Permanent waterproofing agent

Abstract

Organopolysiloxane containing at least one structural unit (i) and / or (vi): where R 6 independently of each other at least one C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, and at least one urea group, and R 7 is independently selected from -CH3, -OH and a -C 1-5 -alkoxy group.

Description

[0001] The invention relates to organopolysiloxanes containing at least one structural unit with at least one C 8-28 -alkyl group and at least one urea group, a process for their preparation, a preparation comprising the organopolysiloxane, and the use as a hydrophobizing agent.

[0002] To make a surface hydrophobic or oleophobic, water-based or solvent-based preparations made from silicone oils, paraffin, fluorocarbon polymers and other additives are usually used to withstand the stresses of rain and splash water during use of the surface.

[0003] While the creation of water-repellent effects with products based on paraffins and silicones only results in hydrophobization, fluorocarbon polymers (FC polymers) also lead to dirt and oil repellency.

[0004] Despite the overall good effectiveness of FC polymers, the hydrophobic and oleophobic properties are significantly reduced after washing processes due to the disorientation of the active fluorocarbon residues in the polymer molecules, unless reorientation occurs through thermal treatment. This means that fabrics treated in this way, and especially textiles, must be subjected to heat treatment after washing to reactivate the desired effects. This heat treatment is referred to below as "reactivation."

[0005] Furthermore, fluorocarbon polymer-based formulations are expensive—due, among other things, to their energy-intensive production—and are also suspected of being ecotoxic and toxic to humans, so their use, especially in the clothing sector, is increasingly viewed with skepticism. Therefore, alternative fluorine-free products with comparable property profiles are being sought, with not only good initial hydrophobicity but also the durability of the finish to repeated washing being an important quality feature.

[0006] In EP 3 733 809 A1, preparations based on amino-modified silicones, organopolysiloxanes with a three-dimensional structure and alkylpolysiloxanes are used to achieve water-repellent effects on textile materials.

[0007] WO 2018 / 110667 describes compositions for hydrophobizing substrates, comprising a polymer composed of non-fluorinated (meth)acrylate residues and silicone macromers.

[0008] WO 2008 / 135208 discloses fluorocarbon-free preparations based on hydrophobic reaction products and C8-C 28 Organopolysiloxanes containing -alkyl groups are known.

[0009] WO 2015 / 191326 discloses preparations for hydrophobizing substrates that comprise a wax and a urethane-based compound. The wax can be, for example, a natural or synthetic wax or mixtures thereof.

[0010] These preparations can achieve good water-repellent effects, but relatively high application rates are typically required, which reduces the breathability of the finished textile. Furthermore, similar to textiles treated with fluorocarbon-containing preparations, a thermal treatment (reactivation), e.g., in a tumble dryer or by ironing, is required after washing to restore the original level of effect.

[0011] It is therefore an object of the present invention to provide a compound and preparation which enables good and permanent hydrophobic effects even at low application amounts without the need for reactivation (LAD effect, "Laundry / Air Dry", M. Rasch et al., Melliand Textilberichte 6 / 2005, pp. 456-459).

[0012] Surprisingly, this object was achieved by an organopolysiloxane containing at least one structural unit with at least one long-chain alkyl group and at least one urea group. Furthermore, the effect could be enhanced in the inventive preparations containing an inventive organopolysiloxane. Even small amounts of the inventive organopolysiloxane result in outstanding hydrophobicity on the substrate. Furthermore, the inventive preparations exhibit excellent adhesion to the substrate, so that the effect level hardly changes over time (effect permanence) and can be maintained even during use, e.g., through abrasion, washing, etc.

[0013] Surprisingly, it has also been shown that the effect level can be kept constant even without reactivation measures (LAD effect).

[0014] It has further been shown that flame-resistant fibers, such as Trevira CS and textiles made therefrom, do not lose their flame resistance even after application of the compound or preparation according to the invention, although the flame protection is generally impaired by the application of an FC-free hydrophobic agent.

[0015] In one aspect, the invention relates to an organopolysiloxane containing at least one structural unit (i) and / or (vi): where R 6 independently of each other at least one C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, and at least one urea group, and R 7 is independently selected from -CH3, -OH, and a -C 1-5 -alkoxy group, preferably -CH3.

[0016] R 6 preferably contains at least one C 8-28-Alkylurea group according to the present formula:more preferably, R 6 at least one C 14-20 -alkylurea group, even more preferably a C 16-18 -alkylurea group.

[0017] In a preferred embodiment, R 6 a formula selected from and where R 10 independently H or R 11 is, R 11 independently of each other -C(O)-NH-C 8-28 -Alkyl, more preferably -C(O)-NH-C 14-20 -Alkyl, even more preferably -C(O)-NH-C 16-18 -alkyl, provided that R 6 at least one R 11 contains, k is 2-4, preferably 2-3 and I 2-4, preferably 2-3.

[0018] Furthermore, the organopolysiloxane according to the invention may contain at least one structural unit selected from and, where R 5 independently of each other a C 8-28-Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, R 8 is independently selected from and R 6 and R 7 , k and I are as defined above.

[0019] The organopolysiloxane preferably has the following end groups independently of one another:orwherein R 5 , R 6 , R 7 and R 8 as defined above.

[0020] In a preferred embodiment, the molar proportion of structural unit (i) in the organopolysiloxane is in the range of 25-100 mol%, more preferably 50-100 mol%, assuming that all structural units in the organopolysiloxane add up to 100 mol%.

[0021] Furthermore, the molar proportion of structural unit (vi) is preferably in the range of 25-100 mol%, more preferably 50-100 mol%.

[0022] In another embodiment, the molar fraction of the structural unit (ii) in the organopolysiloxane is in the range of 0-50 mol%, more preferably 0-30 mol%.

[0023] The molar fraction of the structural unit (iii) can be in the range of 0-40 mol%, preferably 0-20 mol% in the organopolysiloxane.

[0024] The molar fraction of the structural unit (iv) and / or (vii) is preferably in the range of 0-20 mol%, more preferably 0-10 mol%.

[0025] In one embodiment, the molar fraction of the structural unit (v) is in the range of 0-50 mol%, preferably 0-30 mol%.

[0026] The organopolysiloxane according to the invention preferably has a (protonatable) total basic nitrogen content of 0-3 wt.%, preferably 0-1.5 wt.%, even more preferably 0.01-0.05 wt.%. The titration for determining the basic nitrogen content is known to the person skilled in the art.

[0027] In a further aspect, the invention relates to a process for producing an organopolysiloxane according to the invention, comprising the steps a) providing an organopolysiloxane and / or alkoxysilane having NCO-reactive primary and / or secondary amine groups, b) reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 -alkyl isocyanate; and c) optionally hydrolysis / condensation of the alkoxysilane obtained in step b) to the organopolysiloxane.

[0028] In particular, the invention relates to a process for producing an organopolysiloxane comprising the steps a') Providing an organopolysiloxane having NCO-reactive primary and / or secondary amine groups and b') reacting the organopolysiloxane according to a') with C 8-28 -Alkyl isocyanate, preferably C 14-20 -alkyl isocyanate, more preferably C 16-18 -Alkyl isocyanate.

[0029] Alternatively or additionally, the procedure may include: a'') Providing an alkoxysilane having NCO-reactive primary and / or secondary amine groups, b'') reacting the alkoxysilane according to a'') with C 8-28 -alkyl isocyanate and c'') Hydrolysis / condensation of the alkoxysilane obtained in step b'') to the organopolysiloxane.

[0030] The organopolysiloxane according to step a') can be prepared by equilibration in the presence of (C 1-5-Alkoxy)silanes having at least one NCO-reactive primary and / or secondary amine group. The equilibration reaction is preferably base-catalyzed and is described, for example, in EP 1 136 513 B1, Example 1. Organooligo- or organopolysiloxanes together with alkoxysilanes having at least one NCO-reactive primary and / or secondary amine group can be used as reactants in the equilibration reaction. The equilibration is preferably carried out in the presence of an organopolysiloxane containing structural units (ii), (iii), and / or (v), preferably in the presence of metal hydroxide and water.

[0031] Alternatively, organopolysiloxanes can be obtained by hydrolysis and condensation of alkoxysilanes containing at least one NCO-reactive primary and / or secondary amine group. Alkoxysilanes may also be present in the hydrolysis reaction, leading to structural units (ii), (iii), and / or (v). To shift the equilibrium during hydrolysis toward the product side, the resulting alcohol can be distilled off, optionally under reduced pressure.

[0032] In the process according to the invention, the alkoxysilane in step a'') is preferably a (C 1-5 -Alkoxy)silane having at least one NCO-reactive primary and / or secondary amine group, more preferably selected from and / or where R 7 and R 8 as defined above.

[0033] The reaction according to step b') and b'') between the linear or branched C 8-28The reaction of the alkyl isocyanate and the NCO-reactive primary and / or secondary amine group is preferably carried out by adding the alkyl isocyanate to the amino groups while stirring. The reaction can be carried out in bulk or in solvents such as ethyl acetate, isopropyl acetate, acetone, tetrahydrofuran, methyl ethyl ketone, methyl propyl ketone, toluene, xylene, dipropylene glycol dimethyl ether, methoxypropyl acetate, etc. To accelerate the reaction, the reaction mixture can be heated to 40-140 °C if necessary. Suitable catalysts are, in particular, di-n-butyltin dilaurate, tin(II) octoate, dibutyltin diacetate, potassium octoate, zinc dilaurate, bismuth trilaurate or tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyldipropanolamine, pentamethyldipropylenetriamine, N-methylimidazole or N-ethylmorpholine.

[0034] The molar stoichiometry between C 8-28-alkyl isocyanate and NCO-reactive primary or secondary amine groups is preferably chosen so that 50-100 mol%, preferably 80-100 mol%, particularly preferably 90-100 mol% of the amino groups react with the NCO groups of the C 8-28 -alkyl isocyanate. In a non-stoichiometric reaction, protonatable amino groups therefore remain in the organopolysiloxane. The protonatable basic nitrogen content is between 0 and 3 wt.% (see above).

[0035] Step c'') is preferably carried out in the presence of a catalyst, preferably KOH, NaOH, optionally at elevated temperature, e.g. 40-140°C.

[0036] In step c), the alkoxysilane obtained in step b) is hydrolyzed and subsequently condensed. Alkoxysilanes may also be present in the hydrolysis reaction, leading to structural units (ii), (iii), and / or (v). To shift the equilibrium during hydrolysis toward the product side, the resulting alcohol can be distilled / condensed, optionally under reduced pressure.

[0037] In a further aspect, the present invention relates to an organopolysiloxane obtainable by the process according to the invention.

[0038] In a further aspect, the invention relates to a preparation comprising (1) at least one reaction product (S) obtainable by reacting at least one compound (A) of Formula (I) and / or the formula (II) and / or the formula (III) and / or the formula (IV) where R 1 = -XYZ or -Z, with X = -(CH2)n'' -,or Z = -(CH2) m -CH3, R 3 = -XYZ, -Z or -YZ, with the proviso that if -YZ is the meaning in the residue R 2 n is replaced by n", R 4 = -XYZ or -(CH2) n' H is, B 1 = -VWZ or -Z, with V = -(CH2) n'' - orist, B 2 = -(CH2) n'' -NH2, or Q = -(CH2) n'' - is, R s independently of one another -OH, -YZ,or, with the proviso that at least one radical R s in formula (III) is an OH group, and n, n', n", n''' 335 and m are each independently an integer, with n0-2, n' 0-4, n'' 1-4, n''' 0-4 and m 8-30, preferably 12-26, more preferably 14-22, with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mole. (2) at least one organopolysiloxane according to the invention, (3) optionally at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), (4) if necessary, at least one liquid medium, in particular water or an organic solvent and (5) if necessary, at least one emulsifier.

[0039] The preparation according to the invention is preferably free from fluorine compounds.

[0040] The preparation is preferably in the form of a dispersion, preferably in the form of an aqueous dispersion. The solids content of the dispersion is preferably 10-40 wt.%, more preferably 15-30 wt.%.

[0041] The reaction product (S) is preferably hydrophobic. The term "hydrophobic" in the context of the present invention defines compounds that are typically essentially insoluble in water at 20°C. Saturated solutions of the "hydrophobic" reaction products (S) preferably contain up to 1 g of dissolved compound per liter of water (20°C), more preferably up to 0.5 g / l, and even more preferably up to 0.2 g / l.

[0042] The reaction product (S) is obtainable by reacting at least one compound (A) with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC).

[0043] The compound (A) of formula (I) is preferably obtained by reacting polyhydric alcohols (a1) with carboxylic acids (b1) or with alkyl isocyanates (b2). Preferred examples of polyhydric alcohols (a1) are glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, or sugars, such as glucose, preferably glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, and / or pentaerythritol, more preferably glycerol.

[0044] The compound (A) of formula (II) is preferably obtained by reacting alkanolamine (a2) and / or alkylamine (a3) ​​with carboxylic acid (b1) and / or alkyl isocyanate (b2). Preferred alkanolamines (a2) are 2-amino-2,3-propanediol, 2-amino-2-methyl-1,3-propanediol, diethanolamine, dipropanolamine, diisopropanolamine, ethanolpropanolamine, triethanolamine, triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, aminoethylethanolamine, aminopropylethanolamine, alkyltris(hydroxyethyl)propylenediamine, and alkyldihydroxyethylamine with preferably 12-24 carbon atoms in the alkyl radical, as well as their ethoxylation products. Particularly preferred are diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, aminoethylethanolamine and aminopropylethanolamine, more preferably triethanolamine.

[0045] Examples of alkylamines (a3) ​​are bis(aminoethyl)amine, bis(aminopropyl)amine and their polymeric homologues, aminoethylaminopropylamine, bis(aminopropyl)ethylenediamine, tris(aminoethyl)amine, tris(aminopropyl)amine, trisaminononane, aminopropylstearylamine, and aminopropylbisstearylamine. Bis(aminoethyl)amine, bis(aminopropyl)amine, aminoethylaminopropylamine, bis(aminopropyl)ethylenediamine, and aminopropylstearylamine are preferred, especially bis(aminoethyl)amine.

[0046] The carboxylic acids (b1) used to prepare compound (A) can be saturated, unsaturated, unbranched, or branched and preferably have 10-32 carbon atoms, more preferably 12-24 carbon atoms. Preference is given to unbranched, saturated carboxylic acids with preferably 10-32 carbon atoms, more preferably 12-24 carbon atoms, such as capric, undecanoic, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Lauric, palmitic, stearic, and behenic acid are particularly preferred.

[0047] The alkyl isocyanates (b2) used to prepare formulas (I) and (II) are preferably unbranched, with the alkyl radical preferably having 9-31, in particular 11-23, carbon atoms. A particularly preferred alkyl isocyanate is stearyl isocyanate.

[0048] Instead of the compound (A) prepared using the polyhydric alcohols (a1) or the alkanolamines (a2) or the alkylamines (a3) ​​and the carboxylic acids (b1) or the alkyl isocyanates (b2), compounds having one active hydrogen atom and two hydrophobic radicals, such as Guerbet alcohols, bis(dodecyl)amine and preferably bis(octadecyl)amine, can also be used.

[0049] Compounds of formula (III) are sorbitan esters obtained by reacting sorbitol with C 10 -C 32 -carboxylic acids, preferably with C 14 -C 28 -Carboxylic acids particularly preferably with C 16 -C 24Carboxylic acids can be obtained by dehydration. Depending on the stoichiometry, mono-, di-, or triesters, as well as mixtures thereof, can be formed. If necessary, alkoxylated derivatives can also be used. For the reaction with the unblocked or at least partially blocked di-, tri-, or polyisocyanate (IC), it is necessary that at least one reactive OH group is present in the sorbitan ester. Furthermore, it is possible to react 1,4-sorbitan anhydride with C 10 -C 32 -alkyl isocyanates, preferably with C 14 -C 28 -alkyl isocyanates, particularly preferably with C 16 -C 24 -alkyl isocyanates to obtain compounds of formula (III).

[0050] Compounds of formula (IV) are alkyl citrates obtained by the esterification of citric acid with long-chain C 10 -C 32 -alcohols, preferably with C 14 -C 28 -Alcohols especially preferred in C 16 -C24 -alcohols can be obtained.

[0051] At least one compound (A) is reacted with at least one unblocked or at least partially blocked di-, tri-, or polyisocyanate (IC) to form the hydrophobic reaction product (S), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mole. Examples of unblocked or partially blocked isocyanates are described in DE 100 17 651 A1, paragraphs

[0032] -

[0037] .

[0052] Particularly preferred, unblocked di-, tri- or polyisocyanates (IC) are, for example, 2,4-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), longer-chain homologues of diphenylmethane diisocyanate (polymer MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, mixtures, such as mixtures of MDI and polymer MDI, and derivatives thereof. Dimer diisocyanate is available from Cognis Corp., 300 Brookside Avenue, Ambler, PA 19002, USA, under the designation DDI 1410.

[0053] Isocyanate derivatives (IC) include, for example, cyclized oligo- or polyisocyanates. Cyclized oligo- or polyisocyanates can be prepared using the known cyclization methods described by W. Siefken (Liebigs Annalen der Chemie 562, 1949, pages 75-136), whereby the oligo- or polyisocyanates can be open-chain or cyclic. Such derivatives can be prepared from the above-mentioned di-, tri-, and polyisocyanates by linking them using urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione, or iminoxadiazinedione structures. Hexamethylene diisocyanate trimers, diphenylmethane diisocyanate trimers, and urethanes derived from 2,4-tolylene diisocyanate, which still contain free NCO groups, are preferred.

[0054] It is also possible to derivatize partial amounts of the isocyanate groups with polyalkoxy monoalkyl ethers to form urethanes using appropriate catalyst systems in order to improve the emulsifiability of component (1) in water. Polyethylene glycol monomethyl ethers with preferably 4-20 ethylene oxide units, optionally with additional 2-6 propylene oxide units, can be used. Catalysts known to the person skilled in the art based on tertiary amines and / or organotin compounds, such as dibutyltin dilaurate, dioctyltin dilaurate, or diacetate, can be used.

[0055] Preferred derivatives are hexamethylene diisocyanate trimers, diphenylmethane diisocyanate trimers, urethanes from 2,4-tolylene diisocyanate with free NCO groups, and di-, tri- or polyisocyanate (IC) modified with polyalkoxy monoalkyl ether, in particular di-, tri- or polyisocyanate modified with polyethylene oxide monoalkyl ether.

[0056] As an alternative to isocyanates modified with polyalkoxy monoalkyl ethers, tertiary alkanolamines can be used as additives to improve the cationic charge of the reaction products (S) and thus the self-emulsifying properties without compromising the overall properties. Dimethylaminoethanol is particularly suitable for this purpose.

[0057] The isocyanate (IC) can also be partially or completely blocked (see, for example, DE 100 17 651 A1, paragraph

[0042] ). Preferred blocking agents are sodium bisulfite, methyl ethyl ketoxime, 3,5-dimethylpyrazole, N-tert-butylbenzylamine, especially 3,5-dimethylpyrazole.

[0058] The blocking is carried out by reacting di-, tri- or polyisocyanate (IC) with the blocking agent in the melt or in an organic solvent (LM) inert towards isocyanates, preferably under a protective gas atmosphere and in the presence of a suitable catalyst, as described for example in EP 0 159 117 B1 or DE 44 41 418 A1.

[0059] The molar ratio of the free NCO groups of the di-, tri- or polyisocyanates (IC) to be blocked to the reactive groups of the blocking agent is preferably in a stoichiometric excess of up to 2:1, preferably up to 3:1.

[0060] To prepare the reaction product (S), the molar ratio of free isocyanate (NCO) groups in the polyisocyanate (IC) to isocyanate-reactive groups in compound (A) is adjusted to 1:1 to 1:1.3, preferably 1 to 1.1. The isocyanate-reactive groups in compound (A) are preferably hydroxyl groups, primary and / or secondary amino groups.

[0061] In a preferred embodiment, the preparation contains component (1) at 10-90 wt.%, more preferably 20-80 wt.%, even more preferably 25-65 wt.%, based on the total mass of components (1) and (2).

[0062] As component (2) the organopolysiloxane (2) according to the invention is used, which is described in detail above.

[0063] In one embodiment, component (2) makes up 10-90 wt.%, preferably 20-80 wt.%, more preferably 30-70 wt.%, based on the total mass of components (1) and (2).

[0064] The addition of component (3) to the preparations (Z) according to the invention is optional. The unblocked di-, tri-, or polyisocyanates (IC) suitable for component (3) have already been described above for the preparation of the reaction product (S) in component (1). Compounds of this type are referred to as boosters and improve the water repellency of the treated fabrics.

[0065] At the same time, due to the polyfunctionality of the polyisocyanate, crosslinking with the -OH, -COOH or -NH2 groups always present on most substrates and unreacted functional groups of component (1) is achieved, which significantly improves the resistance to washing processes and increases the resistance to abrasion.

[0066] Component (3) can be used in both unblocked and blocked forms. The unblocked forms of component (3) are primarily used in applications involving nonpolar media, as this prevents unwanted, premature reaction of the free NCO groups with the reactive active hydrogen atoms of the application medium.

[0067] If component (3) is to be applied from application media to fabrics bearing NCO-reactive groups, it is often necessary to protect these by blocking with suitable blocking agents. In these cases, component (3) is produced by processes in which the free NCO groups of di-, tri-, or polyisocyanates are completely blocked with a blocking agent and, if appropriate, in an organic solvent. To achieve complete blocking, a slight stoichiometric excess of blocking agent is usually used. If products for aqueous applications are to be produced, the blocked di-, tri-, or polyisocyanates, if appropriate dissolved in an organic solvent, must be converted into emulsion form using suitable emulsifiers (= component (5)).

[0068] Examples of suitable conventional and known blocking agents are known from DE-A-100 17 651 A1, paragraph 0042 and are already described in the description of the preparation of the reaction product (S) in component (1).

[0069] In a particular embodiment, unblocked di-, tri-, or polyisocyanates can be used as boosters whose self-emulsifying ability in water is improved by partial reaction of the isocyanate groups with polyalkoxy monoalkyl ethers with the aid of appropriate catalyst systems to form urethanes. By attaching hydrophilic side chains to the di-, tri-, or polyisocyanates, the HLB value of the urethane produced in this way is modified so favorably that the inherently water-insoluble compound acquires self-emulsifying properties. With the hydrophilic side chains, a certain selection of the type and amount of the residue is advantageous. Preferably, between 4 and 20 ethylene oxide residues are used, optionally together with 2-6 propylene oxide residues, although these can also be present in blocks within the alkoxy chain. However, with such mixed alkoxylated side chains, the proportion of ethylene oxide always predominates over that of propylene oxide.As catalysts for the urethane synthesis, the systems known to the person skilled in the art based on tertiary amines and / or organotin compounds, such as dibutyltin dilaurate, dioctyltin dilaurate or diacetate, can be used.

[0070] When applied, the urethanes produced in this way spontaneously form fine-particle emulsions upon introduction into water. They exhibit high shear stability and good compatibility with the other components of an application liquor. Due to the reactivity of the remaining, unreacted NCO groups with water, these special forms can only have limited pot lives in the application liquor, up to a maximum of 8 hours.

[0071] The addition of component (3) is carried out particularly in cases where particularly high demands are placed on the wash resistance of the treated fabrics.

[0072] Preferably, 0-50 wt.%, preferably 1-35 wt.%, more preferably 5-35 wt.%, of component (3) is used, based on the total mass of components (1), (2), and (3). Component (3) can also be used directly from solvent-containing, anhydrous media without formulation aids.

[0073] Preferably, 5-35% of component (3) is used, which can be used directly and without formulation aids for application from solvent-containing, anhydrous media. If application is from an aqueous medium, emulsions of component (3) with a solids content of 15-35% by weight are preferably used. These emulsions are prepared using emulsifiers (= component (5)) based on ethoxylated fatty amines, optionally in quaternary form, and optionally other emulsifying aids, such as solubilizing agents based on ethylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether, or n-methylpyrrolidone. Emulsification can be carried out with the aid of high-pressure homogenization machines.

[0074] Component (4) is optional. The liquid medium is preferably water or an organic solvent. Suitable organic solvents are preferably inert solvents such as esters, e.g., ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, or amyl acetate; ketones, e.g., acetone methyl ethyl ketone; and saturated hydrocarbons, such as, e.g., n-hexane, n-heptane, or n-octane.

[0075] The preparation (Z) according to the invention can further comprise at least one emulsifier. Component (5) is to be used in particular when the preparation is in the form of a suspension, in particular a dispersion or emulsion. The surfactants ensure the most homogeneous distribution of the phases, in particular the oil phase, in the aqueous phase. Non-ionic, cationic, or anionic surfactants are used as emulsifiers. Preferred non-ionic, anionic, or cationic emulsifiers are ethoxylation products of fatty acids, fatty acid amides, fatty alcohols, fatty amines (the latter also being suitable in the form of their salts with low-molecular-weight organic acids or mineral acids), as well as quaternary ammonium compounds such as cetylbenzyldimethylammonium chloride and, preferably, ethoxylated octadecylammonium chloride. Such emulsifiers are described, for example, in the "Römpp Lexikon Chemie," 10th edition, 2nd volume, pages 1149 and 1150.

[0076] If necessary, the pH of the preparation is adjusted to a pH of 3 - 8 with at least one acid selected from organic acid, such as acetic acid, citric acid, or lactic acid, or mineral acid, such as hydrochloric acid, etc.

[0077] Component (5) can be added separately or incorporated into the preparation together with components (1), (2), and optionally (3) and optionally (4). The individual components (1), (2), and optionally (3) are preferably prepared separately using component (5) as a solution or suspension, e.g., dispersion or emulsion, more preferably an emulsion, more preferably an oil-in-water emulsion, and then formulated into the preparation according to the invention.

[0078] The usual application amounts of component (5) are preferably 0-25 wt.%, preferably 1-20 wt.%, more preferably 2-15 wt.%, based on the total amount of components (1), (2), optionally (3) and (5).

[0079] To produce the emulsions, known methods for forming secondary emulsions are used. The emulsification temperature is typically above the melting range of the active substances of components (1), (2), and optionally (3), preferably between 50 and 80 °C. To produce the finest, most stable emulsions possible, a coarse pre-emulsion is often first prepared, the particles of which are then reduced to the required average particle size of between 0.1 and 10 µm with the aid of high-pressure homogenizers.

[0080] If desired, the inert organic solvents added as reaction medium for the preparation of components (2) and optionally (3), such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate or amyl acetate, can be removed by distillation after emulsification in order to avoid emittable organic hydrocarbons.

[0081] A further object of the invention is the use of the preparation according to the invention and the organopolysiloxane according to the invention as hydrophobizing agents, in particular as hydrophobizing agents on flat structures or fibers, such as textile substrates, linear textiles, such as yarns, threads or ropes, paper, leather and mineral flat structures.

[0082] The preparation or the organopolysiloxane is preferably applied to the fabrics for hydrophobization in amounts of 0.5-3 wt. %, preferably 0.5-2.5 wt. %, particularly preferably 0.5-2.0 wt. % of the solid substance of the preparation according to the invention, based on the weight of the fabric to be treated. Typically, a liquor of the desired concentration is applied by forced administration of an aqueous medium on the padder with liquor pickups of 40-100%, followed by pre-drying at 80-110 °C, and a subsequent heat treatment at 130-170 °C for 1-5 minutes. The duration of the heat treatment depends on the temperatures used.

[0083] Fibers within the meaning of the present invention are natural fibers as well as synthetic fibers. Natural fibers are preferably cotton, wool, or silk. Synthetic fibers are synthetically produced from natural or synthetic polymers and are preferably regenerated fibers, polyester, polyolefin, preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramid, such as Kevlar or Nomex, polyacrylonitrile, elastane, or viscose.

[0084] A textile within the meaning of the invention is made from multiple fibers. The textile is preferably linear or flat. A "linear textile" is understood to mean, for example, a yarn, a twisted yarn, or a rope. Flat textiles are preferably fleece, felt, woven fabrics, knitted fabrics, and braids. According to the invention, textiles can also contain mixtures of natural fibers and synthetic fibers. Particularly preferred are flat structures made from textile substrates, such as woven fabrics, knitted fabrics, shape-consolidated fibers, and fleece ("nonwoven").

[0085] When applied to textile fabrics, the preparations according to the invention can also be combined with textile auxiliaries commonly used in the textile industry. Particularly noteworthy are agents that improve crease-reducing properties, for example, methylol compounds of dihydroxyethylene urea or methylol melamine ethers with varying degrees of methylolation. Other suitable textile auxiliaries include those that improve flame resistance or impart a preferred hand to the fabric. However, the desired fabric hand can be achieved solely through the inventive combination of components (1)-(3), which is why additional textile auxiliaries can be dispensed with in these cases.

[0086] The sheet materials can also consist of paper, which can be produced by known papermaking methods and from all raw materials commonly used in this field. The preparations according to the invention can be applied either as an additive to the paper pulp or by application to the surface of the machine-finished paper by means of coating systems using roller, doctor blade, or air brush coating methods, followed by infrared, hot air, or cylinder drying.

[0087] Leather fabrics are also well suited for finishing with the preparations according to the invention and organopolysiloxanes. If the application takes place in the finishing processes downstream of the tannery, this can be done using conventional application methods or by spraying or impregnating.

[0088] The treatment of other surfaces is also possible. For example, mineral surfaces, such as unglazed tiles, ceramic parts, or even wall surfaces, can be given excellent water repellency by impregnating them with the finishing solution according to the invention.

[0089] In another embodiment, the preparation according to the invention or the organopolysiloxane according to the invention can be used as an additive in paints, varnishes, or plasters. The proportion of the preparation according to the invention or the organopolysiloxane is typically 1-10 wt.% solids based on the total composition.

[0090] In a further aspect, the invention relates to a process for hydrophobizing substrates, comprising applying the preparation according to the invention or the organopolysiloxane to a substrate, in particular to a sheet-like structure, more preferably to a textile substrate, paper, leather or mineral substrate.

[0091] The treatment of the fabrics can be carried out by various methods, e.g. by applying a liquor of the preparation according to the invention or of the organopolysiloxane by spraying, paddling, brushing or sponge application, dipping, impregnating, painting, or optionally also in foam form.

[0092] In general, deposits of 0.5-3 wt.%, but preferably 0.5-2.5 wt.%, more preferably 0.5-2.0 wt.% of the solid substance of the preparation according to the invention or of the organopolysiloxane, based on the weight of the sheet to be treated, are used.

[0093] Alternatively, the preparation / organopolysiloxane can be applied to a textile substrate by forced application or by exhaustion.

[0094] Furthermore, the preparation / organopolysiloxane can be used for the post-treatment of washed textiles.

[0095] Many ready-made items are washed either in domestic washing machines or in industrial washing machines. The latter applies particularly to the workwear of members of the fire service, police, military, and other professions, who frequently spend time outdoors and are thus exposed to the elements. Garments that are usually treated with oil-, water-, and dirt-repellent finishes lose these properties during washing. Therefore, these properties are often restored through subsequent treatment with repellents. The preparations according to the invention can be used for this application.

[0096] The treatment of industrially washed, ready-made articles takes place in the washing or spin-drying drum by pouring a liquor containing the inventive preparations onto the spin-dry laundry items, followed by tumble drying. In domestic washing machines, the finishing can be carried out using the usual post-treatment rinse cycle or a dosing ball system.

[0097] The invention further relates to the use of the preparations according to the invention as a finish on flat structures, with the proviso that the application is carried out from organic solvents by impregnation or dipping.

[0098] Many garments are not washed but are cleaned in organic solvents. Similar to the post-treatment of washed items, the hydrophobic properties can be restored by refreshing them with products based on the organopolysiloxanes and preparations according to the invention.

[0099] The treatment of the finished articles cleaned in organic solvents takes place in the cleaning drum of the dry cleaning machine by pouring or spraying a solution of the inventive preparations onto the spin-dry, cleaned articles, followed by tumble drying at elevated temperatures. The chemical nature of the cleaning agent is irrelevant, meaning the treatment can be carried out on modern machines in closed systems using perchloroethylene or on machines suitable for treatment with hydrocarbon-based solvents, such as Isopar J.

[0100] The invention further relates to the use of the preparations / organopolysiloxanes according to the invention as a finish on flat structures, with the proviso that the application is carried out from organic solvents by means of spraying methods.

[0101] Instead of treating textile fabrics after washing or cleaning processes by applying the preparations / organopolysiloxanes according to the invention from continuous, aqueous or solvent-based liquors, the preparations according to the invention can also be applied using various spraying methods for use in the home (consumer care sector). For this purpose, repellent agents formulated in organic solvents and propellant gases are available from spray cans or via pump mechanisms. Particularly for the shoe care sector, a significant improvement in water repellency and thus in wearer comfort can be achieved. Examples

[0102] The following examples illustrate the invention. The finishes were applied to textile fabrics on a laboratory padder of type LFV 350 / 2 "RFA" (Benz, Switzerland), followed by drying and heat treatment on a laboratory stenter of type TKF 15 / M 350 (Benz, Switzerland). The liquor pick-up was determined by weighing the finished test samples before and after application.

[0103] The hydrophobic effects were not tested immediately after application, but only after conditioning the substrates in a standard atmosphere (ISO 139) for 24 hours to eliminate any influences on these properties caused by overdrying. The application quantities and the heat treatment conditions, along with the achieved repellency effects, are listed in Tables 3a to 3c.

[0104] Water repellency was tested on the textile fabrics using a spray test according to AATCC Standard Test Method 22. The test according to AATCC Standard Test Method 22 is performed by spraying distilled water under controlled conditions onto the textile substrate to be tested and then visually comparing the wetting pattern to images of an assessment standard listed in the test method. The numerical values ​​given refer to the surface appearance after spraying the water and have the following meaning: 100 No adhesion of water drops or wetting of the upper surface 90 Occasional adhesion of water drops or wetting of the upper surface 80 Wetting of the upper surface at the points of impact of the water 70 Partial wetting of the entire upper surface 50 Complete wetting of the entire upper surface 0 Complete wetting of the entire upper and lower surface (wetting).

[0105] To test the resistance of the finished fabrics to washing processes, the test samples were washed at 60°C according to DIN EN ISO 6330:2013 and then dried according to drying methods A and F (see Table 3a & 3c).

[0106] To test the abrasion resistance of the hydrophobic finish, the water repellency of the samples in their original state was first determined using a spray test (AATCC Standard Test Method 22). The samples were then subjected to abrasion testing based on the abrasion test according to DIN EN ISO 12947-2. For this purpose, the respective samples were clamped in a Martindale test instrument, and a knitted fabric was rubbed against the samples for 2000 cycles at a load of 790 kg (corresponding to a nominal pressure of 12 kPa). After abrasion, the hydrophobic effect of the samples was determined again using a spray test (AATCC Standard Test Method 22) (see Table 3a).

[0107] To investigate the influence of hydrophobic agents on the flame-retardant properties of specific fibers, the test samples were tested according to DIN 4102, Part 1 (building material class B2: normally flammable building materials) (see Table 3b). For this purpose, the textile is stretched over a flame and observed to determine whether the flame tip reaches the measuring mark at a height of 15 cm within 20 seconds (flame burning time: 15 seconds). This test is performed a total of five times in both the warp and weft directions of the textile.

[0108] The following commercially available products were used: Borchi Kat 24: versatile bismuth carboxylate catalyst, IMCD Deutschland GmbH RUCO-LINK XCR: Solids content 25%, aqueous emulsion of a 3,5-dimethylpyrazole-blocked aliphatic polyisocyanate; Rudolf GmbH Ethoquad HAT / 25: Polyoxyethylene(15)(hydrogenated tallow)methylammonium chloride, Julius Hoesch GmbH & Co. KG Disponil A 1080: fatty alcohol ethoxylate (C 12 / 14 , 10 EO), solids content 80%, BASF Arquad 2C75: Dicocodimethylammonium chloride in isopropanol, solids content 75%, Julius Hoesch GmbH & Co. KG Examples for the preparation of component (1) compound (A):

[0109] General preparation procedure for compound (A) of formula (I), (II), (III) and / or (IV)

[0110] In a suitably sized three-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer, the components (a1, a2, or a3) and (b1) listed in Table 1a are melted in the quantities in grams specified therein under a protective gas atmosphere and with stirring. The mixture is then heated to the final temperature (T) specified in Tables 1a and 1b and stirred until no more water of reaction distills off and the acid number (AN) specified in Table 1a is reached. If necessary, 0.1% sulfuric acid can be added as a catalyst for the esterification reactions. No catalyst is required for the amidation reactions. The resulting condensation product is poured out and, after cooling, processed into flakes. Compound (A):Special preparation procedure for compound (A) of formula (I) and / or (II) using alkyl isocyanates (b2) and further processing to the reaction product (S)

[0111] In a suitably sized three-necked flask equipped with a reflux condenser, adjustable stirrer, internal thermometer, and dropping funnel, the components (a1) and (b2) listed in Table 1a are placed in grams of isopropyl acetate (solvent). Subsequently, 0.05% of 1,4-diazabicyclo(2,2,2)octane is added as a catalyst, based on the total amount of components, and the mixture is stirred at 80°C until no NCO band is detectable in the IR spectrum. Subsequently, the amounts in grams of component (IC) specified in Table 1a are added to the mixture to produce the reaction product (S) and stirring is continued at 80°C until no NCO band is visible in the IR spectrum. Reaction products (S) (= component (1)): General preparation procedure for reaction products (S) from a compound (A) and unblocked or partially blocked di-, tri- or polyisocyanates (IC)

[0112] In a suitably sized three-necked flask equipped with a reflux condenser, adjustable stirrer, internal thermometer, and dropping funnel, the components (A) and (IC) listed in Tables 1a and 1b are placed in isopropyl acetate (LM) in the amounts specified therein (in grams). Subsequently, 0.05% of 1,4-diazabicyclo(2,2,2)octane is added as a catalyst, based on the total amount of components, and the mixture is stirred at 65°C until no NCO band is detectable in the IR spectrum. Special manufacturing instructions for the reaction products (S) used in emulsions (E) 3 and 9

[0113] To prepare the emulsion (E) 3 according to Table 1a, a reaction product (S) is used, during the preparation of which (reaction of the compound (A) with the isocyanate (IC)) the amount in grams of dimethylaminoethanol indicated in Table 1a is added.

[0114] To prepare the emulsion (E) 9 according to Table 1a, a reaction product (S) is used, during the preparation of which (reaction of the compound (A) with the isocyanate (IC)) the amount in grams of bisoctadecylamine indicated in Table 1a is added. Emulsions (E): General preparation instructions for emulsions (E) from component (1) or the reaction products (S) and component (2)

[0115] Oily phase: In a suitably sized beaker, the quantities in grams of reaction product (S), present in the aforementioned isopropyl acetate, and component (2) specified in Table 1a are placed and heated to 65-70°C while stirring until a clear, homogeneous solution is obtained. The reaction product (S) to be used may need to be melted at 65-70°C prior to use to obtain a homogeneous product.

[0116] Aqueous phase: In a suitably sized beaker, the amounts in grams of emulsifiers (Em) (= component (5)) given in Table 1a are dissolved in the given amount of water at 65°C.

[0117] Both phases are stirred using a high-speed stirrer to form a coarse pre-emulsion. The mixture is then homogenized at 65°C in a high-pressure homogenizer at 300-500 bar until an average particle size between 0.1 and 10 micrometers is achieved. The solvent is then removed by azeotropic distillation on a rotary evaporator under vacuum. If necessary, the pH of the resulting emulsion is adjusted to 5-7 with 60% acetic acid. The resulting white emulsion is filtered through a 20 micrometer filter and adjusted to a solids content of 25% with water. Examples for the preparation of component (2)Organopolysiloxane (2-1)

[0118] 11.1 g (0.13 mol) of an amino-containing organopolysiloxane (I) are treated with 49.7 g of isopropyl acetate under a nitrogen atmosphere. 0.06 g of Borchi catalyst is dissolved in this mixture with stirring. Subsequently, 39.1 g (0.13 mol) of stearyl isocyanate is added in portions to allow for easy management of the exothermic reaction. After the exothermic reaction has subsided, the reaction mixture is heated to 80 °C for a further 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. This yields 94.3 g of a compound that no longer contains any protonatable basic nitrogen. This compound is used to prepare emulsions (E) 1, 4 & 7 in Table 1a.

[0119] Amino group-containing organopolysiloxane (I): Organopolysiloxane (2-2)

[0120] 12.4 g (0.13 mol) of an amino-containing organopolysiloxane (II) are treated with 49.0 g of isopropyl acetate under a nitrogen atmosphere. 0.06 g of Borchi catalyst is dissolved in this mixture with stirring. Subsequently, 38.5 g (0.130 mol) of stearyl isocyanate is added in portions to allow for easy management of the exothermic reaction. After the exothermic reaction has subsided, the reaction mixture is heated to 80 °C for a further 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. This yields 92.8 g of a compound that no longer contains any protonatable basic nitrogen. This compound is used to prepare emulsions (E) 2, 5 & 9 in Table 1a.

[0121] Amino group-containing organopolysiloxane (II): Organopolysiloxane (2-3)

[0122] 16.6 g (0.12 mol) of an amino-containing organopolysiloxane (III) are treated with 52.5 g of isopropyl acetate under a nitrogen atmosphere. 0.07 g of Borchi catalyst is dissolved in this mixture with stirring. Subsequently, 30.9 g (0.10 mol) of stearyl isocyanate is added in portions to allow for easy management of the exothermic reaction. After the exothermic reaction has subsided, the reaction mixture is heated to 80 °C for a further 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. This yields 96.7 g of a compound containing 0.54 wt. % protonatable basic nitrogen. This compound is used to prepare emulsions (E) 3, 6 & 8 in Table 1a.

[0123] Amino group-containing organopolysiloxane (III): Preparation of the preparations according to the invention (Z)

[0124] The emulsions (E) listed in Table 2a, containing components (1), (2) and (5), are optionally mixed with component (3) and optionally with water in the stated weight ratios, to give the preparations (Z) listed in Table 2a.

[0125] The preparations Z 19 - Z 20 (not according to the invention) described in Table 2b were prepared with emulsions from the patents WO 2008 / 135208 A1 (composition according to Example 5 from Table 1a) instead of the emulsions with component (2) and serve for comparison. Finishing examplesApplication of water-based preparations (Z) on textile fabrics:

[0126] Equipment conditions and test results are listed in Tables 3a, 3b and 3c. Table 2a: Mixing ratios of the preparations according to the invention (Z) Parts by weight of emulsion (E) containing components (1), (2), (4) and (5) Weight partsComponent (3)RUCO-LINK XCR parts by weight water Preparation (Z) 80 of (E) 1 - 20 1 (according to the invention) 80 of (E) 1 20 - 2 (according to the invention) 80 of (E) 2 - 20 3 (according to the invention) 80 of (E) 2 20 - 4 (according to the invention) 80 of (E) 3 - 20 5 (according to the invention) 80 of (E) 3 20 - 6 (according to the invention) 80 of (E) 4 - 20 7 (according to the invention) 80 of (E) 4 20 - 8 (according to the invention) 80 of (E) 5 - 20 9 (according to the invention) 80 of (E) 5 20 - 10 (according to the invention) 80 of (E) 6 - 20 11 (according to the invention) 80 of (E) 6 20 - 12 (according to the invention) 80 of (E) 7 - 20 13 (according to the invention) 80 of (E) 7 20 - 14 (according to the invention) 80 of (E) 8 - 20 15 (according to the invention) 80 of (E) 8 20 - 16 (according to the invention) 80 of (E) 9 - 20 17 (according to the invention) 80 of (E) 9 20 - 18 (according to the invention) Table 2b: Preparations not according to the invention (Z) Products Parts by weight Component (3) RUCO-LINKXCR parts by weight of water Preparation (Z) 80 Example 5 from WO 2008 / 135208 A1 - 20 19 (not according to the invention) 80 Example 5 from WO 2008 / 135208 A1 20 - 20 (not according to the invention)

[0127] The following points are the subject of the invention: 1. Organopolysiloxane containing at least one structural unit (i) and / or (vi): where R 6 independently of each other at least one C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, and at least one urea group, and R 7 is independently selected from -CH3, -OH and a -C 1-5 -alkoxy group. 2. Organopolysiloxane according to item 1, wherein R 6 at least one C 8-28 -Alkylurea group more preferably a C 14-20 -alkylurea group, even more preferably a C 16-18 -alkylurea group. 3. Organopolysiloxane according to item 1 or 2, wherein R 6 is selected from, and where R 10 independently H or R 11 is, R 11 independently of each other -C(O)-NH-C 8-28 -alkyl, with the proviso that R 6 at least one R 11 contains, k is 2-4, preferably 2-3 and I 2-4, preferably 2-3. 4. Organopolysiloxane according to any one of the preceding points, wherein the organopolysiloxane further contains at least one structural unit selected from and, wherein R 5 independently of each other a C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, R 8 is independently selected from and R 6 and R 7 as defined above. 5. Organopolysiloxane according to any one of the preceding points, wherein the organopolysiloxane is independently provided with end groups selected from or is cut off, whereby R 5 , R 6 , R 7 and R 8 as defined above. 6. Organopolysiloxane according to one of the preceding points, wherein the molar proportion of structural unit (i) is in the range of 25-100 mol%, preferably 50-100 mol%. 7. Organopolysiloxane according to any one of the preceding points, wherein the molar proportion of structural unit (vi) is in the range of 25-100 mol%, preferably 50-100 mol%. 8. Organopolysiloxane according to any one of the preceding points, wherein the molar fraction of the structural unit (ii) is in the range of 0-50 mol%, preferably 0-30 mol%. 9. Organopolysiloxane according to any one of the preceding points, wherein the molar fraction of the structural unit (iii) is in the range of 0-40 mol%, preferably 0-20 mol%. 10. Organopolysiloxane according to any one of the preceding points, wherein the molar fraction of the structural unit (iv) and / or (vii) is in the range of 0-20 mol%, preferably 0-10 mol%. 11. Organopolysiloxane according to one of the preceding points, wherein the molar fraction of the structural unit (v) is in the range of 0-50 mol%, preferably 0-30 mol%. 12. Organopolysiloxane according to any one of the preceding points, wherein the total basic nitrogen content measured by titration is 0-3 wt.%, preferably 0-1.5 wt.%, particularly preferably 0.01-0.5 wt.%. 13. A process for preparing an organopolysiloxane according to any one of items 1-13, comprising the steps a) providing an organopolysiloxane and / or alkoxysilane having NCO-reactive primary and / or secondary amine groups, b) reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 -alkyl isocyanate; and c) optionally hydrolysis / condensation of the alkoxysilane obtained in step b) to the organopolysiloxane. 14. Process according to item 13, wherein the organopolysiloxane according to a) is prepared by equilibration in the presence of or by hydrolysis / condensation of (C 1-5 -alkoxy)silanes having at least one NCO-reactive primary and / or secondary amine group. 15. Procedure according to point 13, whereby the (C 1-5 -Alkoxy)silane with at least one NCO-reactive primary and / or secondary amine group, the structure and / or where R 7 and R 8 as defined above. 16. Process according to any one of items 14-15, wherein the equilibration takes place in the presence of an organopolysiloxane containing structural units (ii), (iii), and / or (v) in the presence of a catalyst and water. 17. Process according to any one of items 13-16, wherein step b) is preferably carried out in the presence of di-n-butyltin dilaurate, tin(II) octoate, dibutyltin diacetate, potassium octoate, zinc dilaurate, bismuth trilaurate or tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyldipropanolamine, pentamethyldipropylenetriamine, N-methylimidazole or N-ethylmorpholine, optionally at elevated temperature, e.g. 40-140°C. 18. Organopolysiloxane obtainable by a process according to any of items 13-17. 19. Preparation comprehensive (1) at least one reaction product (S) obtainable by reacting at least one compound (A) of and / or the and / or the and / or the where R 1 = -XYZ or -Z, with X = -(CH2) n'' -, or Z = -(CH2) m -CH3, R 3= -XYZ, -Z or -YZ, with the proviso that if -YZ is the meaning in the residue R 2 n is replaced by n, R 4 = -XYZ or -(CH2) n' H is, B 1 = -VWZ or -Z, with or B 2 = -(CH2) n'' -NH2, or B 3 = -VWZ, -Z or B 4 = -VWZ orist, Q = -(CH2) n'' - is, R 5 independently of each other -OH, -YZ,or, with the proviso that at least one radical R 5 in formula (III) is an OH group, and n, n', n'', n''' and m are each independently an integer, with n0-2, n' 0-4, n'' 1-4, n''' 0-4 and m 8-30, preferably 12-26, more preferably 14-22, with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mole. (2) at least one organopolysiloxane according to any one of items 1-12 or 18, (3) optionally at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), (4) if necessary, at least one liquid medium, in particular water or an organic solvent and (5) if necessary, at least one emulsifier. 20. Preparation according to item 19, wherein component (1) constitutes 10-90 wt.%, preferably 20-80 wt.%, more preferably 25-65 wt.%, based on the total mass of components (1) and (2). 21. Preparation according to any one of items 19-20, wherein component (2) makes up 10-90 wt.%, preferably 20-80 wt.%, more preferably 30-70 wt.%, based on the total mass of components (1) and (2). 22. Preparation according to any one of items 19-21, wherein component (3) constitutes 0-50 wt.%, preferably 1-35 wt.%, more preferably 5-35 wt.%, based on the total mass of components (1), (2) and (3). 23. Preparation according to any one of items 19-22, wherein component (5) makes up 0-25 wt.%, preferably 1-20 wt.%, more preferably 2-15 wt.%, based on the total mass of components (1), (2), optionally (3) and (5). 24. Preparation according to any one of items 19-23 in the form of a dispersion, preferably in the form of an aqueous dispersion. 25. Preparation according to any one of items 19-24, wherein the solids content of the dispersion is 10-40 wt.%, preferably 15-30 wt.%. 26. Preparation according to one of points 19-25, wherein the polyisocyanate (IC) is selected from the group consisting of 2,4-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), higher-chain homologues of diphenylmethane diisocyanate (polymer MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate and mixtures, such as mixtures of MDI and polymer MDI, and derivatives thereof. 27. Preparation (Z) according to any one of items 19-26, wherein for the reaction product (S) the molar ratio of free isocyanate (NCO) groups in the polyisocyanate (IC) to isocyanate-reactive groups in compound (A) is set to 1:1 to 1:1.3, preferably 1 to 1.1. 28. Preparation (Z) according to item 27, wherein the isocyanate-reactive groups are hydroxy groups, primary and / or secondary amino groups. 29. Preparation (Z) according to any one of items 19-28, wherein the organic solvent according to component (4) is selected from esters, e.g. ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate or amyl acetate, ketones, e.g. acetone, methyl ethyl ketone and saturated hydrocarbons, such as n-hexane, n-heptane or n-octane. 30. Preparation according to any one of items 19-29, wherein the emulsifier according to component (5) is selected from anionic, cationic and non-ionic surfactants. 31. Preparation according to any one of items 19-30, which preparation is free from fluorine compounds. 32. Use of the organopolysiloxane according to any one of items 1-12 or 18 or of the preparation according to any one of items 19-31 as a hydrophobic agent 33. Use according to point 32 as a water repellent on fabrics, in particular textile substrates, paper, leather and mineral fabrics. 34. Use according to point 33 as an additive in paints, varnishes or plasters. 35. A process for the hydrophobization of substrates, comprising applying the preparation Z according to any one of items 19-31 or the organopolysiloxane according to any one of items 1-12 or 18 to a substrate, preferably a sheet-like structure, more preferably a textile substrate, paper, leather or mineral substrate. 36. Process according to item 35, wherein the application is carried out by spraying, dipping, impregnating, brushing or sponging. 37. A process according to item 35 or 36, wherein the preparation is applied to a textile substrate by forced application or by exhaustion. 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] EP 3 733 809 A1

[0006] WO 2018 / 110667

[0007] WO 2008 / 135208

[0008] WO 2015 / 191326

[0009] EP 1 136 513 B1

[0030] DE 100 17 651 A1 [0051, 0057, 0068] EP 0 159 117 B1

[0058] DE 44 41 418 A1

[0058] WO 2008 / 135208 A1 [0125, 0126] Cited non-patent literature

[0000] LAD effect, "Laundry / Air Dry", M. Rasch et al., Melliand Textilberichte 6 / 2005, pp. 456-459

[0011] W. Siefken (Liebigs Annalen der Chemie 562, 1949, pages 75-136

[0053] Römpp Lexikon Chemie“, 10th edition, 2nd volume, pages 1149 and 1150

[0075] DIN EN ISO 6330:2013

[0105]

Claims

[1] Organopolysiloxane containing at least one structural unit (i) and / or (vi): where R 6 independently of each other at least one C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, and at least one urea group, and R 7 is independently selected from -CH3, -OH and a -C 1-5 -alkoxy group. [2] Organopolysiloxane according to claim 1, wherein R 6 at least one C 8-28 -Alkylurea group more preferably a C 44-20 -alkylurea group, even more preferably a C 16-18 -alkylurea group and is in particular selected fromand where R 10 independently H or R 11 is, R 11 independently of each other -C(O)-NH-C 8-28 -Alkyl, with the proviso that R 6at least one R 11 contains, k is 2-4, preferably 2-3 and I 2-4, preferably 2-3. [3] Organopolysiloxane according to any one of the preceding claims, wherein the organopolysiloxane further comprises at least one structural unit selected from and, wherein R 5 independently of each other a C 8-28- Alkyl group, preferably C 14-20 -alkyl group, more preferably C 16-18 -alkyl group, R 8 is independently selected from and R 6 and R 7 as defined above. [4] Organopolysiloxane according to one of the preceding claims, wherein the molar fraction of structural unit (i) is in the range of 25-100 mol%, preferably 50-100 mol% and / or the molar fraction of structural unit (vi) is in the range of 25-100 mol%, preferably 50-100 mol% and / or the molar fraction of structural unit (ii) is in the range of 0-50 mol%, preferably 0-30 mol% and / or the molar fraction of structural unit (iii) is in the range of 0-40 mol%, preferably 0-20 mol% and / or the molar fraction of structural unit (iv) and / or (vii) is in the range of 0-20 mol%, preferably 0-10 mol% and / or the molar fraction of structural unit (v) is in the range of 0-50 mol-%, preferably 0-30 mol-%. [5] Organopolysiloxane according to any one of claims 1-4 obtainable by a process comprising the steps a) providing an organopolysiloxane and / or alkoxysilane having NCO-reactive primary and / or secondary amine groups, b) reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 -alkyl isocyanate; and c) optionally hydrolysis / condensation of the alkoxysilane obtained in step b) to the organopolysiloxane. [6] Organopolysiloxane according to claim 5, wherein the organopolysiloxane according to a) is prepared by equilibration in the presence of or by hydrolysis / condensation of (C 1-5 -alkoxy)silanes having at least one NCO-reactive primary and / or secondary amine group, wherein the (C 1-5 -Alkoxy)silane having at least one NCO-reactive primary and / or secondary amine group, preferably has the structure and / or, where R 7 and R 8 as defined above. [7] Preparation comprehensive (1) at least one reaction product (S) obtainable by reacting at least one compound (A) of the formula (II) and / or of the formula (III) and / or the formula (IV) where R 1= -XYZ or -Z, with X = -(CH2) n'' -,or Z = -(CH2) m -CH3, R 3 = -XYZ, -Z or -YZ, with the proviso that if -YZ is the meaning in the residue R 2 n is replaced by n", R 4 = -XYZ or -(CH2) n' H is, B 1 = -VWZ or -Z is, withororis, B 2 = -(CH2) n ··-NH2, or B 3 = -VWZ, -Z orist, B 4 = -VWZ orist, Q = -(CH2) n'' - is, R s independently of each other -OH, -YZ,or, with the proviso that at least one radical R s in formula (III) is an OH group, and n, n', n", n''' and m are each independently an integer, with n0-2, n' 0-4, n' 1-4, n''' 0-4 and m 8-30, preferably 12-26, more preferably 14-22, with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mole, wherein the preparation is preferably free of fluorine compounds. (2) at least one organopolysiloxane according to any one of claims 1-4, (3) optionally at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), (4) if necessary, at least one liquid medium, in particular water or an organic solvent and (5) if necessary, at least one emulsifier. [8] Preparation according to claim 7, wherein component (1) makes up 10-90 wt.%, preferably 20-80 wt.%, more preferably 25-65 wt.%, based on the total mass of components (1) and (2) and / or component (2) makes up 10-90 wt.%, preferably 20-80 wt.%, more preferably 30-70 wt.%, based on the total mass of components (1) and (2) and / or component (3) makes up 0-50 wt.%, preferably 1-35 wt.%, more preferably 5-35 wt.%, based on the total mass of components (1), (2) and (3) and / or component (5) makes up 0-25 wt.%, preferably 1-20 wt.%, more preferably 2-15 wt.%, based on the total mass of components (1), (2), optionally (3) and (5). [9] Preparation according to any one of claims 7-8 in the form of a dispersion, preferably in the form of an aqueous dispersion, wherein the solids content of the dispersion is preferably 10-40 wt%, more preferably 15-30 wt%. [10] Preparation according to one of claims 7-9, wherein the polyisocyanate (IC) is selected from the group consisting of 2,4-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), higher-chain homologues of diphenylmethane diisocyanate (polymer MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate and mixtures, such as mixtures of MDI and polymer MDI, and derivatives thereof. [11] Preparation (Z) according to any one of claims 7-10, wherein for the reaction product (S) the molar ratio of free isocyanate (NCO) groups in the polyisocyanate (IC) to isocyanate-reactive groups in compound (A) is set to 1:1 to 1:1.3, preferably 1 to 1.1, wherein the isocyanate-reactive groups are preferably hydroxyl groups, primary and / or secondary amino groups. [12] Organopolysiloxane according to any one of claims 1-6 or the preparation according to any one of claims 7-11 for use as a hydrophobizing agent, in particular on fabrics, in particular textile substrates, paper, leather and mineral fabrics or as an additive in paints, varnishes or plasters.

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