Effect - persistent hydrophobizing agent

Abstract

The present invention relates to at least one C 8~28 The present invention relates to organopolysiloxanes which contain at least one structural unit having an alkyl group and at least one urea group, to a process for their preparation, to preparations which contain said organopolysiloxanes, and to their use as hydrophobizing agents.

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane containing at least one structural unit having at least one C 8~28 alkyl group and at least one urea group, a method for producing the same, a preparation containing the organopolysiloxane, and use as a hydrophobizing agent.

[0002] In order to cope with exposure to rain or water splashes during use of a planar structure, aqueous or solvent-based preparations of silicone oil, paraffin, fluorocarbon polymers and other additives are usually used to hydrophobize or oleophobize the planar structure.

[0003] When a water-repellent effect is produced by paraffin and silicone-based products, only hydrophobization occurs, but in the case of fluorocarbon polymers (FC polymers), additional antifouling and oil-repellent effects also occur.

[0004] The effect level of FC polymers is generally good, but after washing treatment, since the orientation of the active fluorocarbon groups in the polymer molecules is disturbed, the hydrophobic and oleophobic effects are significantly reduced unless reorientation occurs by heat treatment. That is, in order to reactivate the desired effects, it is necessary to perform heat treatment on such treated planar structures, particularly textiles, after washing. This heat treatment is hereinafter referred to as "reactivation".

[0005] Furthermore, fluorocarbon polymer-based preparations are costly, especially due to energy-intensive production, and there are concerns about their toxicity to the environment and the human body, so their use is being viewed increasingly critically, particularly in the clothing field. Therefore, alternative fluorine-free products having an equivalent property profile are sought, and in that case, not only good initial hydrophobicity but also the durability of the finishing process against repeated washing are important quality characteristics.

[0006] In European Patent Application Publication No. 3733809, preparations based on amino-modified silicone, organopolysiloxane having a three-dimensional structure, and alkylpolysiloxane are used to obtain a water-repellent effect on textile materials.

[0007] International Publication No. 2018 / 110667 describes a composition for hydrophobizing a substrate, which contains a polymer composed of a non-fluorinated (meth)acrylate group and a silicone macromer.

[0008] From International Publication No. 2008 / 135208, fluorocarbon-free preparations based on hydrophobic reaction products and C8 - C 28 alkyl group-containing organopolysiloxanes are known.

[0009] International Publication No. 2015 / 191326 discloses a preparation for hydrophobizing a substrate, which contains a urethane-based compound in addition to wax. The wax may be, for example, natural wax, synthetic wax, or a mixture thereof.

[0010] Although good water-repellent effects can be obtained using such preparations, usually a relatively large amount of usage is required, thereby reducing the breathability of the finished textile. Furthermore, in order to restore the original effect level, similar to the case of textiles treated with fluorocarbon-containing preparations, after washing, heat treatment (reactivation) such as using a tumble dryer or ironing must be performed.

[0011] Therefore, an object of the present invention is to provide compounds and preparations that enable a good and sustainable hydrophobic effect with a small amount of usage without requiring reactivation (LAD effect, "Laundry / Air Dry", M. Rasch et al., Melliand Textilberichte 6 / 2005, p.456 - 459).

[0012] Surprisingly, this problem could be solved by an organopolysiloxane containing at least one structural unit having at least one long-chain alkyl group and at least one urea group. Furthermore, this effect can be enhanced in the preparation according to the invention containing the organopolysiloxane according to the invention. The organopolysiloxane according to the invention causes excellent hydrophobization of the substrate even in a small amount of use. Furthermore, since the preparation according to the invention causes excellent adhesion to the substrate, the effect level hardly changes over time (effect persistence), and can also be maintained even during application due to, for example, abrasion or washing.

[0013] Also, surprisingly, it has been found that the effect level can be kept constant without taking reactivation measures (LAD effect).

[0014] Also, for example, flame-retardant fibers such as Trevira CS and textiles made therefrom generally have reduced flame retardancy by the application of a FC-free hydrophobizing agent, but it has been found that they do not lose their flame retardancy even after the application of the compound or preparation according to the invention.

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

[0016] R 6 is preferably of the formula: [Chemical formula] at least one C by 8~28 including an alkylurea group, more preferably, R 6 is at least one C 14~20 alkylurea group, even more preferably C 16~18 including an alkylurea group.

[0017] In a preferred embodiment, R 6 is [Chemical formula] selected from the formula [wherein, R 10 are independently of each other, H or R 11 and R 11 are 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, but provided that R 6 includes at least one R 11 and k is 2 to 4, preferably 2 to 3, l is 2 to 4, preferably 2 to 3].

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

[0019] The organopolysiloxane, independently of one another, preferably has the following terminal groups:

Chemical formula

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

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

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

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

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

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

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

[0027] In a further aspect, the invention relates to a process for preparing an organopolysiloxane according to the invention, a) providing an organopolysiloxane and / or an alkoxysilane having NCO-reactive primary and / or secondary amino groups; b) reacting the organopolysiloxane and / or alkoxysilane according to a) with a C 8~28 alkyl isocyanate; c) optionally, hydrolyzing / condensing the alkoxysilane obtained in step b) to obtain an organopolysiloxane and a process comprising these steps.

[0028] In particular, the invention a’) providing an organopolysiloxane having NCO-reactive primary and / or secondary amino groups; b’) reacting the organopolysiloxane according to a’) with a C 8~28 alkyl isocyanate, preferably a C 14~20 alkyl isocyanate, more preferably a C 16~18 alkyl isocyanate; and a process for preparing an organopolysiloxane comprising these steps.

[0029] Alternatively or additionally, the process comprises a’’) providing an alkoxysilane having NCO-reactive primary and / or secondary amino groups; b’’) reacting the alkoxysilane according to a’’) with a C 8~28The step of reacting with an alkyl isocyanate, and c'') the step of hydrolyzing / condensing the alkoxysilane obtained in step b'') to obtain an organopolysiloxane can include.

[0030] The organopolysiloxane according to step a') can be obtained by equilibration in the presence of an (C 1~5 alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group. The equilibration reaction is preferably carried out using a base catalyst and is described, for example, in Example 1 of European Patent No. 1136513. As starting materials, in the equilibration reaction, an organooligosiloxane or an organopolysiloxane can be used together with an alkoxysilane having at least one NCO-reactive primary and / or secondary amino group. Preferably, the equilibration is carried out in the presence of an organopolysiloxane containing structural units (ii), (iii), and / or (v), preferably in the presence of a metal hydroxide and water.

[0031] Also, the organopolysiloxane can be obtained by hydrolysis and condensation of an alkoxysilane having at least one NCO-reactive primary and / or secondary amino group. In this hydrolysis reaction, an alkoxysilane that generates structural units (ii), (iii) and / or (v) may further be added. In order to shift the equilibrium in the hydrolysis to the product side, the alcohol obtained can be distilled off under reduced pressure if necessary.

[0032] In the process according to the invention, the alkoxysilane in step a'') is preferably an (C 1~5 alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group, more preferably

Chemical formula

[0033] The reactions according to steps b') and b'') are carried out between a linear or branched C 8~28 alkyl isocyanate and an NCO-reactive primary and / or secondary amino group, preferably with the alkyl isocyanate being added to the amino group under stirring. In this case, the reaction can be carried out in bulk or, for example, in a solvent such as ethyl acetate, isopropyl acetate, acetone, tetrahydrofuran, methyl ethyl ketone, methyl propyl ketone, toluene, xylene, dipropylene glycol dimethyl ether, methoxypropyl acetate. To accelerate the reaction, the reaction mixture can be temperature-controlled at 40 to 140 °C if necessary. As the catalyst, in particular, di-n-butyltin dilaurate, tin(II) octoate, dibutyltin diacetate, potassium octoate, zinc dilaurate, bismuth trilaurate or a tertiary amine, for example 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyldipropanolamine, pentamethyldipropylenetriamine, N-methylimidazole or N-ethylmorpholine is applicable.

[0034] C 8~28 The molar stoichiometry between the alkyl isocyanate and the NCO-reactive primary or secondary amino group is preferably such that 50 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% of the amino groups react with the NCO groups of the alkyl isocyanate. Thus, in a non-stoichiometric reaction, protonable amino groups remain in the organopolysiloxane. The content of protonable basic nitrogen is 0 to 3% by weight (see above). 8~28 is selected to react with the NCO groups of the alkyl isocyanate. Therefore, in a non-stoichiometric reaction, protonable amino groups remain in the organopolysiloxane. The content of protonable basic nitrogen is 0 to 3% by weight (see above).

[0035] Step c'') is preferably carried out in the presence of a catalyst, preferably KOH, NaOH, optionally with an increase in temperature, for example at 40 to 140 °C.

[0036] In step c''), the alkoxysilane obtained in step b'') is hydrolyzed and then condensed. In the hydrolysis reaction, an alkoxysilane that generates structural units (ii), (iii), and / or (v) may be added. In order to shift the equilibrium in the hydrolysis to the product side, the obtained alcohol can be distilled off / condensed under reduced pressure as necessary.

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

[0038] In a further aspect, the present invention is (1) Formula (I)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0039] The preparation according to the invention preferably does not contain fluorine compounds.

[0040] The preparation is preferably in the form of a dispersion, preferably in the form of an aqueous dispersion. In this case, the solid content of the dispersion is preferably 10 to 40% by weight, more preferably 15 to 30% by weight.

[0041] The reaction product (S) is preferably hydrophobic. The expression "hydrophobic" in the sense of the present invention typically defines a compound that is substantially insoluble in water at 20°C. A saturated solution of the "hydrophobic" reaction product (S) preferably contains at most 1 g, more preferably at most 0.5 g / l, even more preferably at most 0.2 g / l of the dissolved compound per liter of water (20°C).

[0042] The reaction product (S) can be obtained by reacting at least one compound (A) with at least one di-, tri- or polyisocyanate (IC) that is not blocked or at least partially blocked.

[0043] The compound (A) of formula (I) is preferably obtained by reacting a polyhydric alcohol (a1) with a carboxylic acid (b1) or an alkyl isocyanate (b2). Preferred examples of the polyhydric alcohol (a1) are glycerin, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol or saccharides such as glucose, preferably glycerin, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol and / or pentaerythritol, more preferably glycerin.

[0044] The compound (A) of formula (II) is preferably obtained by reacting an alkanolamine (a2) and / or an alkylamine (a3) with a carboxylic acid (b1) and / or an 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, preferably those having 12 to 24 carbon atoms in the alkyl group, and their ethoxylated products. Particularly preferred are diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, aminoethylethanolamine, and aminopropylethanolamine, and more preferably triethanolamine.

[0045] Examples of alkylamine (a3) are bis(aminoethyl)amine, bis(aminopropyl)amine and their polymeric homologs, aminoethyliminopropylamine, bis(aminopropyl)ethylenediamine, tris(aminoethyl)amine, tris(aminopropyl)amine, trisaminononane, aminopropylstearylamine, and aminopropylbisstearylamine. Here, bis(aminoethyl)amine, bis(aminopropyl)amine, aminoethylaminopropylamine, bis(aminopropyl)ethylenediamine, and aminopropylstearylamine are preferred, and particularly bis(aminoethyl)amine is preferred.

[0046] The carboxylic acid (b1) used in the production of the compound (A) may be saturated or unsaturated, may be unbranched or branched, and preferably has 10 to 32 carbon atoms, more preferably 12 to 24 carbon atoms. Preferably, it is an unbranched saturated carboxylic acid, preferably having 10 to 32 carbon atoms, more preferably 12 to 24 carbon atoms, for example, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid are used. Here, lauric acid, palmitic acid, stearic acid and behenic acid are particularly preferred.

[0047] The alkyl isocyanate (b2) used in the production of the formulas (I) and (II) is preferably unbranched, and in that case, the alkyl group preferably has 9 to 31 carbon atoms, particularly 11 to 23 carbon atoms. A particularly preferred alkyl isocyanate is stearyl isocyanate.

[0048] Instead of the compound (A) produced using the polyhydric alcohol (a1) or alkanolamine (a2) or alkylamine (a3) and the carboxylic acid (b1) or alkyl isocyanate (b2), a compound having an active hydrogen atom and two hydrophobic groups, for example, gerb alcohol, bis(dodecyl)amine and preferably bis(octadecyl)amine can also be used.

[0049] The compound of formula (III) is sorbitol and C 10 ~C 32 carboxylic acid, preferably C 14 ~C 28 carboxylic acid, particularly preferably C 16 ~C 24It is a sorbitan ester obtained by reaction with a carboxylic acid under dehydration of water. Here, depending on the stoichiometry, mono-, di- or triesters, as well as mixtures thereof, can be formed. Optionally, alkoxylated derivatives can also be used. For the reaction with unblocked or at least partially blocked di-, tri- or polyisocyanates (IC), it is necessary that there is at least one reactive OH group in the sorbitan ester. Further, 1,4-sorbitan hydride is C 10 ~C 32 alkyl isocyanate, preferably C 14 ~C 28 alkyl isocyanate, particularly preferably C 16 ~C 24 alkyl isocyanate can be reacted to obtain a compound of formula (III).

[0050] The compound of formula (IV) is an alkyl citrate obtained by esterification of citric acid with a long-chain C 10 ~C 32 alcohol, preferably C 14 ~C 28 alcohol, particularly preferably C 16 ~C 24 alcohol.

[0051] At least one hydrophobic reaction product (S) is obtained by reacting at least one compound (A) with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), where the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is 1.8 to 10 per mole. Examples of unblocked or partially blocked isocyanates are described in German Patent Application Publication No. 10017651, paragraphs

[0032] to

[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), higher chain homologues of diphenylmethane diisocyanate (polymeric MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, mixtures, for example, mixtures of MDI and polymeric MDI, and derivatives thereof. Dimer diisocyanate is available under the name DDI 1410 from Cognis Corp., 300 Brookside Avenue, Ambler, PA 19002, USA.

[0053] Derivatives of isocyanate (IC) include, for example, cyclic oligo- or polyisocyanates. The production of cyclic oligo- or polyisocyanates can be carried out by known cyclization methods by W. Siefken (Liebigs Annalen der Chemie 562, 1949, p.75-136), where the oligo- or polyisocyanate may be open-chain or cyclic. Such derivatives can be produced from the above-mentioned di-, tri- and polyisocyanates by bonding using urethane structure, allophanate structure, urea structure, biuret structure, uretdione structure, amide structure, isocyanurate structure, carbodiimide structure, uretonimine structure, oxadiazinetrione structure or iminooxadiazinedione structure. Preferably, hexamethylene diisocyanate trimer, diphenylmethane diisocyanate trimer, and urethanes of 2,4-tolylene diisocyanate still having free NCO groups are used.

[0054] In addition, in order to improve the emulsifiability of component (1) in water, it is possible to form urethane by derivatizing a partial amount of isocyanate groups with a polyalkoxymonoalkyl ether using an appropriate catalyst system. In this case, polyethylene glycol monomethyl ether having preferably 4 to 20 ethylene oxide units and optionally further 2 to 6 propylene oxide units can be used. A system known to those skilled in the art based on a tertiary amine and / or an organotin compound, such as dibutyltin dilaurate, dioctyltin dilaurate or dioctyltin diacetate, can be used as a catalyst.

[0055] Preferred derivatives are hexamethylene diisocyanate trimer, diphenylmethane diisocyanate trimer, urethane of 2,4-tolylene diisocyanate having free NCO groups, and polyalkoxymonoalkyl ether-modified di-, tri- or polyisocyanates (IC), especially polyethylene oxide monoalkyl ether-modified di-, tri- or polyisocyanates.

[0056] By using a tertiary alkanolamine as an additive substance as an alternative to the isocyanate modified with a polyalkoxymonoalkyl ether, the cationic charge of the reaction product (S) can be improved, and thus the self-emulsifiability can be improved without impairing the overall properties. In this case, dimethylaminoethanol is particularly suitable.

[0057] The isocyanate (IC) may further be partially or completely blocked (see, for example, German Patent Application Publication No. 10017651, 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 a di-, tri- or polyisocyanate (IC) with a blocking agent, for example as described in European Patent No. 0 159 117 or German Patent Application Publication No. 4 441 418, in the melt or in an organic solvent (LM) which is inert to isocyanates, preferably in the presence of a suitable catalyst under a protective gas atmosphere.

[0059] The molar ratio of the free NCO groups of the di-, tri- or polyisocyanate (IC) to be blocked to the reactive groups of the blocking agent is above the stoichiometric amount, preferably at most 2:1, more preferably at most 3:1.

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

[0061] In a preferred embodiment, the preparation contains component (1) in an amount of 10 to 90% by weight, more preferably 20 to 80% by weight, even more preferably 25 to 65% by weight, based on the total weight of components (1) and (2).

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

[0063] In one embodiment, component (2) accounts for 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total weight of components (1) and (2).

[0064] The addition of component (3) in the preparation (Z) according to the invention is optional. Unblocked di-, tri- or polyisocyanates (IC) suitable for component (3) have already been described above in the production of the reaction product (S) of component (1). Compounds of this type are called boosters and cause an improvement in the water repellency on the treated planar structure. At the same time, due to the polyfunctionality of the polyisocyanate, crosslinking occurs between the -OH groups, -COOH groups or -NH2 groups that are always present on most substrates and the unreacted functional groups of component (1), thereby significantly improving the durability against washing treatment and increasing the abrasion resistance.

[0065] Component (3) can be used in both non-blocked and blocked forms. The non-blocked form of component (3) is mainly used when using non-polar media, because in this case, an undesirable early reaction between the free NCO groups and the reactive hydrogen atoms of the used medium is avoided.

[0066] When component (3) is applied from the use medium to a planar structure having NCO-reactive groups, it is often necessary to protect them by blocking with a suitable blocking agent. In such cases, the production of component (3) is carried out by completely blocking the free NCO groups of the di-, tri- or polyisocyanate with a blocking reagent and optionally in an organic solvent. To achieve complete blocking, usually a blocking agent slightly in excess of the stoichiometric amount is used. When producing products for aqueous applications, the blocked di-, tri- or polyisocyanate needs to be dissolved in an organic solvent if necessary and converted into an emulsion form using a suitable emulsifier (= component (5)).

[0067] Examples of suitable common and known blocking agents are known from German Patent Application Publication No. 10017651, paragraph 0042 and have already been described in the description of the production of the reaction product (S) of component (1).

[0068] In a particular embodiment, an unblocked di-, tri- or polyisocyanate that improves the self-emulsifying ability in water by partially reacting a polyalkoxymonoalkyl ether with an isocyanate group using a suitable catalyst system can be used as a booster. By attaching a hydrophilic side chain to the di-, tri- or polyisocyanate, the HLB value of the urethane thus produced is advantageously changed, and a compound that is itself insoluble in water acquires self-emulsifying properties. In the hydrophilic side chain, a predetermined selection of the type and amount of groups is advantageous. Preferably, 4 to 20 ethylene oxide groups are used together with optionally 2 to 6 propylene oxide groups, and these may also be present in a blocked form within the alkoxy chain. However, in the case of such a mixed alkoxylated side chain, the proportion of ethylene oxide always exceeds the proportion of propylene oxide. As a catalyst for urethane synthesis, systems known to those skilled in the art based on tertiary amines and / or organotin compounds such as dibutyltin dilaurate, dioctyltin dilaurate or dioctyltin diacetate can be used.

[0069] In use, the urethane thus produced, when introduced into water, spontaneously forms a fine emulsion with high stability against shear forces and good compatibility with other components of the applied treatment liquid. Due to the reaction of the remaining unreacted NCO groups with water, in such a specific form, only a limited pot life of up to 8 hours in the applied treatment liquid is possible.

[0070] The addition of component (3) is particularly carried out when particularly high requirements are imposed on the wash resistance of the treated planar structure.

[0071] Advantageously, component (3) is used in an amount of 0 to 50% by weight, preferably 1 to 35% by weight, more preferably 5 to 35% by weight, based on the total weight of components (1), (2) and (3). Component (3) can also be used directly from a medium that contains a solvent but does not contain water, without a compounding aid.

[0072] Advantageously, component (3) is used in an amount of 5 to 35%, which can be used directly from a solvent-containing but water-free medium without compounding aids for application. When administration is carried out from an aqueous medium, an emulsion of component (3) having a solids content of preferably 15 to 35% by weight is used, which is optionally an emulsifier (= component (5)) based on a quaternary form of ethoxylated fatty amine, and optionally other emulsification aids such as ethylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether or a solubilizer based on n-methylpyrrolidone. Here, emulsification can be carried out using a high-pressure homogenizer.

[0073] Component (4) is optional. The liquid medium is preferably water or an organic solvent. Suitable organic solvents are preferably inert solvents such as esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate or amyl acetate, ketones such as acetone methyl ethyl ketone and saturated hydrocarbons such as n-hexane, n-heptane or n-octane.

[0074] The preparation (Z) according to the invention can further comprise at least one emulsifier. Component (5) is particularly used when the preparation is in the form of a suspension, in particular a dispersion or an emulsion. The surfactant ensures that the phase, in particular the oil phase, is distributed as uniformly as possible in the aqueous phase. In particular, nonionic, cationic or anionic surfactants are used as emulsifiers. Preferred nonionic, anionic or cationic emulsifiers are ethoxylated products of fatty acids, fatty acid amides, fatty alcohols, fatty amines, the latter also being in the form of their salts with low molecular weight organic or mineral acids, and furthermore quaternary ammonium compounds, such as cetylbenzyldimethylammonium chloride, and preferably ethoxylated octadecylammonium chloride. Such emulsifiers are described, for example, in "Roempp Lexikon Chemie", 10th edition, volume 2, pages 1149 and 1150.

[0075] If necessary, the pH value of the preparation is adjusted to 3 to 8 using at least one acid selected from organic acids such as acetic acid, citric acid or lactic acid, or mineral acids such as hydrochloric acid.

[0076] Component (5) can be added separately or introduced into the preparation together with components (1), (2) and optionally (3) and optionally (4). The individual components (1), (2) and optionally (3) are preferably produced separately using component (5) as a solution or suspension, for example a dispersion or an emulsion, more preferably an emulsion, more preferably a water-in-oil emulsion, and then incorporated into the preparation according to the invention.

[0077] The usual application amount of component (5) is advantageously 0 to 25% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on the total amount of components (1), (2), optionally (3) and (5).

[0078] For the production of the emulsion, known methods for the formation of the secondary emulsion are used. Usually, the emulsification temperature exceeds the melting range of the active substances of the components (1), (2) and optionally (3), and is preferably 50 to 80 °C. In order to produce an emulsion that is as fine and particularly stable as possible, first a coarsely divided pre-emulsion is produced, and then its particles are often reduced to the required average particle size of 0.1 to 10 μm using a high-pressure homogenizer.

[0079] If desired, the inert organic solvent added as a reaction medium for the production 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 to avoid possible organic hydrocarbons.

[0080] A further subject of the present invention is the use of the preparation according to the present invention and the organopolysiloxane according to the present invention as a hydrophobizing agent, particularly as a hydrophobizing agent in planar structures or fibers, such as textile substrates, linear textiles, such as yarns, twisted yarns or strings, paper, leather and mineral-based planar structures.

[0081] The preparation or organopolysiloxane is preferably applied to the planar structure for hydrophobization, and the solid substance of the preparation according to the present invention is applied in an amount of 0.5 to 3% by weight, preferably 0.5 to 2.5% by weight, particularly preferably 0.5 to 2.0% by weight based on the weight of the planar structure to be treated. Usually, the treatment liquid is applied from an aqueous medium to a padding machine with a treatment liquid absorption rate of 40 to 100% by forced application at the desired concentration, and then pre-dried at 80 to 110 °C, followed by heat treatment at 130 to 170 °C for 1 to 5 minutes. The time of the heat treatment depends on the temperature applied respectively.

[0082] Fibers in the sense of the present invention are natural fibers and artificial fibers. Natural fibers are preferably cotton, wool or silk. Synthetic fibers or artificial fibers are synthetically produced from natural or synthetic polymers, preferably regenerated fibers, polyester, polyolefin, preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramide, for example Kevlar or Nomex, polyacrylonitrile, elastane or viscose.

[0083] Textiles in the sense of the present invention are made from a plurality of fibers. Preferably, the textile is linear or planar. "Linear textile" means, for example, yarn, twisted yarn or string. Planar textiles are preferably fleece, felt, woven fabric, knitted fabric and braided fabric. According to the present invention, the textile can also contain a mixture of natural fibers and synthetic fibers. Particularly preferred is, for example, a planar structure composed of a textile substrate such as woven fabric, knitted fabric, form-reinforcing fiber, fleece ("non-woven fabric").

[0084] When applied to a textile planar structure, the preparation according to the present invention can also be combined with textile auxiliaries commonly used in the textile industry. Examples include agents for improving wrinkle resistance, such as methylol compounds of dihydroxyethylene urea, or methylol melamine ethers with different degrees of methylolation. Furthermore, textile auxiliaries include those that improve flame retardancy or give a preferred feel to the planar structure. However, the desired feel of the article can be achieved only by the combination of components (1) to (3) according to the present invention, so in these cases, additional textile auxiliaries can be omitted.

[0085] The planar structure may also be made of paper, which can be manufactured from all basic materials customary in this field of application by known papermaking methods. In this case, the preparation according to the invention can be applied as an additive to paper lumps, or also by means of a coating system with a coating process using a roller, doctor blade or airbrush followed by infrared, hot air or cylinder drying, applied to the surface of the paper smoothed mechanically.

[0086] Similarly, planar structures made of leather are very suitable for the finishing with the preparation according to the invention and organopolysiloxanes. When applied in the finishing process downstream of the tanning factory, this can be done using known application methods or by spraying or impregnation.

[0087] Also, the treatment of other planar structures is similarly possible. For example, excellent water repellency can be imparted to mineral-based planar structures such as unglazed tiles, ceramic parts or even wall surfaces by impregnation with the finishing treatment liquid according to the invention.

[0088] In another embodiment, the preparation according to the invention or the organopolysiloxane according to the invention can be used as an additive in paints, lacquers or plasters. Usually, the proportion of the preparation or organopolysiloxane according to the invention is 1 to 10% by weight of solid matter based on the total composition.

[0089] In a further aspect, the invention relates to a method for hydrophobizing a substrate, which comprises applying a preparation or an organopolysiloxane according to the invention to a substrate, in particular a planar structure, more preferably a textile substrate, paper, leather or a mineral-based substrate.

[0090] The treatment of the planar structure can be carried out in various ways. For example, the application of the treatment liquid of the preparation or organopolysiloxane according to the invention can be carried out by spraying, slope padding, brush coating or sponge coating, dipping, impregnation, brush painting or, if necessary, in a foamed form.

[0091] Generally, the preparation according to the invention or the solid substance of the organopolysiloxane is used in an application amount of 0.5 to 3% by weight, but preferably 0.5 to 2.5% by weight, more preferably 0.5 to 2.0% by weight, based on the weight of the planar structure to be treated.

[0092] Also, the preparation / organopolysiloxane can be applied to the textile substrate by means of forced application or extraction methods.

[0093] Furthermore, the preparation / organopolysiloxane can be used for the after-treatment of washed textiles.

[0094] Many ready-made products are washed either at home in a domestic washing machine or in an industrial washing machine. The latter is widely applicable to work clothes of members of the fire department, police, army, and other occupations that often have to be outdoors and are thus exposed to the elements. Usually, the properties of clothes that have been finished with oil-repellent, water-repellent, and stain-resistant treatments are lost during washing. Therefore, these properties are frequently restored by post-treatment with a hydrophobizing agent. The preparation according to the invention can be used for this purpose.

[0095] The treatment of industrially washed ready-made products is carried out in a washing drum or a spin-drying drum by pouring the treatment liquid of the preparation according to the invention onto the dewatered wet laundry and then drying it in a tumbler. In a domestic washing machine, the finishing can be carried out by means of a normal after-treatment rinsing step or a dispenser ball system.

[0096] A further subject of the invention is the use of the preparation according to the invention as a finishing agent for planar structures, provided that the use is carried out in an impregnation or dipping process from an organic solvent.

[0097] Many clothes are intended for cleaning with organic solvents rather than by washing. As in the case of the after-treatment of washed articles, in this case too, the hydrophobicity can be restored by refreshing with products based on the organopolysiloxanes and preparations according to the invention.

[0098] The treatment of ready-made articles cleaned with organic solvents is carried out by pouring or spraying the treatment liquid of the preparation according to the invention onto the wet articles cleaned and de-liquored in the cleaning drum of a dry-cleaning machine and then removing the solvent at a high temperature in a tumbler. Here, the chemical properties of the cleaning agent are not important, i.e. the treatment can be carried out on a state-of-the-art machine in a closed system using perchloroethylene or on a machine suitable for treatment with a hydrocarbon solvent such as Isopar J, for example.

[0099] A further subject of the invention is the use of the preparation / organopolysiloxane according to the invention as a finishing agent for planar structures, provided that the use is carried out by a spraying method from an organic solvent.

[0100] Instead of treating textile planar structures after the washing or cleaning process by applying the preparation / organopolysiloxane according to the invention from a continuous aqueous or solvent-containing treatment liquid, for use in the household goods sector (consumer care sector), the application of the preparation according to the invention can also be carried out by various spraying methods. For this purpose, a hydrophobizing agent formulated in an organic solvent and a propellant by means of a spray can or a pump mechanism are provided. In particular, in the field of shoe care, a considerable improvement in water repellency and thus in wearing comfort can be achieved.

[0101] Examples The following examples illustrate the present invention. The application of the finishing agent to the textile planar structure was carried out using a laboratory padding machine of type LFV 350 / 2 "RFA" (Benz, Switzerland), and the subsequent drying and heat treatment were carried out on a laboratory tension frame of type TKF 15 / M 350 (Benz, Switzerland). The determination of the treatment liquid absorption rate was carried out by measuring the weights of the finished test samples before and after application.

[0102] The test of the hydrophobic effect was carried out not immediately after application, but after conditioning the substrate in a standard atmosphere (ISO 139) for 24 hours, in order to equalize the influence of overdrying on these properties. The application amounts and heat treatment conditions are shown in Tables 3a to 3c together with the hydrophobic effect to be achieved.

[0103] For the textile planar structure, the water repellency was tested by a spray test in accordance with AATCC Standard Test Method 22. This test in accordance with AATCC Standard Test Method 22 is carried out by spraying distilled water onto the textile substrate to be tested under controlled conditions, and then visually comparing the image of the evaluation criteria described in the test method with the wetting pattern. Here, the given numerical values relate to the appearance of the surface after spraying water and have the following meanings: 100 = No adhesion of water droplets and no wetting on the upper surface 90 = Adhesion of water droplets and wetting on the upper surface are sometimes seen 80 = The upper surface is wet at the location where water droplets adhere 70 = The entire upper surface is partially wet 50 = The entire upper surface is completely wet 0 = The entire upper and lower surfaces are completely wet (soaked state).

[0104] To examine the durability of the finished planar structure against washing treatment, the test samples were washed at 60 °C in accordance with DIN EN ISO 6330:2013 and then dried according to drying method A or F (see Tables 3a and 3c).

[0105] To examine the abrasion resistance of the hydrophobic finish, first, the water repellency of the samples in their initial state was measured using a spray test (AATCC standard test method 22). Subsequently, the samples were rubbed by an abrasion test in accordance with DIN EN ISO 12947-2. For this purpose, each sample was clamped in a Martindale tester, and the knitted fabric was rotated 2000 times under a load of 790 kg (equivalent to a nominal pressure of 12 kPa) to rub against the sample. After friction, the hydrophobic effect of the sample was examined again by a spray test (AATCC standard test method 22) (see Table 3a).

[0106] To examine the influence of the hydrophobizing agent on the flame retardant effect of specific fibers, the test samples were tested in accordance with DIN 4102 Part1 (Building material class B2: Building materials with standard flammability) (see Table 3b). For this purpose, the textile was spread above the flame, and it was observed whether the tip of the flame reached a measurement mark at a height of 15 cm within 20 seconds (flame burning time: 15 seconds). This test was performed a total of 5 times each in the warp and weft directions of the textile.

[0107] The following commercial products were used: Borchi Kat 24: Versatile bismuth carboxylate catalyst, IMCD Deutschland GmbH RUCO-LINK XCR: Aqueous emulsion of 3,5-dimethylpyrazole-block aliphatic polyisocyanate with a solids content of 25%; 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

[0108] Production Example of Component (1) Compound (A): General Production Regulations for Compound (A) of Formula (I), (II), (III) and / or (IV) In a three-necked flask of appropriate dimensions equipped with a distillation cooler, an adjustable stirrer, and an internal thermometer, the components (a1, a2, or a3) and (b1) shown in Table 1a are melted under a protective gas and with stirring in the amounts in grams shown in the table. Then, this mixture is heated to the final temperature (T) shown in Tables 1a and 1b, and further stirred until no more reaction water distills off and the acid value (SZ) shown in Table 1a is reached. In the esterification reaction, 0.1% sulfuric acid can be added as a catalyst if necessary. In the amidation reaction, no catalyst addition is required. The resulting condensate is taken out and processed into flakes after cooling.

[0109] Compound (A): Specific Production Regulations for Compound (A) of Formula (I) and / or (II) Using Alkyl Isocyanate (b2), and Generation of Reaction Product (S) by Further Treatment In a three-necked flask of appropriate dimensions equipped with a reflux condenser, an adjustable stirrer, an internal thermometer, and a dropping funnel, the components (a1) and (b2) in the amounts in grams shown in Table 1a are introduced into isopropyl acetate (solvent (LM)). Then, 0.05% of 1,4-diazabicyclo(2,2,2)octane is added as a catalyst based on the total amount of each component, and this mixture is stirred at 80 °C until no NCO band is detected in the IR spectrum.

[0110] Then, in order to produce the reaction product (S), the component (IC) in the amount in grams shown in Table 1a is added to this mixture, and it is further stirred at 80 °C until no NCO band is detected in the IR spectrum.

[0111] Reaction Product (S) (= Component (1)): General Production Regulations for Reaction Product (S) of Compound (A) with Unblocked or Partially Blocked Di-, Tri- or Polyisocyanate (IC) In a three-necked flask of appropriate dimensions equipped with a reflux condenser, an adjustable stirrer, an internal thermometer, and a dropping funnel, the components (A) and (IC) shown in Table 1a and Table 1b are introduced into isopropyl acetate (LM) in the amounts in grams shown in the table. Then, 0.05% of 1,4-diazabicyclo(2,2,2)octane is added as a catalyst based on the total amount of each component, and this mixture is stirred at 65 °C until the NCO band is no longer detected in the IR spectrum.

[0112] Specific Production Regulations for Reaction Product (S) Used in Emulsions (E) 3 and 9 For the reaction product (S) used in the production of emulsion (E)3 according to Table 1a, during its production (the reaction of compound (A) and isocyanate (IC)), dimethylaminoethanol in the amount in grams shown in Table 1a is further added.

[0113] For the reaction product (S) used in the production of emulsion (E)9 according to Table 1a, during its production (the reaction of compound (A) and isocyanate (IC)), bisoctadecylamine in the amount in grams shown in Table 1a is further added.

[0114] Emulsion (E): General Production Regulations for Emulsion (E) Composed of Component (1) or Reaction Product (S) and Component (2) Oil phase: Charge a glass beaker of appropriate dimensions with the reaction product (S) and component (2) present in the isopropyl acetate described above in the amounts in grams shown in Table 1a, and heat to 65 - 70 °C with stirring until a clear and homogeneous solution is obtained. To obtain a homogeneous product, the reaction product (S) to be used must be melted at 65 - 70 °C before use if necessary.

[0115] Water phase: Dissolve the emulsifier (Em) (= component (5)) in the amount in grams shown in Table 1a in a specified amount of water at 65 °C in a glass beaker of appropriate dimensions.

[0116] Stir both phases with a high-speed stirrer to form a coarse pre-emulsion, and then homogenize at 65 °C with a high-pressure homogenizer at 300 - 500 bar until an average particle size of 0.1 - 10 micrometers is achieved. Then, remove the solvent (LM) by azeotropic distillation with a rotary evaporator under vacuum. If necessary, adjust the pH value of the obtained emulsion to 5 - 7 with 60% acetic acid, filter the obtained white emulsion through a 20-micrometer filter, and adjust the solid content to 25% with water.

[0117] Production Example of Component (2) Organopolysiloxane (2-1) Mix 11.1 g (0.13 mol) of the amino group-containing organopolysiloxane (I) with 49.7 g of isopropyl acetate under a nitrogen atmosphere. Dissolve 0.06 g of the Borchi catalyst in this mixture with stirring. Then, add 39.1 g (0.13 mol) of stearyl isocyanate little by little so that the exotherm can be well controlled. After the exotherm subsides, heat this reaction mixture at 80 °C for an additional 2 hours. When no isocyanate is detected (IR), cool this reaction mixture. A compound of 94.3 g that no longer contains protonatable basic nitrogen is obtained. Use this compound to produce emulsions (E) 1, 4, and 7 in Table 1a.

[0118] Amino group-containing organopolysiloxane (I):

Chemical formula

[0119] Organopolysiloxane (2-2) 12.4 g (0.13 mol) of amino group-containing organopolysiloxane (II) is mixed with 49.0 g of isopropyl acetate under a nitrogen atmosphere. 0.06 g of Borchi catalyst is dissolved in this mixture with stirring. Then, 38.5 g (0.130 mol) of stearyl isocyanate is added little by little so that the exotherm can be well controlled. After the exotherm subsides, this reaction mixture is further heated to 80 °C for 2 hours. When no isocyanate is detected (IR), this reaction mixture is cooled. 92.8 g of a compound that no longer contains protonatable basic nitrogen is obtained. Using this compound, emulsions (E) 2, 5, and 9 in Table 1a are produced.

[0120] Amino group-containing organopolysiloxane (II):

Chemical formula

[0121] Organopolysiloxane (2-3) 16.6 g (0.12 mol) of amino group-containing organopolysiloxane (III) is mixed with 52.5 g of isopropyl acetate under a nitrogen atmosphere. 0.07 g of Borchi catalyst is dissolved in this mixture with stirring. Then, 30.9 g (0.10 mol) of stearyl isocyanate is added little by little so that the exotherm can be well controlled. After the exotherm subsides, this reaction mixture is further heated to 80 °C for 2 hours. When no isocyanate is detected (IR), this reaction mixture is cooled. 96.7 g of a compound containing 0.54 wt% of protonatable basic nitrogen is obtained. Using this compound, emulsions (E) 3, 6, and 8 in Table 1a are produced.

[0122] Amino group-containing organopolysiloxane (III):

Chemical formula

[0123] Production of Preparation (Z) According to the Invention The emulsion (E) described in Table 2a containing components (1), (2) and (5) is mixed with component (3) as required and also with water as required in a predetermined weight ratio to obtain the preparation (Z) described in Table 2a.

[0124] The preparations Z19 - Z20 (not according to the present invention) described in Table 2b were produced with the emulsion of International Publication No. 2008 / 135208 (composition according to Example 5 of Table 1a) instead of the emulsion having component (2), and this is used for comparison.

[0125] Finishing process examples Application of Aqueous Preparation (Z) to Textile Sheet Structures The finishing state and test results are shown in Tables 3a, 3b and 3c.

[0126]

Table 1-1

[0127]

Table 1-2

[0128]

Table 2

[0129]

Table 3

[0130]

Table 4

[0131]

Table 5

[0132]

Table 6

[0133] The following items are the subject of the present invention: 1. At least one structural unit (i) and / or (vi): [Chemical formula] [wherein, R 6 are, independently of one another, at least one C 8~28 alkyl group, preferably a C 14~20 alkyl group, more preferably a C 16~18 alkyl group and at least one urea group, R 7 are, independently of one another, selected from -CH3, -OH, and -C 1~5 alkoxy group] An organopolysiloxane containing the same.

[0134] 2. R 6 is at least one C 8~28 alkylurea group [Chemical formula] , more preferably a C 14~20 alkylurea group, even more preferably a C 16~18 alkylurea group, the organopolysiloxane according to item 1.

[0135] 3. R 6 is [Chemical formula] [wherein, R 10 are, independently of one another, H or R 11 and, R 11 are, independently of one another, -C(O)-NH-C 8~28 alkyl, provided that R 6 contains at least one R 11 and, k is 2 to 4, preferably 2 to 3, l is 2 to 4, preferably 2 to 3, and is selected from the organopolysiloxane according to item 1 or 2.

[0136] 4. The organopolysiloxane is

Chemical formula

Chemical formula

[0137] 5. The organopolysiloxane is independently of each other

Chemical formula

[0138] 6. The molar ratio of the structural unit (i) is in the range of 25 to 100 mol%, preferably 50 to 100 mol%, and is the organopolysiloxane according to any one of items 1 to 5.

[0139] 7. The molar ratio of the structural unit (vi) is in the range of 25 to 100 mol%, preferably 50 to 100 mol%, of the organopolysiloxane according to any one of items 1 to 6.

[0140] 8. The molar ratio of the structural unit (ii) is in the range of 0 to 50 mol%, preferably 0 to 30 mol%, of the organopolysiloxane according to any one of items 1 to 7.

[0141] 9. The molar ratio of the structural unit (iii) is in the range of 0 to 40 mol%, preferably 0 to 20 mol%, of the organopolysiloxane according to any one of items 1 to 8.

[0142] 10. The molar ratio of the structural unit (iv) and / or (vii) is in the range of 0 to 20 mol%, preferably 0 to 10 mol%, of the organopolysiloxane according to any one of items 1 to 9.

[0143] 11. The molar ratio of the structural unit (v) is in the range of 0 to 50 mol%, preferably 0 to 30 mol%, of the organopolysiloxane according to any one of items 1 to 10.

[0144] 12. The total basic nitrogen content measured by titration is 0 to 3% by weight, preferably 0 to 1.5% by weight, particularly preferably 0.01 to 0.5% by weight, of the organopolysiloxane according to any one of items 1 to 11.

[0145] 13. A method for producing the organopolysiloxane according to any one of items 1 to 12, a) providing an organopolysiloxane and / or an alkoxysilane having an NCO-reactive primary and / or secondary amino group; and b) reacting the organopolysiloxane and / or alkoxysilane according to a) with a C 8~28 alkyl isocyanate; c) Optionally, hydrolyzing / condensing the alkoxysilane obtained in step b) to obtain an organopolysiloxane; A method comprising.

[0146] 14. The organopolysiloxane according to a) is obtained by equilibration in the presence of an (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group or by its hydrolysis / condensation, the method according to item 13. 1~5 A method according to item 13, obtained by equilibration in the presence of an (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group or by its hydrolysis / condensation.

[0147] 15. The (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group is of the structure 1~5 An (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group is of the structure

Chemical formula

[0148] 16. The equilibration is carried out in the presence of a catalyst and water in the presence of an organopolysiloxane containing structural units (ii), (iii), and / or (v), the method according to item 14 or 15.

[0149] 17. 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 a tertiary amine, such as 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyldipropanolamine, pentamethyldipropylenetriamine, N-methylimidazole or N-ethylmorpholine, optionally increasing the temperature, for example, at 40-140 °C, the method according to any one of items 13 to 16.

[0150] 18. An organopolysiloxane obtainable by the method according to any one of items 13 to 17.

[0151] A preparation comprising: (1) Formula (I) [Chemical formula] and / or Formula (II) [Chemical formula] and / or Formula (III) [Chemical formula] and / or Formula (IV) [Chemical formula] [wherein, R 1 = -X-Y-Z or -Z, where [Chemical formula] and R 3 = -X-Y-Z, -Z or -Y-Z, provided that when it means -Y-Z, the group R 2 is replaced by replacing n with n'' in R 4 = -X-Y-Z or -(CH2) n’ H and B 1 = -V-W-Z or -Z, where [Chemical formula] and [Chemical formula] and [Chemical formula] and [Chemical formula] and Q=-(CH2) n’’ - and R s are, independently of one another, -OH, -YZ, [Chemical formula] wherein, however, at least one group R in formula (III) s is assumed to be an OH group, n, n’, n’’, n’’’ and m are each independently an integer, where n = 0 to 2, n’ = 0 to 4, n’’ = 1 to 4, n’’’ = 0 to 4, and m = 8 to 30, preferably 12 to 26, more preferably 14 to 22] at least one compound (A) is reacted with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC) to obtain at least one reaction product (S), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is 1.8 to 10 per mole, reaction product (S), (2) at least one organopolysiloxane according to any one of items 1 to 12 or item 18, (3) optionally, at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), (4) optionally, at least one liquid medium, in particular water or an organic solvent, (5) optionally, at least one emulsifier and a preparation.

[0152] 20. Component (1) accounts for 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 25 to 65% by weight, based on the total weight of components (1) and (2), of the preparation according to item 19.

[0153] 21. The preparation according to item 19 or 20, wherein the component (2) accounts for 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight based on the total weight of the components (1) and (2).

[0154] 22. The preparation according to any one of items 19 to 21, wherein the component (3) accounts for 0 to 50% by weight, preferably 1 to 35% by weight, more preferably 5 to 35% by weight based on the total weight of the components (1), (2) and (3).

[0155] 23. The preparation according to any one of items 19 to 22, wherein the component (5) accounts for 0 to 25% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight based on the total weight of the components (1), (2), optionally (3) and (5).

[0156] 24. The preparation according to any one of items 19 to 23, which is in the form of a dispersion, preferably in the form of an aqueous dispersion.

[0157] 25. The preparation according to any one of items 19 to 24, wherein the solid content of the dispersion is 10 to 40% by weight, preferably 15 to 30% by weight.

[0158] 26. The preparation according to any one of items 19 to 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 (polymeric MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, and mixtures, for example, a mixture of MDI and polymeric MDI, and derivatives thereof.

[0159] 27. For the reaction product (S), the molar ratio of the free isocyanate (NCO) groups in the polyisocyanate (IC) to the isocyanate-reactive groups in the compound (A) is adjusted to 1:1 to 1:1.3, preferably 1 to 1.1, the preparation (Z) according to any one of items 19 to 26.

[0160] 28. The isocyanate-reactive groups are hydroxy groups, primary and / or secondary amino groups, the preparation (Z) according to item 27.

[0161] 29. The organic solvent by the component (4) is selected from esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate or amyl acetate, ketones such as acetone, methyl ethyl ketone and saturated hydrocarbons such as n-hexane, n-heptane or n-octane, the preparation (Z) according to any one of items 19 to 28.

[0162] 30. The emulsifier by the component (5) is selected from anionic, cationic and nonionic surfactants, the preparation (Z) according to any one of items 19 to 29.

[0163] 31. The preparation does not contain a fluorine compound, the preparation according to any one of items 19 to 30.

[0164] 32. Use of the organopolysiloxane according to any one of items 1 to 12 or item 18, or the preparation according to any one of items 19 to 31 as a hydrophobizing agent.

[0165] 33. Use according to item 32 as a hydrophobizing agent in a planar structure, in particular a textile substrate, paper, leather and a mineral-based planar structure.

[0166] 34. Use according to item 33 as an additive in a paint, lacquer or plaster.

[0167] 35. A method for hydrophobizing a substrate, comprising applying to the substrate, preferably a planar structure, more preferably a textile substrate, paper, leather or a mineral-based substrate, the preparation Z according to any one of items 19 to 31, or the organopolysiloxane according to any one of items 1 to 12 or item 18.

[0168] 36. The method according to item 35, wherein the application is carried out by spraying, dipping, impregnating, brushing or by sponge coating.

[0169] 37. The method according to item 35 or 36, wherein the preparation is applied to the textile substrate by forced application or the draw-down method.

Claims

1. A preparation, wherein the preparation is (1) Formula (I) 【Chemical Formula 1】 and / or Formula (II) 【Chemical Formula 2】 and / or Formula (III) 【Chemical Formula 3】 and / or Formula (IV) 【Chemical Formula 4】 [wherein, R １ = -X - Y - Z or -Z, where 【Chemical Formula 5】 and R ３ = -X - Y - Z, -Z or -Y - Z, provided that when it means -Y - Z, the group R ２ replaces n with n'' in R ４ = -X - Y - Z or -(CH ２ ) ｎ’ H and B １ = -V - W - Z or -Z, where 【Chemical Formula 6】 and 【Chemical Formula 7】 and 【Chemical Formula 8】 and 【Chemical Formula 9】 and Q = -(CH ２ ) ｎ’’ - and R ｓ are, independently of each other, -OH, -YZ, 【Chemical Formula 10】 provided that at least one group R ｓ in Formula (III) is an OH group n, n', n'', n''', and m are each independently an integer, where n = 0 to 2, n' = 0 to 4, n'' = 1 to 4, n''' = 0 to 4, and m = 8 to 30], at least one compound (A) is reacted with at least one unblocked or at least partially blocked di-, tri-, or polyisocyanate (IC), and at least one reaction product (S) obtained thereby, where the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is 1.8 to 10 per mole, and the preparation is free of fluorine compounds, reaction product (S), and (2) at least one structural unit (i) and / or (vi): [Chemical Formula 11] [In the formula, R ６ are each independently at least one C ８～２８ alkyl group and at least one urea group, R ７ are each independently -CH ３ , -OH, and -C １～５ alkoxy group selected from] including at least one organopolysiloxane, (3) optionally, at least one unblocked or at least partially blocked di-, tri-, or polyisocyanate (IC), (4) optionally, at least one liquid medium, (5) optionally, at least one emulsifier and a preparation containing.

2. The R of the organopolysiloxane ６ is at least one C ８～２８ alkylurea group [Chemical Formula 12] The preparation according to claim 1, comprising

3. The organopolysiloxane is 【Chemical Formula 13】 [wherein R ５ is, independently of one another, C ８～２８ an alkyl group, R ８ is, independently of one another, 【Chemical Formula 14】 selected from R ７ is as defined above, k is 2 to 4 or 2 to 3, l is 2 to 4 or 2 to 3], and further comprises at least one structural unit selected from the preparation according to claim 1 or 2.

4. The molar ratio of the structural unit (i) is in the range of 25 to 100 mol%, and / or the molar ratio of the structural unit (vi) is in the range of 25 to 100 mol%, and / or the molar ratio of the structural unit (ii) is in the range of 0 to 50 mol%, and / or the molar ratio of the structural unit (iii) is in the range of 0 to 40 mol%, and / or the molar ratio of the structural unit (iv) and / or (vii) is in the range of 0 to 20 mol%, and / or the molar ratio of the structural unit (v) is in the range of 0 to 50 mol%. The preparation according to claim 3.

5. A method for producing the preparation according to any one of claims 1 to 4, a) providing an organopolysiloxane and / or an alkoxysilane having an NCO-reactive primary and / or secondary amino group; b) reacting the organopolysiloxane and / or alkoxysilane according to a) with a C ８～２８ alkyl isocyanate; c) Optionally, hydrolyzing / condensing the alkoxysilane obtained in step b) to obtain an organopolysiloxane; The method for producing the organopolysiloxane comprising The method for producing a preparation comprising

6. The organopolysiloxane according to a) is obtained by equilibration in the presence of an (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group, or by its hydrolysis / condensation, and the (alkoxy)silane having at least one NCO-reactive primary and / or secondary amino group has the structure １～５ [wherein, １～５ R and R are as defined above], and the method according to claim 5. 【Chemical Formula 15】 [wherein, R ７ and R ８ are as defined above], and the method according to claim 5.

7. Component (1) accounts for 10 to 90% by weight based on the total weight of components (1) and (2), or component (2) accounts for 10 to 90% by weight based on the total weight of components (1) and (2), or component (3) accounts for 0 to 50% by weight based on the total weight of components (1), (2) and (3), or the said component (5) accounts for 0 to 25% by weight based on the total weight of components (1), (2), optionally (3) and (5), and the preparation according to any one of claims 1 to 4.

8. The preparation according to any one of claims 1 to 4 and 7, which is in the form of a dispersion, and the solid content of the dispersion is 10 to 40% by weight.

9. 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 (polymeric MDI), 4-methylcyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, and mixtures thereof, and the preparation according to any one of claims 1 to 4, 7 and 8.

10. For the reaction product (S), the molar ratio of the free isocyanate (NCO) groups in the polyisocyanate (IC) to the isocyanate-reactive groups in the compound (A) is adjusted to 1:1 to 1:1.3, and the isocyanate-reactive groups are hydroxy groups, primary and / or secondary amino groups, and the preparation according to any one of claims 1 to 4, 7 to 9.

11. Use of the preparation according to any one of claims 1 to 4, 7 to 10 as a hydrophobizing agent for planar structures or as an additive in paints, lacquers or plasters.

12. A method for hydrophobizing a substrate without using a fluorocarbon polymer, which comprises applying to the substrate the preparation according to any one of claims 1 to 4, 7 to 10.

13. The method according to claim 12, wherein the application is carried out by spraying, dipping, impregnating, brushing or sponge coating.

14. The method according to claim 12 or 13, wherein the preparation is applied to a textile substrate by forced application or extraction method.

15. The preparation according to any one of claims 1 to 4, 7 to 10, wherein the organopolysiloxane is fluorine-free and functions as a hydrophobizing agent for a textile substrate.

16. At least one C of the organopolysiloxane ８～２８ alkyl group is a C １４～２０ alkyl group or a C １６～１８ alkyl group, the preparation according to any one of claims 1 to 4, 7 to 10.

17. At least one C of the organopolysiloxane ８～２８ alkylurea group is a C １４～２０ alkylurea group or a C １６～１８ alkylurea group, the preparation according to claim 2.

18. R of the organopolysiloxane ６ is 【Chemical Formula 16】 [In the formula, R １０ are, independently of one another, H or R １１ and R １１ are, independently of one another, -C(O)-NH-C ８～２８ alkyl, provided that R ６ contains at least one R １１ and k is 2 to 4 or 2 to 3, l is 2 to 4 or 2 to 3], the preparation according to claim 2.

19. The method according to claim 12, wherein the hydrophobizing agent is fluorine-free, the substrate is a textile substrate, and the hydrophobization of the substrate does not contain a fluorocarbon polymer.

20. The preparation according to claim 1, wherein the at least one liquid medium in (4) is water or an organic solvent.

21. The preparation according to claim 8, wherein the solid content of the dispersion is 15 to 30% by weight.

22. The preparation according to claim 10, wherein for the reaction product (S), the molar ratio of the free isocyanate (NCO) groups in the polyisocyanate (IC) to the isocyanate-reactive groups in the compound (A) is adjusted to 1:1.1.

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