a high degree of flexibility using this method of analysis. High elasticity and resistance were achieved even without the addition of D groups, which can be provided with component (Ü).

[0121] Fig. 5 shows (left) a plate made of stainless steel X6Crl7 on which a layer of 3Z50 was formed, (center) a plate made of stainless steel X6Crl7 on which a layer of 3Z25 was formed, and (right) a plate made of stainless steel X6Crl7 on which a layer of 3Z0 was formed, each after mandrel bending tests. The mandrel bending tests confirmed the high flexibility of the layers, which increases with increasing D-group content.

[0122] Table 5 shows an overview of the mandrel bending tests performed. These mandrel bending tests provide information about flexibility. The term "hardener" in Table 5 refers to the hardener component produced according to Example 4. Table 5 (g) Determination of layer thickness

[0123] The layer thicknesses of the coatings produced according to Examples 6 and 7 were determined using the PosiTector 6000 GP coating thickness gauge from DeFelsko. For the coatings produced using compositions 3Z0, 3Z25, and 3Z50, layer thicknesses of 8 to 15 μm were determined. The deviations can be explained by the manual application. Due to the different proportions of D groups, no significant change in the dry layer thickness was observed. (h) Determination of adhesion strength

[0124] The adhesion strength of the coatings produced according to Examples 6 and 7 was determined according to DIN EN ISO 4624:2016-08

[0025] . The determined adhesion strength values ​​were highly dependent on the substrate used. Plates made of stainless steel X6Crl7 have a smooth, mirror-like surface, which reduces the adhesion. CU3 panels have a rougher surface, which increases the adhesion of the coating to the substrate. However, the sanding pattern and grit of the sandpaper influenced the results. The different drying times of the samples also led to differing results. The results are shown in Table 6. The term "hardener" in Table 6 refers to the hardener component prepared according to Example 4. Table 6 (i ) Determination of non-stick properties

[0125] The non-stick properties of the coatings produced according to Examples 6 and 7 were investigated. The adhesive strength analysis according to DIN EN ISO 4624:2016-08 showed that after a certain drying time, the epoxy resin used could be removed with virtually no residue. The coatings remained completely intact.

[0126] This behavior was first observed after a drying time of the coating of approximately six weeks, although shorter drying times may also be sufficient. To accelerate this process, the samples were subsequently dried in a drying cabinet at 60 °C. After five days of such drying, the non-stick effect on stainless steel and CU3 was observed for coatings made of 3Z50. Seven weeks after application, the effect was also observed for the samples made of 3Z25, which were After seven weeks, including approximately six weeks of drying at 60 °C, the non-stick effect compared to an epoxy resin was also observed for coatings of 3Z0 on stainless steel and CU3, and for coatings of 3Z50 on stainless steel.

[0127] Fig. 6A showed a layer formed from 3Z50 on a plate made of the copper alloy CU3 and peeled off after drying. Fig. 6B showed a layer formed from 3Z50 on a plate made of the copper alloy CU3 and peeled off after drying.

[0128] Additionally, the non-stick effect was tested using various varnishes and permanent markers. All applied varnishes could be removed from the coating when wet. Table 7 shows the varnishes and permanent markers used to test the non-stick effect of the coatings. Table 7

[0129] Attempts were made to remove the applied paints with a spatula. This was easily achieved with the coated samples for the gold bronze spray paint and the green spray paint. In contrast, the black spray paint was difficult to scrape off the coated surface. The coating was not damaged. Compared to an uncoated stainless steel plate, all paints were significantly easier to remove. The uncoated stainless steel alloy was severely scratched due to the mechanical stress.

[0130] Fig. 7A shows the scraping off of the golden bronze spray with a spatula. It can be seen that the effect paint detached very well and compactly from the surface coated with 3Z25. Fig. 7B, left, shows a plate made of the copper alloy CU3 on which a layer of 3Z25 was formed and paints applied, which were scraped off with a spatula, as shown in Fig. 7B, right. The golden effect paint and the green spray paint were easily removed. The black spray paint, on the other hand, was difficult to scrape off. The coating was not affected by the scraping.

[0131] Significant differences were observed when applying the permanent markers. When using the STAEDTLER permanent marker, a significant non-stick effect was observed on plates coated with a third composition according to the invention. For this purpose, a drawing was applied to plates made of X6Crl7 stainless steel using the permanent marker. One plate was uncoated, a second plate had a layer of 3Z25, and a third plate had a layer of 3Z50. The plates had a surface area of ​​10 cm x 10 cm.

[0132] However, no difference was detectable when applying the edding permanent marker compared to the uncoated plate. For this purpose, a drawing was applied to each plate made of X6Crl7 stainless steel using an edding permanent marker. A first plate was uncoated, a second plate had a layer of 3Z25, and a third plate had a layer of 3Z50. The plates had a surface area of ​​10 cm x 10 cm. On plates, However, on plates on which a layer of a third composition according to the invention was formed, the drawing could be removed significantly more easily with a dry cellulose wipe. For this purpose, attempts were made to remove the drawing applied with the edding permanent marker from the first plate, the second plate, and the third plate. This was only successful with the second and third plates.

[0133] Furthermore, different textiles were each coated with a third composition. After drying, a water-repellent effect was observed, which was caused by the hydrophobization of the surface by the layer of the third composition according to the invention. Figure 8 shows fabric samples of linen (left), cotton (center), and silk (right) to which a layer of 3Z25 was applied, after wetting with water. The water-repellent effect is evident. (j) Viscosity determination

[0134] The viscosity of layers produced according to Examples 6 and 7 was determined. The determination was carried out using a flow cup according to DIN ISO 2431:2020-02

[0026] with an opening of 3 mm. The sol components produced according to Examples 3 to 3B were mixed with a hardener component produced according to Examples 4, 4A, or 4B, and the flow time was determined after a stirring time of 60 minutes and 120 minutes. The first measurement point of the flow time (10 minutes, 20 minutes, or 30 minutes) was chosen in each case to ensure a clear layer containing no solids; therefore, the first measurement points on the abscissa axis differ from one another.

[0135] It is evident from Fig. 9 that the viscosity decreases with increasing D-group content. Over time, the viscosity increases continuously, with the formulation still being applicable even after two hours of stirring. For industrial applications, this results in an application time of approximately one to two hours, although this can be extended by varying the application process or diluting with dried ethanol.

[0136] Table 8 shows the determined kinematic viscosity of third compositions according to the invention. The term "hardener" in Table 8 refers to the hardener component prepared according to Example 4. The reference numerals in parentheses refer to the reference numerals used in Fig. 9. Table 8 k) Determination of the degree of dryness

[0137] The degree of dryness of layers produced according to Examples 6 and 7 was determined. The determination was carried out according to DIN EN ISO 9117-5:2012-11

[0027] , which determines the drying time of a layer. Table 9 shows the degrees of dryness of 3Z0 after application by brush. Table 9 Example 9: Comparison with systems known from DE 10 2019 110 519 Al

[0138] The invention describes a sol-gel formulation containing chitosan. Acetic acid is also provided to catalyze the hydrolysis. The third composition can be provided as a three-component system. The three-component system comprises three separate components: the first mixture, the second mixture, and the second composition. DE 10 2019 110 519 A1, on the other hand, provides a two-component system.

[0139] Compared to layers of the composition described in DE 10 2019 110 519 A1, a layer of the third composition according to the invention dries faster. When applied by brush, degree of dryness 1 for a layer of a third composition according to the invention was achieved after approximately 20 minutes. With the system described in DE 10 2019 110 519 A1, degree of dryness 1 was only achieved after approximately 80 minutes.

[0140] Coatings made from the third composition according to the invention exhibit higher adhesion according to DIN EN ISO 4624:2016-08 than coatings made from the system described in DE 10 2019 110 519 Al. For coatings made from the third composition according to the invention, values ​​between 16.5 MPa and 23.1 MPa were obtained on the copper alloy, depending on the D-group content. On this copper alloy, values ​​of up to 14.0 MPa were achieved for the formulation described in DE 10 2019 110 519 Al.

[0141] The third composition according to the invention has a higher viscosity according to ISO 2431:2020-02 than the system described in DE 10 2019 110 519 A1. Depending on the D-group content and the chitosan used, the third compositions according to the invention have a kinematic viscosity after mixing of 13.8 mm 2 / s up to 37.9 mm 2 / s. For the sol-hardener mixture described in patent DE 102019 110 519 Al, a kinematic viscosity of 2.5 mm 2 / s reached.

[0142] Layers made from the third composition according to the invention have higher elasticity according to DIN EN ISO 1519:2011-04 than layers made from the system described in DE 10 2019 110 519 Al. For layers made from the third composition according to the invention, a minimum mandrel diameter of 12 mm or 16 mm could be used. For layers made from the system described in DE 10 2019 110 519 Al, severe cracking was already observed at a mandrel diameter of 32 mm. Fig. 10 shows the results of mandrel bending tests with coated X6Crl7 stainless steel plates, from left to right: plate with a layer of 3Z50, plate with a layer of 3Z25, plate with a layer of 3Z0, plate with a layer of a formulation described in DE 10 2019 110 519 Al. It turns out that the layers of the third composition according to the invention are more flexible than the layer of the system described in patent DE 10 2019 110 519 A1. literature [1] E. Kroke, K. Kraushaar, F. Gellrich, DE 10 2019 110 519 Al, 2020 [2] J. Ondruschka, M. Trutnau, T. Bley, Chem. Tech. Eng. 2008, 80, 811-820 [3] P. Sanmartm, F. Cappitelli, R. Mitchell, Constr. Build. Mater. 2014, 71, 363-374 [4] L. Giacomucci, F. Toja, P. Sanmartin, L. Toniolo, B. Prieto et al. Biodegradation 2012, 23, 705-716 [5] S. Amrutkar, A. More, S. Mestry, S. T. Mhaske, J. Coat. Technol. Res. 2022, 19 (3), 717-739 [6] S. Rossi, M. Fedel, S. Petrolli, F. Deflorian, J. Build. Eng. 2016, 5, 104-113 [7] V. Gomes, A. Dionisio, JS Pozo-Antonio, Prog. Org. Coat. 2017, 113, 90-109 [8] J. Scheerder, N. Visscher, T. Nabuurs, T.; Overbeek, A. Novel, J. Coat. Technol. Res. 2005, 2, 617-625 [9] HD Clercg, AE Charola, V. Hydrobhobe V: Water Repellent Treatment of Building Materials, Universität Freiburg; 2008

[0010] O. Garcia, K. Malaga, J. Cult. Herd. 2012, 13, 77 -82

[0011] P. Dewan, Bombay Technol. 2009, 59, 79-83

[0012] M. Licchelli, SJ Marzolla, A. Poggi, C. Zanchi, J. Cult. Heritage. 2011, 12, 34-43

[0013] J. Harenburg, A. Kuhrt, F. Meier, DE 10 2004 059 152 Al, 2004

[0014] S. Donath, H. Militz, C. Mai, C, Wood Sei. Technol. 2004, 38, 555-566

[0015] JF Destino, CM Gatley, AK Craft, M. R: Detty, FV Bright, Langmuir 2015, 31, 3510-3517

[0016] CP Stallard, KA McDonnell, OD Onayemie, JP O'Gara, DP Dowling, Biointerphases 2012, 7, 1-12

[0017] C. Guo, H. Ding, M. Xie, H. Zhang, X. Hong, L. Sun, F. Ding, Colloids Surf. A 2021, 615, 1-8

[0018] CA Damon, CM Gatley, JJ Beres, JA Finlay, SC Franco, AS Clare, M. R. Detty, Biofouling 2016, 32, 883-896

[0019] R. Ciriminna, A. Scurria, M. Pagliaro, Coatings 2022, 12, 1034

[0020] P. Sathe, K. Laxman, MTZ Myint, S. Dobretsov, J. Richter, J. Dutta, Sci. Rep. 2017, 7, 1-12

[0021] C. Carl, AJ Poole, MJ Vucko, MR Willimas, S. Whalan, R. de Nys, Biofouling, 2012, 28, 1077-1091

[0022] G. Engelhardt, H. Jancke, D. Hoebbel, W. Wieker, Z. Chem. 1974, 14, 109-110.

[0023] DIN German Institute for Standardization, Coating materials - Cross-cut test, 2020, Beuth Verlag GmbH, Berlin.

[0024] DIN German Institute for Standardization, Coating materials - Mandrel bending tests (cylindrical mandrel), 2011, Beuth Verlag GmbH, Berlin.

[0025] DIN German Institute for Standardization, Coating materials - Tear-off test to determine adhesion strength, 2016, Beuth Verlag GmbH, Berlin.

[0026] DIN German Institute for Standardization, Coating materials - Determination of flow time using flow cups, 2019, Beuth Verlag GmbH, Berlin.

[0027] DIN German Institute for Standardization, Coating materials - Drying test - Part 5: Modified Bandow-Wolff method, 2012, Beuth Verlag GmbH, Berlin.

[0028] J. Goeke, Thermal energy storage in building technology, Springer Vieweg, Wiesbaden, 2021.

[0029] Bayer, IS On the Durability and Wear Resistance of Transparent Superhydrophobic Coatings. CoatingslQl'l , 7, 12.

[0030] Zhong X, Hu H, Yang L, Sheng J, Fu H. Robust Hyperbranched Polyester-Based Anti-Smudge Coatings for Self-Cleaning, Anti-Graffiti, and Chemical Shielding. ACS Appl Mater Interfaces. 2019 Apr 17; 11(15): 14305-14312.

Claims

Patent claims 1. A composition prepared by reacting a first mixture with a second mixture, wherein (a) the first mixture is a mixture of at least the components (ai) a chitosan; and (a2) an aqueous solution of an acid, wherein the acid is a carboxylic acid, an inorganic acid or a mixture thereof; and (b) the second mixture is a mixture of at least components (bi) of a compound of general formula I, (Formula I) where R 1 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 2 , R 3 and R 4 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (b2) a (3-glycidyloxypropyl)trialkoxysilane; is.

2. Composition according to claim 1, characterized in that the second mixture is a mixture of at least component (bi), component (b2) and one component (bi), wherein component (bi) is a compound of general formula (II) (Formula II) where R 5 and R 6are 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 7 and R 8 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms.

3. Composition according to claim 1 or claim 2, characterized in that the alkoxy group of the (3-glycidyloxypropyl)trialkoxysilane is selected from the group consisting of methoxy, ethoxy, n-propoxy, / .w-propoxy, / .w-butoxy, / .w-butoxy, / .w-butoxy and / .w-butoxy.

4. Composition according to one of the preceding claims, characterized in that component (a2) is aqueous acetic acid or aqueous hydrochloric acid.

5. Composition according to one of the preceding claims, characterized in that component (b1) is methyltriethoxysilane and that component (b2) is (3-glycidyloxypropyl)triethoxysilane.

6. Composition according to one of claims 2 to 5, characterized in that component (b1) is methyltriethoxysilane, that component (b2) is (3-glycidyloxypropyl)triethoxysilane and that component (b1) is dimethyldiethoxysilane.

7. Composition according to one of the preceding claims, characterized in that the first mixture and the second mixture are reacted in a mass ratio m i : m2 = 1 : 0.5 to 4.

8. Composition according to one of the preceding claims, characterized in that to obtain the first mixture, component (ai) and component (a2) are present in a mass ratio m ai : m a 2 = 1 : 30 to 130 can be mixed.

9. Composition according to one of the preceding claims, characterized in that to obtain the second mixture, component (b1) and component (b2) are mixed in a mass ratio mt,i : mt,2 = 10 to 30 :

1.

10. Composition according to one of claims 2 to 9, characterized in that to obtain the second mixture, component (bi), component (bs) and component (b2) are mixed in a mass ratio mt,i : mt,3 : mt,2 = 10 to 20 : 3 to 13 :

1.

11. 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 10 and the second composition is a mixture of at least the components (ci) an alkanol; (C2) a (3-glycidyloxypropyl)trialkoxysilane; and (C3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR 9 )4, Zr(OR 10 )4, titanium acetylacetonate and mixtures thereof, wherein R 9 and R 10 a branched or unbranched alkyl group having 1 to 10 carbon atoms; is.

12. A composition according to claim 11, characterized in 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 claim 11 or claim 12 by reacting the first composition with the second composition.

14. Use of a composition according to any one of claims 1 to 10 or claim 13 for coating a substrate surface or forming a shaped body.

15. A method for producing a composition according to claim 13, characterized in that the first composition is mixed with the second composition.

16. Three-component system, comprising (a) a first mixture of at least the components (ai) a chitosan; and (a2) an aqueous solution of an acid, wherein the acid is a carboxylic acid or an inorganic acid; (b) a second mixture of at least the components (bi) a compound of general formula I, (Formula I) where R1 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 2 , R 3 and R 4 are each independently a branched or unbranched alkyl group having 1 to 6 carbon atoms; and (b2) a (3-glycidyloxypropyl)trialkoxysilane; and (c) a third mixture of at least the components (ci) an alkanol; (C2) a (3-glycidyloxypropyl)trialkoxysilane; and (C3) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti(OR 9 )4, Zr(OR 10)4, titanium acetylacetonate and mixtures thereof, wherein R 9 and R 10 a branched or unbranched alkyl group having 1 to 10 carbon atoms.

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