Permanent effect hydrophobizing agents

Abstract

The present invention relates to organopolysiloxanes comprising at least one structural unit having at least one C 8‑28 alkyl group and at least one urea group, to a process for the preparation of said organopolysiloxanes, to formulations comprising said organopolysiloxanes, and to the use thereof as hydrophobizing agents.

Description

[0001] The present invention relates to comprising at least one having at least one C 8-28 An organopolysiloxane comprising an alkyl group and at least one urea group as structural units, a method for preparing said organopolysiloxane, an formulation comprising said organopolysiloxane, and its use as a hydrophobic agent.

[0002] Water-based or solvent-based formulations made from silicone oils, paraffins, fluorocarbon polymers, and other additives are typically used to hydrophobize or oleophobize planar structures in order to maintain their resistance to stress from rain and splashing water during use of the planar structure.

[0003] While products based on paraffin and silicone only produce hydrophobicity when creating a water-repellent effect, fluorocarbon polymers (FC polymers) also cause the repulsion of dirt and oil.

[0004] Although FC polymers generally exhibit good overall performance, their hydrophobic and oleophobic properties are significantly reduced after washing due to the loss of orientation of active fluorocarbon residues in the polymer molecules, unless reoriented through heat treatment. This means that planar structures, especially textiles, must undergo heat treatment after washing to reactivate the desired effects. This heat treatment is referred to below as "reactivation."

[0005] Furthermore, fluorocarbon polymer-based formulations—due, among other things, to their energy-intensive preparation—are expensive and are also suspected of being ecotoxicous and toxic to humans, making their application, especially in the apparel sector, increasingly perceived as dangerous. Therefore, there is a search for alternative fluorine-free products with similar performance characteristics, where good initial hydrophobicity and the resistance of the topcoat to repeated washing are important quality features.

[0006] In EP 3 733 809 A1, formulations based on amino-modified silicones, organopolysiloxanes with three-dimensional structures, and alkyl polysiloxanes are used to achieve water-repellent effects on textile materials.

[0007] WO 2018 / 110667 describes compositions for hydrophobicating substrates, the compositions comprising polymers composed of nonfluorinated (meth)acrylate residues and silicone macromonomers.

[0008] As known from WO 2008 / 135208, based on hydrophobic reaction products and containing C8-C... 28 Fluorocarbon-free formulations of alkyl organopolysiloxanes.

[0009] WO 2015 / 191326 discloses formulations for hydrophobizing a substrate, which include, in addition to waxes, carbamate-based compounds. The waxes may be, for example, natural or synthetic waxes or mixtures thereof.

[0010] These agents can achieve good water-repellent effects; however, they usually require relatively large amounts, which reduces the air permeability of the finished textiles. Furthermore, similar to the case of textiles treated with fluorocarbon-containing agents, heat treatment (reactivation) is performed after washing, for example in a washer-dryer or by ironing, to restore the original performance level.

[0011] Therefore, the object of this invention is to provide compounds and formulations that can achieve good and permanent hydrophobic effects at small amounts without the need for reactivation (LAD effect, “Laundry / Air Dry”, M. Rasch et al., Mellin and Textilberichte 6 / 2005, pp. 456-459).

[0012] Surprisingly, this objective can be achieved by an organopolysiloxane comprising 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 formulations of the present invention comprising the organopolysiloxane according to the invention. Even small amounts of the organopolysiloxane of the present invention have already facilitated significant hydrophobicity on the substrate. The formulations of the present invention also promote excellent adhesion to the substrate, such that the level of effect hardly changes over time (the effect is permanent) and is maintained even in applications such as grinding, washing, etc.

[0013] Furthermore, it has been unexpectedly shown that the effect level can remain unchanged even without reactivation measures (LAD effect).

[0014] Furthermore, it has been shown that even after the application of the compounds or formulations of the present invention, less flammable fibers such as Trevira CS and especially the textiles prepared therein do not suffer a loss in their flame retardancy, although generally the fire resistance deteriorates due to the application of hydrophobic agents without FC.

[0015] In one aspect, the present invention relates to organopolysiloxanes comprising at least structural units (i) and / or (vi):

[0016]

[0017] in

[0018] R 6 Each contains at least one C independently 8-28 Alkyl, preferably C 14-20Alkyl, more preferably C 16-18 Alkyl group and at least one urea group, and

[0019] R 7 They are independently selected from -CH3, -OH and -C. 1-5 Alkyl group, preferably -CH3.

[0020] R 6 Preferably, it contains at least one C according to the following formula 8-28 Alkyl urea:

[0021]

[0022] R 6 More preferably, it contains at least one C 14-20 Alkyl urea, still more preferably C 16-18 Alkyl urea group.

[0023] In a preferred embodiment, R 6 It is a formula selected from the following items

[0024] and

[0025]

[0026] in

[0027] R 10 H or R are independent of each other. 11 ,

[0028] R 11 They are independently -C(O)-NH-C 8-28 -alkyl, more preferably -C(O)-NH-C 14-20 Alkyl groups, preferably -C(O)-NH-C 16-18 alkyl,

[0029] The prerequisite is that R 6 Contains at least one R 11 ,

[0030] k is 2-4, preferably 2-3, and

[0031] l is 2-4, preferably 2-3.

[0032] In addition, the organopolysiloxane according to the present invention further comprises at least one structural unit selected from the following:

[0033] and

[0034] ,in

[0035] R 5Each contains C independently 8-28 Alkyl, preferably C 14-20 Alkyl, more preferably C 16-18 alkyl,

[0036] R 8 Selected independently from each other

[0037]

[0038] and

[0039] R 6 and R 7 k and l are defined as above.

[0040] The organopolysiloxanes preferably have the following terminal groups independently of each other:

[0041] or

[0042] in

[0043] R 5 R 6 R 7 and R 8 As defined above.

[0044] In a preferred embodiment, the molar percentage of structural unit (i) in the organopolysiloxane is in the range of 25-100 mol%, more preferably 50-100 mol%, provided that the total number of all structural units in the organopolysiloxane is 100 mol.

[0045] In addition, the molar percentage of the structural unit (vi) is preferably in the range of 25-100 mol%, more preferably 50-100 mol%.

[0046] In another embodiment, the molar percentage of structural unit (ii) in the organopolysiloxane is in the range of 0-50 mol%, more preferably 0-30 mol%.

[0047] The molar percentage of structural unit (iii) can be in the range of 0-40 mol%, preferably 0-20 mol%, in the organopolysiloxane.

[0048] The molar percentage of structural units (iv) and / or (vii) is preferably in the range of 0-20 mol%, more preferably 0-10 mol%.

[0049] In one embodiment, the molar percentage of the structural unit (v) is in the range of 0-50 mol%, preferably 0-30 mol%.

[0050] The organopolysiloxane according to the invention preferably has a (protonable) basic total nitrogen content of 0-3% by weight, preferably 0-1.5% by weight, and still more preferably 0.01-0.05% by weight. Titration methods for determining the basic nitrogen content are known to those skilled in the art.

[0051] In another aspect, the present invention relates to a method for preparing an organopolysiloxane according to the present invention, the method comprising the following steps:

[0052] a) Provide organopolysiloxanes and / or alkoxysilanes having primary and / or secondary amine groups with NCO reactivity.

[0053] b) Reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 Alkyl isocyanate reaction; and

[0054] c) Optionally, the alkoxysilane obtained in step b) is hydrolyzed / condensed to synthesize the organopolysiloxane.

[0055] This invention particularly relates to a method for preparing organopolysiloxanes, the method comprising the following steps:

[0056] a') Provides organopolysiloxanes with primary and / or secondary amine groups that are reactive with NCO.

[0057] b') Make the organopolysiloxane according to a') with C 8-28 Alkyl isocyanate, preferably C 14-20 Alkyl isocyanate, more preferably C 16-18 Alkyl isocyanate reaction.

[0058] Alternatively or supplementally, the method may include:

[0059] a") provides alkoxysilanes with primary and / or secondary amine groups that are reactive with NCO.

[0060] b") makes the alkoxysilane according to a") react with C 8-28 Alkyl isocyanate reaction, and

[0061] c") hydrolyzes / condenses the alkoxysilane obtained in step b") to synthesize the organopolysiloxane.

[0062] It can be achieved by using (C) groups having at least one primary and / or secondary amine group with NCO reactivity. 1-5The organopolysiloxane according to a') is obtained by equilibration in the presence of an alkoxysilane. The equilibration reaction is preferably base-catalyzed and is illustrated, for example, in EP 1 136 513 B1, Example 1. In the equilibration reaction, the organosiloxane or organopolysiloxane can be used as reactants with an alkoxysilane having at least one primary and / or secondary amino group. Preferably, the equilibration is carried out in the presence of organopolysiloxanes containing structural units (ii), (iii), and / or (v), and more preferably in the presence of a metal hydroxide and water.

[0063] Alternatively, organopolysiloxanes can be obtained by hydrolysis and condensation of alkoxysilanes having at least one NCO-reactive primary and / or secondary amine group. The hydrolysis reaction may also involve the presence of alkoxysilanes that result in structural units (ii), (iii), and / or (v). To shift the equilibrium towards the product side during hydrolysis, the resulting alcohol may be distilled off under pressure, if appropriate.

[0064] In the method according to the invention, the alkoxysilane in step a'') is preferably a (C) alkoxysilane having at least one primary and / or secondary amine group with NCO reactivity. 1-5 Alkoxysilanes, more preferably selected from the following:

[0065] and / or

[0066] Where R 7 and R 8 As defined above.

[0067] In straight chain or branched chain C 8-28 The reaction between the alkyl isocyanate and the NCO-reactive primary and / or secondary amine groups according to steps b') and b'') is preferably carried out as follows, such that the alkyl isocyanate is added to the amino group under stirring. Here, the reaction is also carried out 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, etc. To accelerate the reaction, the reaction mixture can be heated to 40-140°C where appropriate. Catalysts particularly considered are di-n-butyltin laurylate, tin(II) octanoate, dibutyltin diacetate, potassium octanoate, zinc dilaurate, bismuth trilaurate, or tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyl dipropanolamine, pentamethyldipropylenetriamine, N-methylimidazolium, or N-ethylmorpholine.

[0068] C 8-28The molar ratio between the alkyl isocyanate and the NCO-reactive primary or secondary amine group is preferably selected such that 50-100 mol%, preferably 80-100 mol%, and particularly preferably 90-100 mol%, of the amino group is C 8-28 The NCO groups of alkyl isocyanates react away. Therefore, even under non-stoichiometric reaction conditions, protonable amino groups still exist in organopolysiloxanes. The content of protonable basic nitrogen is between 0 and 3% by weight (see above).

[0069] Step c") is preferably carried out in the presence of a catalyst (preferably KOH or NaOH) at an elevated temperature (e.g., 40-140°C) when appropriate.

[0070] In step c"), the alkoxysilane obtained according to step b") is hydrolyzed and subsequently condensed. Alkoxysilanes leading to structural units (ii), (iii), and / or (v) may also be present during the hydrolysis reaction. To shift the equilibrium towards the product side during hydrolysis, the resulting alcohol may be distilled off / concentrated under pressure, if appropriate.

[0071] In another aspect, the present invention relates to organopolysiloxanes that can be obtained according to the method of the present invention.

[0072] In another aspect, the present invention relates to formulations comprising:

[0073] (1) At least one reaction product (S), said reaction product being capable of reacting with at least one compound (A) of the following formula.

[0074] Formula (I)

[0075] and / or formula (II) ,

[0076] and / or formula (III)

[0077] And / or form (IV)

[0078] Where R 1 =-XYZ or -Z, where

[0079] X = -(CH2) n" -,

[0080] Y= or

[0081] Z = -(CH2) m -CH3,

[0082] R 2 = ,

[0083] R 3 = -XYZ, -Z, or -YZ, provided that residue R is represented as -YZ. 2 In the text, n is replaced by n"

[0084] R 4 = -XYZ or -(CH2) n' H,

[0085] B 1 = -VWZ or -Z,

[0086] in

[0087] V = or ,

[0088] W =

[0089] or ,

[0090] B 2 = -(CH2) n" -NH2 or ,

[0091] B 3 = -VWZ, -Z or ,

[0092] B 4 = -VWZ or ,

[0093] Q = -(CH2) n" -,

[0094] R S They are independent of each other as -OH, -YZ,

[0095] or

[0096] ,

[0097] The prerequisite is that at least one residue R in equation (III) S It is an OH group, and

[0098] n, n', n", n''', and m are all independent integers, where

[0099] n = 0-2,

[0100] n' = 0-4,

[0101] n" = 1-4,

[0102] n''' = 0-4 and

[0103] m = 8-30, preferably 12-26, especially preferably 14-22.

[0104] It is obtained by reaction 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.

[0105] (2) At least one organopolysiloxane according to the present invention,

[0106] (3) Optionally at least one unblocked or at least partially blocked di, tri, or polyisocyanate (IC).

[0107] (4) Optionally at least one liquid medium, particularly water or an organic solvent, and

[0108] (5) Optionally at least one emulsifier.

[0109] The formulations according to the present invention are preferably free of fluorine compounds.

[0110] The formulation is preferably in the form of a dispersion, more preferably in the form of an aqueous dispersion, wherein the solid content of the dispersion is preferably 10-40% by weight, more preferably 15-30% by weight.

[0111] The reaction product (S) is preferably hydrophobic. In the context of this invention, the term "hydrophobic" defines a compound that is typically substantially insoluble in water at 20°C. A saturated solution of a "hydrophobic" reaction product (S) preferably contains at most 1 g of dissolved compound per liter of water (20°C), more preferably at most 0.5 g / L, and still more preferably at most 0.2 g / L.

[0112] The reaction product (S) can be obtained by reacting at least one compound (A) with at least one unblocked or at least partially blocked di, tri, or polyisocyanate (IC).

[0113] Compound (A) of formula (I) is preferably obtained by reacting a polyol (a1) with a carboxylic acid (b1) or with an alkyl isocyanate (b2). Preferred examples of the polyol (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.

[0114] Compound (A) of formula (II) is preferably obtained by reacting an alkanolamine (a2) and / or an alkylamine (a3) ​​with a carboxylic acid (b1) or with 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'-tetratetra(2-hydroxypropyl)ethylenediamine, aminoethylethanolamine, aminopropylethanolamine, alkyltri(hydroxyethyl)propylenediamine, and alkyl dihydroxyethylamine having preferably 12-24 carbon atoms in the alkyl residue, and their ethoxylated products. Particularly preferred are diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, aminoethylethanolamine, and aminopropylethanolamine, more preferably triethanolamine.

[0115] Examples of alkylamines (a3) ​​are bis(aminoethyl)amine, bis(aminopropyl)amine and their polymeric homologues, aminoethyliminopropylamine, bis(aminopropyl)ethylenediamine, tri(aminoethyl)amine, tri(aminopropyl)amine, triaminononane, aminopropylstearylamine, and aminopropyldistearatelamine. Bis(aminoethyl)amine, bis(aminopropyl)amine, aminoethylaminopropylamine, bis(aminopropyl)ethylenediamine, and aminopropylstearylamine are preferred herein, especially bis(aminoethyl)amine.

[0116] The carboxylic acid (b1) used to prepare compound (A) can be saturated, unsaturated, unbranched, or branched, and preferably has 10-32 carbon atoms, more preferably 12-24 carbon atoms. Unbranched saturated carboxylic acids having preferably 10-32 carbon atoms, more preferably 12-24 carbon atoms, such as decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid are preferred here. Lauric acid, palmitic acid, stearic acid, and behenic acid are preferred in this context.

[0117] The alkyl isocyanate (b2) used to prepare formulas (I) and (II) is preferably unbranched, wherein the alkyl residues preferably have 9-31, especially 11-23, carbon atoms. A particularly preferred alkyl isocyanate is stearyl isocyanate.

[0118] Instead of using a compound (A) prepared with a polyol (a1) or an alkanolamine (a2) or an alkylamine (a3) ​​and a carboxylic acid (b1) or an alkyl isocyanate (b2), a compound having an active hydrogen atom and two hydrophobic residues (e.g., Guerbert alcohol), bis(dodecyl)amine, and preferably bis(octadecyl)amine, may also be used.

[0119] The compound of formula (III) is obtained by reacting sorbitol with C 10 -C 32 Carboxylic acid, preferred and C14 -C 28 Carboxylic acids, particularly preferred and C 16 -C 24 Sorbitol esters are obtained by the reaction of carboxylic acids under hydrolysis conditions. Monoesters, diesters, or triesters, and mixtures thereof, can be produced depending on the stoichiometry. Alkoxylated derivatives may also be used where appropriate. For reactions with unblocked or at least partially blocked di, tri, or polyisocyanates (ICs), it is essential that at least one reactive OH group is present in the sorbitol ester. Additionally, 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 preferred with C 16 -C 24 Alkyl isocyanate reaction to achieve compound of formula (III).

[0120] The compound of formula (IV) is formed by the reaction of citric acid with a long-chain C 10 -C 32 Alcohols, preferred and C 14 -C 28 Alcohols, especially preferred and C 16 -C 24 Alkyl citrate esters obtained by esterification of alcohols.

[0121] A hydrophobic reaction product (S) is produced by reacting at least one compound (A) 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. Examples of unblocked or at least partially blocked isocyanates are described in paragraphs

[0032] -

[0037] of DE 100 17651 A1.

[0122] Particularly preferred unblocked di, tri, or polyisocyanates (ICs) include, for example, 2,4-tolyl 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 trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanates, mixtures thereof, such as mixtures of MDI and polymer MDI, and derivatives thereof. Dimeric diisocyanate is available under the name DDI 1410 from CognisCorp., Inc., 300 Brookside Avenue, Ambier, PA 19002, USA.

[0123] Derivatives of isocyanates (IC) include, for example, cyclized oligomeric or polyisocyanates. The preparation of cyclized oligomeric or polyisocyanates can be carried out according to cyclization methods known from W. Siefken (Liebigs Annalen der Chemie 562, 1949, pp. 75-136), wherein the oligomeric or polyisocyanate can exist in open-chain or cyclic form. Such derivatives can be prepared from the aforementioned di, tri, and polyisocyanates by means of a combination of urethane, urea, urea, biuret, urea diketone, amide, isocyanurate, carbodiimide, urea ketone imide, oxadiazine trione, or iminooxadiazine dione structures. Hexadecimalide diisocyanate trimers, diphenylmethane diisocyanate trimers, and urethanes formed from 2,4-tolyl diisocyanate, still possessing free NCO groups, are preferred.

[0124] Alternatively, with the aid of a corresponding catalyst system, a portion of the isocyanate groups can be derived from polyalkoxy monoalkyl ethers into urethane to improve the emulsifability of component (1) in water. Polyethylene glycol monomethyl ethers having preferably 4-20 ethylene oxide units and optionally additionally 2-6 propylene oxide units can be used here. Catalysts known to those skilled in the art can be tertiary amine-based and / or organotin compounds (e.g., dibutyltin dilaurate, dioctyltin dilaurate, or tin diacetate).

[0125] Preferred derivatives are hexamethylene diisocyanate trimers, diphenylmethane diisocyanate trimers, urethanes formed from 2,4-tolyl diisocyanates having free NCO groups, and di, tri, or polyisocyanates (ICs) modified with polyalkoxy monoalkyl ethers, especially di, tri, or polyisocyanates modified with polyethylene oxide monoalkyl ethers.

[0126] Instead of isocyanates modified with polyalkoxy monoalkyl ethers, tertiary alkanolamines can be used as additives to improve the cationic charge of the reaction product (S) and thereby improve the self-emulsifying properties without affecting the overall performance. Dimethylaminoethanol is particularly suitable here.

[0127] Isocyanates (IC) can also be partially or completely blocked (see, for example, paragraph

[0042] of DE 100 17 651 A1). Preferred protecting agents are sodium bisulfite, methyl ethyl ketoxime, 3,5-dimethylpyrazole, N-tert-butylbenzylamine, especially 3,5-dimethylpyrazole.

[0128] Protection can be achieved by using di, tri, or polyisocyanates (IC) with a protective agent in the melt or in an organic solvent (LM) inert to isocyanates, preferably in a protective atmosphere in the presence of a suitable catalyst, as described in, for example, EP 0 159117 B1 or DE 4441 418 A1.

[0129] The molar ratio of the free NCO groups of the di, tri, or polyisocyanate (IC) to be blocked to the reactive groups of the protecting agent is preferably an excess of at most 2:1, and more preferably at most 3:1.

[0130] To prepare the reaction product (S), the molar ratio of the free isocyanate (NCO) group in the polyisocyanate (IC) to the isocyanate-reactive group in the compound (A) is set to 1.1 to 1:1.3, preferably 1 to 1.1. The isocyanate-reactive group in the compound (A) is preferably hydroxyl, primary and / or secondary amino groups.

[0131] In a preferred embodiment, the formulation comprises 10-90% by weight, more preferably 20-80% by weight, and still more preferably 25-65% by weight of component (1) relative to the total mass of components (1) and (2).

[0132] The organopolysiloxane (2) of the present invention, as detailed above, is used as component (2).

[0133] In one embodiment, component (2) accounts for 10-90% by weight, preferably 20-80% by weight, and more preferably 30-70% by weight, relative to the total mass of components (1) and (2).

[0134] The addition of component (3) to the formulation (Z) of the present invention is optional. Unblocked di, tri, or polyisocyanates (ICs) suitable for use in component (3) have already been described in component (1) when preparing the reaction product (S) above. This type of compound is called an accelerator and they contribute to the improvement of hydrophobicity on the treated planar structure. At the same time, due to the polyfunctionality of polyisocyanates, crosslinking with the -OH, -COOH, or -NH2 groups that are always present on most substrates and the unreacted functional groups of component (1) is facilitated, thereby significantly improving tolerance to the washing process and increasing resistance to abrasion.

[0135] Component (3) can be used in both unprotected and protected forms. The unprotected form of component (3) is mainly used in the case of using nonpolar media, because this avoids the unwanted premature reaction between the free NCO groups and the reactive active hydrogen atoms of the applied medium.

[0136] If component (3) is to be applied from the application medium to a planar structure with NCO reactive groups, it is generally necessary to protect it by blocking it with a suitable blocking agent. In this case, component (3) is prepared by completely blocking the di-, tri-, or polyisocyanate with a blocking agent and, where appropriate, by using an organic solvent. To achieve complete blocking, a small amount of blocking agent in excess is generally used. If a product is to be prepared for aqueous applications, the blocked di-, tri-, or polyisocyanate must be transferred to an organic solvent in emulsion form, where necessary, using a suitable emulsifier (= component (5)).

[0137] Examples of suitable common and known protective agents are known from paragraph 0042 of DE-A-100 17 651 A1 and have been described in the description of the preparation of the reaction product (S) in component (1).

[0138] In one particular embodiment, an unblocked di, tri, or polyisocyanate can be used as an accelerator. Its self-emulsifying ability in water is improved by the partial reaction of the isocyanate group with a polyalkoxy monoalkyl ether in the presence of a corresponding catalyst system to form a urethane. By incorporating a hydrophobic side chain into the di, tri, or polyisocyanate, the HLB value of the urethane thus prepared is advantageously altered, allowing the water-insoluble compound to acquire self-emulsifying properties. In the case of hydrophobic side chains, certain choices regarding the type and amount of residues are advantageous. Preferably, between 4 and 20 ethylene oxide residues are used, optionally together with 2-6 propylene oxide residues, wherein these residues may also exist in block form within the alkoxy chain. However, such mixed alkoxylated side chains always have a larger proportion of ethylene oxide than propylene oxide. Catalysts for the synthesis of urethanes can be based on tertiary amines and / or organotin compounds (e.g., dibutyltin dilaurate, dioctyltin dilaurate, or diacetic acid tin dilaurate) known to those skilled in the art.

[0139] When used, the carbamates prepared in this way spontaneously form a fine-particle emulsion with high shear stability and good compatibility with other components of the applied solution upon introduction into water. Due to the reactivity of residual unreacted NCO groups with water, the effective time in these special forms can only be achieved for a maximum of 8 hours in the applied solution.

[0140] Component (3) is added, especially when the washability of the treated planar structure is required to be particularly high.

[0141] Relative to the total mass of components (1), (2) and (3), component (3) preferably accounts for 0-50% by weight, more preferably 1-35% by weight, and even more preferably 5-35% by weight. Component (3) can also be used directly from a solvent-containing, anhydrous medium and without formulation aids.

[0142] Preferably, 5-35% of component (3) is used directly from a solvent-containing, anhydrous medium and without formulation aids. If applied from an aqueous medium, an emulsion of component (3) having a solids content of 15-35% by weight is preferred, which is prepared using an emulsifier (= component (5)) based on ethoxylated fatty amines, optionally in quaternary ammonium form, and other emulsifying aids (e.g., cosolvents based on ethylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether, or n-methylpyrrolidone). This emulsification can be carried out with the aid of a high-pressure homogenizer.

[0143] Component (4) is optional. The liquid medium is preferably water or an organic solvent. Inert solvents are preferred as suitable organic 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.

[0144] The formulation (Z) of the present invention may also contain at least one emulsifier. Component (5) should be used particularly when the formulation is in the form of a suspension, especially a dispersion or emulsion. Surfactants ensure the most uniform distribution of each phase, especially the oil phase, in the aqueous phase. Nonionic, cationic, or anionic surfactants are used as emulsifiers in particular. Preferred nonionic, cationic, or anionic emulsifiers are ethoxylated products of fatty acids, fatty acid amides, fatty alcohols, and fatty amines, which may also be in the form of their salts with low-molecular-weight organic acids or mineral acids, and quaternary ammonium compounds (e.g., cetylbenzyl dimethyl ammonium chloride, and preferably ethoxylated octadecyl ammonium chloride). Such emulsifiers are described, for example, in "Römpp LexikonChemie," 10th edition, Vol. 2, pp. 1149-1150.

[0145] When appropriate, at least one acid is used to set the pH of the preparation to a pH of 3-8, said acid being selected, for example, organic acids such as acetic acid, citric acid, or lactic acid, or mineral acids, or inorganic acids such as hydrochloric acid.

[0146] Component (5) may be added separately or introduced into the formulation together with components (1), (2) and optionally (3) and optionally (4). Preferably, when using component (5), each component (1), (2) and optionally (3) is prepared as a solution or suspension, such as a dispersion or emulsion, more preferably an emulsion, and more preferably an oil-in-water emulsion, and then formulated into the formulation of the present invention.

[0147] The usual amount of component (5) relative to the total amount of components (1), (2), optionally (3) and (5) is preferably 0-25% by weight, preferably 1-20% by weight, and more preferably 2-15% by weight.

[0148] Emulsions are prepared using known methods for forming secondary emulsions. The emulsification temperature is typically above the melting range of the active substances used in components (1), (2), and optionally (3), preferably between 50 and 80°C. To produce a particularly stable emulsion with the finest possible particles, a coarse-particle pre-emulsion is often prepared first, and then its particles are pulverized to the desired average particle size between 0.1 and 10 μm with the aid of a high-pressure homogenizer.

[0149] If desired, the inert organic solvent (e.g., ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, or amyl acetate) that is fed into the reaction medium used to prepare component (2) and optionally (3) after emulsification can be removed by distillation to avoid the release of organic hydrocarbons.

[0150] Another subject of the invention is the use of the formulations of the invention and the organopolysiloxanes of the invention as hydrophobic agents, particularly as hydrophobic agents on planar structures or fibers (e.g., textile substrates, linear textiles such as yarns, twists or ropes, paper, leather and mineral planar structures).

[0151] The formulation or organopolysiloxane is preferably applied as a solid substance of the formulation of the present invention at a weight of 0.5-3% by weight, preferably 0.5-2.5% by weight, and particularly preferably 0.5-2.0% by weight relative to the planar structure to be treated, to achieve hydrophobicity. Typically, impregnation is performed on a foulard at a desired concentration and absorbance of 40-100% from an aqueous medium by forced feeding, followed by pre-drying at 80-110°C and subsequent heat treatment at 130-170°C for 1-5 minutes. The duration of the heat treatment depends on the temperature used.

[0152] In the context of this invention, the fiber refers to both natural and man-made fibers. Natural fibers are preferably cotton, wool, or silk. Synthetic or man-made fibers are prepared synthetically from natural or synthetic polymers and are preferably recycled fibers, polyesters, polyolefins (preferably polyethylene or polypropylene, more preferably polypropylene), polyamides, polyarylamides such as Kevlar or meta-aramid, polyacrylonitrile, elastic fibers, or adhesive fibers.

[0153] In the sense of this invention, textiles are made of multiple fibers. Textiles are preferably linear or planar. "Linear textiles" are understood, for example, as yarns, twisted threads, or ropes. Planar textiles are preferably pile fabrics, felts, textiles, knitted fabrics, and mesh fabrics. According to the invention, textiles may also contain mixtures of natural and synthetic fibers. Particularly preferred are planar structures formed from textile bases such as textiles, knitted fabrics, fixed-shape fibers, and pile fabrics ("non-woven fabrics").

[0154] When applied to the planar structure of textiles, the formulations of the present invention can also be combined with textile auxiliaries commonly used in the textile industry. It is important to emphasize agents that improve weave characteristics, such as hydroxymethyl compounds of dihydroxyethylidene urea or hydroxymethyl melamine ethers with different degrees of hydroxymethylation. Additionally, textile auxiliaries that improve flame retardancy or impart a preferred hand feel to the planar structure can also be considered. However, the desired hand feel of the product can be achieved solely through the combination of components (1)-(3) of the present invention, thus eliminating the need for additional textile auxiliaries in these cases.

[0155] The planar structure can also be composed of paper, which can be prepared according to known papermaking methods and from basic materials commonly found in this application field. The formulation of the present invention can be used here as an additive to pulp or applied to the surface of machine-polished paper by means of a coating device when using roller coating, blade coating or air brush coating and subsequently infrared drying, hot air drying or cylinder drying.

[0156] The planar structure formed from leather is also well-suited for surface coatings containing the formulation of this invention and organopolysiloxanes. If application is to be carried out in the downstream refining process of a tannery, it can be applied using known application methods or by spraying or dipping.

[0157] The same applies to other planar structures. Thus, mineral planar structures, such as unplated tiles, ceramic tiles, or walls, can achieve outstanding water repellency by impregnating them with the surface coating solution of the present invention.

[0158] In another embodiment, the formulations of the present invention or the organopolysiloxanes of the present invention can be used as additives in dyes, paints, or plasters. The formulations of the present invention or the organopolysiloxanes are typically present in a proportion of 1-10% by weight of solids relative to the total components.

[0159] In another aspect, the present invention relates to a method for hydrophobicating a substrate, comprising applying the formulation of the present invention or an organopolysiloxane to a substrate, preferably a planar structure, more preferably a textile substrate, paper, leather or mineral substrate.

[0160] The treatment of planar structures can be carried out by various methods, such as by applying, immersing, soaking, scraping, or, where appropriate, using the formulations of the present invention or solutions of organopolysiloxanes in foam form.

[0161] Generally, the solid substance of the formulation of the present invention is used at a concentration of 0.5-3% by weight, preferably 0.5-2.5% by weight, and particularly preferably 0.5-2.0% by weight relative to the weight of the planar structure to be treated.

[0162] Alternatively, the formulation / organopolysiloxane can be applied to the textile substrate by means of forced application or exhaust method.

[0163] In addition, the formulation / organopolysiloxane can be used for post-treatment of washed textiles.

[0164] Many finished products are cleaned in the home using household cleaning machines or industrial cleaning machines. The latter largely involves uniforms worn by firefighters, police officers, military personnel, and other professionals, which are often stored outdoors and thus exposed to the external climate. Garments with common oil, water, and dirt-repellent coatings often suffer a loss of these properties due to washing. Therefore, these properties are usually refreshed by post-treatment with a repellent agent. The formulation of the present invention can be used in such applications.

[0165] The treatment of finished products cleaned by industrial methods is carried out in a washing or spin-drying drum by pouring the solution of the formulation of the present invention onto the spun-dry cleaned items and then drying them in the drum. In the case of household cleaning machines, a topcoat can be applied by means of a commonly used post-treatment spraying process or a metering ball system.

[0166] Another subject of the present invention is the application of the formulations of the present invention as a surface coating on a planar structure, provided that the application is carried out from an organic solvent in an impregnation or immersion method.

[0167] Many garments are not washed, but rather cleaned in organic solvents. Similar to the post-treatment of cleaned products, the hydrophobic properties can also be restored here by refreshing with products based on the organopolysiloxanes and formulations of this invention.

[0168] The treatment of the finished product cleaned in organic solvents is carried out in the cleaning drum of a chemical cleaning machine by pouring or spraying the solution of the formulation of the present invention onto the spun-dry cleaned product, followed by solvent removal in the drum at an elevated temperature. Here, the chemical properties of the cleaning agent are important, that is, the treatment can be carried out in a closed system with perchloroethylene on modern machines or in machines suitable for treatment with hydrocarbon-based solvents (e.g., Isopar J).

[0169] Another subject of this invention is the application of the formulation / organopolysiloxane of this invention as a topcoat on a planar structure, provided that the application is carried out from an organic solvent in a spraying method.

[0170] Instead of treating the planar structure of textiles by applying the formulation / organopolysiloxane of the present invention from a continuous aqueous or solvent-containing solution during or after a washing or cleaning process, for applications in the home (consumer laundry and care) field, the application of the formulation of the present invention can also be carried out by means of various spraying methods. For this purpose, a repellent agent formulated in an organic solvent and a foaming gas from a nozzle or via a pump mechanism is provided. Significant improvements in water repellency can be achieved, particularly in the field of shoe cleaning, thereby improving wearing comfort.

[0171] Example

[0172] The following examples illustrate the invention. The application of a topcoat to a planar structure of textile was performed on a laboratory filament of LFV 350 / 2 "RFA" (Benz, Switzerland), followed by drying and heat treatment on a laboratory tensile test frame of TKF 15 / M 350 (Benz, Switzerland). The absorbance of the solution was determined by weighing the test samples with the topcoat before and after application.

[0173] The hydrophobic effect was not tested immediately after application, but rather after the substrate had been conditioned for 24 hours under standard conditions (ISO 139) to mitigate the effects of over-drying on these properties. The application amount and heat treatment conditions, along with the desired hydrophobic effect, are detailed in Tables 3a to 3c.

[0174] Water repellency on a planar structure of textiles is tested 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 onto the textile substrate under controlled conditions and then visually comparing the wetted sample with an image of the scoring criteria detailed in the test method. The values ​​given here refer to the appearance of the surface after water spraying and have the following meanings:

[0175] 100 = No water droplets adhering or the upper surface is wetted

[0176] 90 = Individual water droplets adhering or surface wetting

[0177] 80 = Wetting of the upper surface at the point of water impact

[0178] 70 = Partial wetting of the entire upper surface

[0179] 50 = Complete wetting of the entire upper surface

[0180] 0 = Complete wetting (saturation) of the entire upper and lower surfaces.

[0181] To test the resistance of the coated planar structure to the cleaning process, the test samples were cleaned at 60°C according to DIN EN ISO 6330:2013 and then dried according to drying method A or F (see Tables 3a & 3c).

[0182] To investigate the abrasion resistance of hydrophobic finished materials, the hydrophobicity of the samples in their original state was first determined using a jet test (AATCC standard test method 22). Subsequently, the samples were rubbed according to the friction test in DIN EN ISO 12947-2. For this purpose, the samples were clamped in a Martindale tester and the knitted fabric was rubbed against the samples for 2000 cycles using 790 kg (corresponding to a nominal pressure of 12 kPa). After the friction test, the hydrophobicity of the samples was re-determined using a jet test (AATCC standard test method 22) (see Table 3a).

[0183] To investigate the effect of hydrophobic agents on the flame retardant effect of specific fibers, these test samples were tested according to DIN 4102 Part 1 (Building Materials Class B2: Normally Combustible Building Materials) (see Table 3b). For this purpose, the textiles were spread out above a flame, and it was observed whether the flame tip reached the test mark at a height of 15 cm within 20 seconds (flame burning time: 15 seconds). This test was performed a total of five times in both the warp and weft directions of the textiles.

[0184] The following commercially available products were used:

[0185] Borchi Kat 24: Bismuth polycarboxylate catalyst, IMCD Deutschland GmbH

[0186] RUCO-LINK XCR: Aqueous emulsion of 3,5-dimethylpyrazole-blocked aliphatic polyisocyanate with 25% solids content; Rudolf GmbH

[0187] Ethoquad HAT / 25: Polyoxyethylene (15) (hydrogenated sebum) methyl ammonium chloride, Julius Hoesch GmbH & Co. KG

[0188] Disponil A 1080: Fatty alcohol ethoxide (C 12 / 14 10 EO), solids content 80%, BASF

[0189] Arquad 2C75: Dicocarbamoyldimethylammonium chloride in isopropanol, 75% solids, Julius Hoesch GmbH & Co. KG

[0190] Example of preparing component (1)

[0191] Compound (A):

[0192] General preparation procedure for compound (A) of formulas (I), (II), (III) and / or (IV)

[0193] In a suitably sized three-necked flask equipped with a distillation cooler, adjustable stirrer, and internal thermometer, components (a1, a2, or a3) and (b1) given in Table 1a are melted in grams under a protective gas and with stirring. The mixture is then heated to the final temperatures (T) given in Tables 1a and 1b and stirred continuously until no more reactive water is distilled off and the acid value (SZ) mentioned in Table 1a is achieved. In the esterification reaction, 0.1% sulfuric acid may be added as a catalyst as needed. No catalyst is required in the amidation reaction. The resulting condensation product is cast out and processed into flakes after cooling.

[0194] Compound (A):

[0195] When using alkyl isocyanate (b2) and further processing into reaction product (S), it is used for formula (I) and / or... Or (II) of the special preparation procedure of compound (A)

[0196] In a suitably sized three-necked flask equipped with a reflux cooler, adjustable stirrer, internal thermometer, and dropping funnel, components (a1) and (b2) in grams, as shown in Table 1a, were placed in isopropyl acetate (solvent (LM)). Then, 0.05% of 1,4-diazabicyclo(2,2,2)octane was added as a catalyst, and the mixture was stirred at 80°C until the NCO band was no longer identifiable in the IR spectrum.

[0197] The components (IC) given in Table 1a were then added to the mixture in grams to prepare the reaction product (S), and stirring was continued at 80°C until the NCO bands were no longer identifiable in the IR spectrum.

[0198] Reaction product (S) (= component (1)):

[0199] The reaction product is formed by compound (A) and unblocked or partially blocked di, tri, or polyisocyanates (IC). General preparation procedure for substance (S)

[0200] In a suitably sized three-necked flask equipped with a reflux cooler, adjustable stirrer, internal thermometer, and dropping funnel, components (A) and (IC), as given in Tables 1a and 1b in grams, were placed in isopropyl acetate (LM). Then, 0.05% of 1,4-diazabicyclo(2,2,2)octane was added as a catalyst, and the mixture was stirred at 65°C until the NCO band was no longer identifiable in the IR spectrum.

[0201] Special preparation procedures for the reaction product (S) used in emulsions (E)3 and 9

[0202] To prepare emulsion (E)3 according to Table 1a, the following reaction product (S) is used, with the amount of dimethylaminoethanol given in Table 1a added in grams during its preparation (reaction of compound (A) with isocyanate (IC)).

[0203] To prepare emulsion (E)9 according to Table 1a, the following reaction product (S) is used, with the amount of dioctadecylamine given in Table 1a still added during its preparation (reaction of compound (A) with isocyanate (IC)).

[0204] Emulsion (E):

[0205] General preparation procedure for emulsions (E) formed from component (1) or reaction product (S) and component (2).

[0206] Oil phase: In a beaker of suitable size, place the gram amounts of reaction product (S) (present in the previously described isopropyl acetate) and component (2) as given in Table 1a and heat to 65–70°C with stirring until a clear, homogeneous solution is produced. The reaction product (S) to be used may, in some cases, be melted at 65–70°C before use to obtain a homogeneous product.

[0207] Aqueous phase: Dissolve the amount of emulsifier (Em) (= component (5)) given in Table 1a in the amount of water given at 65°C in a beaker of suitable size.

[0208] The two phases were rapidly stirred to form a coarse-particle pre-emulsion, which was then homogenized at 65°C on a high-pressure homogenizer at 300–500 bar until an average particle size between 0.1 and 10 micrometers was achieved. The solvent (LM) was then removed by azeotropic distillation under vacuum on a rotary evaporator. Where appropriate, the pH of the resulting emulsion was set to 5–7 with 60% acetic acid, and the resulting white emulsion was filtered through a 20-micrometer filter and the solids content was set to 25% with water.

[0209] Examples of preparation of component (2)

[0210] Organopolysiloxane (2-1)

[0211] 11.1 g (0.13 mol) of an amino-containing organopolysiloxane (I) was mixed with 49.7 g of isopropyl acetate under a nitrogen atmosphere. 0.06 g of Borchi catalyst was dissolved in this mixture with stirring. Then, 39.1 g (0.13 mol) of stearyl isocyanate was added fractionally to facilitate exothermic treatment. After the exothermic reaction was complete, the reaction mixture was heated to 80°C for an additional 2 hours. The reaction mixture was cooled if isocyanate was no longer detected by IR. 94.3 g of the compound, no longer containing protonable basic nitrogen, was obtained. The compound was used to prepare emulsions (E) 1, 4 & 7 in Table 1a.

[0212] Amino-containing organopolysiloxanes (I):

[0213]

[0214] Organopolysiloxane (2-2)

[0215] 12.4 g (0.13 mol) of an amino-containing organopolysiloxane (II) was mixed with 49.0 g of isopropyl acetate under a nitrogen atmosphere. 0.06 g of Borchi catalyst was dissolved in this mixture with stirring. Then, 38.5 g (0.130 mol) of stearyl isocyanate was added fractionally to facilitate exothermic treatment. After the exothermic reaction was complete, the reaction mixture was heated to 80°C for an additional 2 hours. The reaction mixture was cooled if isocyanate was no longer detected by IR. 92.8 g of the compound, no longer containing protonable basic nitrogen, was obtained. The compound was used to prepare emulsions (E) 2, 5 & 9 in Table 1a.

[0216] Amino-containing organopolysiloxanes (II):

[0217]

[0218] Organopolysiloxanes (2-3)

[0219] 16.6 g (0.12 mol) of an amino-containing organopolysiloxane (III) was mixed with 52.5 g of isopropyl acetate under a nitrogen atmosphere. 0.07 g of Borchi catalyst was dissolved in this mixture with stirring. Then, 30.9 g (0.10 mol) of stearyl isocyanate was added fractionally to facilitate exothermic treatment. After the exothermic reaction was complete, the reaction mixture was heated to 80°C for an additional 2 hours. The reaction mixture was cooled if isocyanate was no longer detected by IR. 96.7 g of the compound containing 0.54 wt% protonable basic nitrogen was obtained. The compound was used to prepare emulsions (E) 3, 6 & 8 in Table 1a.

[0220] Amino-containing organopolysiloxanes (III):

[0221]

[0222] Preparation of the formulation (Z) of the present invention

[0223] The emulsion (E) containing components (1), (2) and (5) as detailed in Table 2a is optionally mixed with component (3) and optionally with water in the given weight ratio, thereby obtaining the formulation (Z) mentioned in Table 2a.

[0224] The formulations Z 19-Z 20 (not of this invention) detailed in Table 2b were prepared by replacing the emulsion containing component (2) with an emulsion formed from patent WO 2008 / 135208 A1 (the composition of Example 5 according to Table 1a) and used for comparison.

[0225] Finished Product Examples

[0226] Applying water-based formulations (Z) to the planar structure of textiles:

[0227] Finishing conditions and test setups are detailed in Tables 3a, 3b and 3c.

[0228] Table 1a (according to the present invention):

[0229] Preparation of components (1) and (2) and their emulsion (E)

[0230]

[0231]

[0232] Table 2a:

[0233] The mixing ratio of the formulation (Z) of the present invention

[0234]

[0235] Table 2b:

[0236] Formulation not of this invention (Z)

[0237]

[0238] Table 3a:

[0239] Forced application to polyester fabric, 105 g / m 2 Finishing results

[0240] Dosage of formulation (Z): 30 g / L in water

[0241] Drug absorption rate: 70%

[0242] Drying and concentration: 2 minutes at 170°C

[0243]

[0244] According to EN ISO 6330:2000; Drying method A under standard conditions, standard environment (20°C, 65% humidity) (ISO 139)

[0245] See page 24 onwards in the instruction manual.

[0246] Table 3b: 195 g / m² forcibly applied to Trevira CS fibers 2

[0247] Refined results

[0248] Dosage of formulation (Z): 30 g / L in water

[0249] Drug absorption rate: 70%

[0250] Drying and concentration: 2 minutes at 170°C

[0251]

[0252] = Building material grade B2: Normally combustible

[0253] Building materials

[0254] Table 3c:

[0255] 175g / m² of cotton was forcibly applied. 2

[0256] Refined results

[0257] Dosage of formulation (Z): 40 g / L in water

[0258] Drug absorption rate: 80%

[0259]

[0260] = According to EN ISO 6330:2000; Drying method F (drum drying (70°C))

[0261] The following is the subject matter of this invention:

[0262] 1. An organopolysiloxane containing at least structural unit (i) and / or (vi):

[0263] ,

[0264] in

[0265] R 6 Each contains at least one C independently 8-28 Alkyl, preferably C 14-20 Alkyl, more preferably C 16-18 Alkyl group and at least one urea group, and

[0266] R 7 They are independently selected from -CH3, -OH and -C. 1-5 Alkyl group.

[0267] 2. According to point 1, the organopolysiloxane, wherein

[0268] R 6 Contains at least one C 8-28 Alkyl urea, more preferably C 14-20 Alkyl urea, still more preferably C 16-18 Alkyl urea group.

[0269]

[0270] 3. According to point 1 or point 2, the organopolysiloxane, wherein

[0271] R 6 Selected from

[0272] and

[0273]

[0274] in

[0275] R 10 H or R are independent of each other. 11 ,

[0276] R 11 They are independently -C(O)-NH-C 8-28 Alkyl group, provided that R is an alkyl group. 6 Contains at least one R 11 ,

[0277] k is 2-4, preferably 2-3, and

[0278] l is 2-4, preferably 2-3.

[0279] 4. The organopolysiloxane according to any one of the foregoing points, wherein the organopolysiloxane further comprises at least one structural unit selected from the following

[0280] and

[0281] ,in

[0282] R 5 Each contains C independently 8-28 Alkyl, preferably C 14-20 Alkyl, more preferably C 16-18 alkyl,

[0283] R 8 Selected independently from each other

[0284]

[0285] and

[0286] R 6 and R 7 As defined above.

[0287] 5. The organopolysiloxane according to any one of the foregoing points, wherein the organopolysiloxane independently has terminal groups selected from the group consisting of...

[0288] or

[0289] ,in

[0290] The end was blocked, among which

[0291] R 5 R 6 R 7 and R 8 As defined above.

[0292] 6. The organopolysiloxane according to any one of the above points, wherein the molar percentage of structural unit (i) is in the range of 25-100 mol%, preferably 50-100 mol%.

[0293] 7. The organopolysiloxane according to any one of the above points, wherein the molar percentage of the structural unit (vi) is in the range of 25-100 mol%, preferably 50-100 mol%.

[0294] 8. The organopolysiloxane according to any one of the above points, wherein the molar percentage of structural unit (ii) is in the range of 0-50 mol%, preferably 0-30 mol%.

[0295] 9. The organopolysiloxane according to any one of the above points, wherein the molar percentage of structural unit (iii) is in the range of 0-40 mol%, preferably 0-20 mol%.

[0296] 10. The organopolysiloxane according to any one of the above points, wherein the molar proportion of structural units (iv) and / or (vii) is in the range of 0-20 mol%, preferably 0-10 mol%.

[0297] 11. The organopolysiloxane according to any one of the above points, wherein the molar percentage of the structural unit (v) is in the range of 0-50 mol%, preferably 0-30 mol%.

[0298] 12. The organopolysiloxane according to any one of the above points, wherein the total basic nitrogen content, as measured by titration, is 0-3% by weight, preferably 0-1.5% by weight, and particularly preferably 0.01-0.5% by weight.

[0299] 13. A method for preparing an organopolysiloxane according to any one of points 1 to 13, the method comprising the following steps:

[0300] a) Provide organopolysiloxanes and / or alkoxysilanes having primary and / or secondary amine groups with NCO reactivity.

[0301] b) Reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 Alkyl isocyanate reaction; and

[0302] c) Optionally, the alkoxysilane obtained in step b) is hydrolyzed / condensed to synthesize the organopolysiloxane.

[0303] 14. The method according to point 13, wherein the (C) group has at least one primary and / or secondary amine group with NCO reactivity. 1-5 The organopolysiloxane according to a) is obtained by equilibrium in the presence of alkoxysilanes or by hydrolysis / condensation thereof.

[0304] 15. According to the method of point 13, wherein the (C) group has at least one primary and / or secondary amine group with NCO reactivity 1-5 Alkoxysilanes have the following structures

[0305] and / or

[0306] Where R 7 and R 8 As defined above.

[0307] 16. The method according to one of points 14-15, wherein 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).

[0308] 17. The method according to any one of points 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 a tertiary amine such as 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylaminopropyl dipropanolamine, pentamethyldipropylenetriamine, N-methylimidazolium, or N-ethylmorpholine, optionally at an elevated temperature, for example, 40-140°C.

[0309] 18. Organopolysiloxanes that can be obtained according to one of the methods in points 13 to 17.

[0310] 19. Preparations, comprising:

[0311] (1) At least one reaction product (S), said reaction product being capable of reacting with at least one compound (A) of the following formula.

[0312] Formula (I)

[0313] and / or formula (II) ,

[0314] and / or formula (III)

[0315] And / or form (IV)

[0316] Where R 1 = -XYZ or -Z, where

[0317] X = -(CH2) n" -,

[0318] Y = or

[0319] Z = -(CH2) m -CH3,

[0320] R 2 = ,

[0321] R 3 = -XYZ, -Z, or -YZ, provided that residue R is represented as -YZ. 2 In the text, n is replaced by n"

[0322] R 4 = -XYZ or -(CH2) n' H,

[0323] B 1= -VWZ or -Z,

[0324] in

[0325] V = or ,

[0326] W =

[0327] or ,

[0328] B 2 = -(CH2) n" -NH2 or ,

[0329] B 3 = -VWZ, -Z or ,

[0330] B 4 = -VWZ or ,

[0331] Q = -(CH2) n" -,

[0332] R S They are independent of each other as -OH, -YZ,

[0333] or

[0334] ,

[0335] The prerequisite is that at least one residue R in equation (III) S It is an OH group, and

[0336] n, n', n", n''', and m are all independent integers, where

[0337] n = 0-2,

[0338] n' = 0-4,

[0339] n" = 1-4,

[0340] n'" = 0-4 and

[0341] m = 8-30, preferably 12-26, especially preferably 14-22.

[0342] It is obtained by reaction 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.

[0343] (2) At least one organopolysiloxane according to any one of points 1 to 12 or 18,

[0344] (3) Optionally at least one unblocked or at least partially blocked di, tri, or polyisocyanate (IC).

[0345] (4) Optionally at least one liquid medium, particularly water or an organic solvent, and

[0346] (5) Optionally at least one emulsifier.

[0347] 20. The formulation according to point 19, wherein component (1) accounts for 10-90% by weight, preferably 20-80% by weight, and more preferably 25-65% by weight, relative to the total mass of components (1) and (2).

[0348] 21. The formulation according to one of points 19-20, wherein component (2) accounts for 10-90% by weight, preferably 20-80% by weight, and more preferably 30-70% by weight, relative to the total mass of components (1) and (2).

[0349] 22. The formulation according to one of points 19-21, wherein component (3) accounts for 0-50% by weight, preferably 1-35% by weight, and more preferably 5-35% by weight, relative to the total mass of components (1), (2) and (3).

[0350] 23. The formulation according to any one of points 19-22, wherein component (5) accounts for 0-25% by weight, preferably 1-20% by weight, and more preferably 2-15% by weight, relative to the total mass of components (1), (2), optionally (3) and (5).

[0351] 24. The formulation according to any one of points 19-23 is in the form of a dispersion, preferably in the form of an aqueous dispersion.

[0352] 25. The formulation according to any one of points 19-24, wherein the solid content of the dispersion is 10-40% by weight, preferably 15-30% by weight.

[0353] 26. A formulation according to any one of points 19-25, wherein the polyisocyanate (IC) is selected from the group consisting of: 2,4-toluene 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 trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanates, and mixtures, such as mixtures of MDI and polymer MDI, and derivatives thereof.

[0354] 27. The formulation (Z) according to any one of points 19-26, wherein, for the reaction product (S), the molar ratio of the free isocyanate (NCO) group in the polyisocyanate (IC) to the isocyanate-reactive group in the compound (A) is set to 1.1 to 1:1.3, preferably 1 to 1.1.

[0355] 28. The formulation (Z) according to point 27, wherein the isocyanate-reactive group is a hydroxyl, primary and / or secondary amino group.

[0356] 29. The formulation (Z) according to one of points 19-28, wherein the organic solvent of component (4) is selected from esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate or pentyl acetate, ketones such as acetone, methyl ethyl ketone and saturated hydrocarbons such as n-hexane, n-heptane or n-octane.

[0357] 30. A formulation according to one of points 19-29, wherein the emulsifier according to component (5) is selected from anionic, cationic and nonionic surfactants.

[0358] 31. A formulation according to one of points 19-30, wherein the formulation is free of fluorine compounds.

[0359] 32. Use of an organopolysiloxane according to any one of points 1-12 or 18, or an formulation according to any one of points 19-31, as a hydrophobic agent.

[0360] 33. As per the use in point 32, as a hydrophobic agent on planar structures, especially textile substrates, paper, leather and mineral planar structures.

[0361] 34. As used in point 33, as an additive in dyes, paints or plasters.

[0362] 35. A method for hydrophobicating a substrate, comprising applying an formulation Z according to one of points 19-31 or an organopolysiloxane according to one of points 1-12 or 18 to a substrate, preferably a planar structure, more preferably a textile substrate, paper, leather or mineral substrate.

[0363] 36. The method according to point 35, wherein the application is carried out by means of spraying, dipping, impregnation, scraping or application by a sponge.

[0364] 37. The method according to point 35 or 36, wherein the formulation is applied to the textile substrate by means of forced application or by exhaustion.

Claims

1. An organopolysiloxane comprising at least one structural unit (i) and / or (vi): in R 6 Each contains at least one C independently 8-28 Alkyl group and at least one urea group, and R 7 They are selected independently from -CH3 and -C 1-5 Alkyl group.

2. The organopolysiloxane according to claim 1, wherein... R 6 Contains at least one C 8-28 Alkyl urea 。 3. The organopolysiloxane according to claim 2, wherein R 6 Includes C 14-20 Alkyl urea group.

4. The organopolysiloxane according to claim 2, wherein R 6 Includes C 16-18 Alkyl urea group.

5. The organopolysiloxane according to claim 2, wherein R 6 Selected from and in R 10 H or R are independent of each other. 11 , R 11 They are independently -C(O)-NH-C 8-28 Alkyl group, provided that R is an alkyl group. 6 Contains at least one R 11 , k is 2-4, and l is 2-4.

6. The organopolysiloxane according to claim 1, wherein the organopolysiloxane further comprises at least one structural unit selected from the group consisting of... and ,in R 5 C is independent of each other. 8-28 alkyl, R 8 Selected independently from each other and R 6 and R 7 As defined above.

7. The organopolysiloxane according to 6, wherein the molar percentage of structural unit (i) is in the range of 25-100 mol%, and / or the molar percentage of structural unit (vi) is in the range of 25-100 mol%, and / or the molar percentage of structural unit (ii) is in the range of 0-50 mol%, and / or the molar percentage of structural unit (iii) is in the range of 0-40 mol%, and / or the molar percentage of structural units (iv) and / or (vii) is in the range of 0-20 mol%, and / or the molar percentage of structural unit (v) is in the range of 0-50 mol%.

8. The organopolysiloxane according to claim 6, wherein the molar percentage of structural unit (i) is in the range of 50-100 mol%, and / or the molar percentage of structural unit (vi) is in the range of 50-100 mol%, and / or the molar percentage of structural unit (ii) is in the range of 0-30 mol%, and / or the molar percentage of structural unit (iii) is in the range of 0-20 mol%, and / or the molar percentage of structural units (iv) and / or (vii) is in the range of 0-10 mol%, and / or the molar percentage of structural unit (v) is in the range of 0-30 mol%.

9. A method for preparing an organopolysiloxane according to any one of claims 1-8, the method comprising the following steps: a) Provide organopolysiloxanes and / or alkoxysilanes having primary and / or secondary amine groups with NCO reactivity. b) Reacting the organopolysiloxane and / or alkoxysilane according to a) with C 8-28 Alkyl isocyanate reaction; and c) Optionally, the alkoxysilane obtained in step b) is hydrolyzed / condensed to synthesize the organopolysiloxane.

10. The method according to claim 9, wherein the (C) group has at least one primary and / or secondary amine group with NCO reactivity. 1-5 The organopolysiloxane according to a) is obtained by equilibrium in the presence of alkoxysilanes or by hydrolysis / condensation of said silanes, wherein the (C) siloxane has at least one NCO-reactive primary and / or secondary amine group. 1-5 Alkoxysilanes have the following structures and / or , where R 7 and R 8 As defined above.

11. Preparations, including (1) At least one reaction product (S), said reaction product being capable of reacting with at least one compound (A) of the following formula. Equation (I) and / or formula (II) , and / or formula (III) And / or form (IV) Where R 1 = -XYZ or -Z, where X=-(CH2) n" -, Y= or Z = -(CH2) m -CH3, R 2 = ， R 3 = -XYZ, -Z, or -YZ, provided that, in the case of -YZ, residue R 2 In the text, n is replaced by n" R 4 = -XYZ or -(CH2) n' H, B 1 = -VWZ or -Z, where V = or , W = or , B 2 = -(CH2) n" -NH2 or , B 3 = -V - W - Z, -Z or , B 4 = -VWZ or , Q = -(CH2) n" -, R S They are independent of each other as -OH, -YZ, or ， The prerequisite is that at least one residue R in equation (III) S It is an OH group, and n, n', n", n''', and m are all independent integers, where n=0-2， n'=0-4， n"=1-4， n'''=0-4 and m=8-30， Obtained by reaction with at least one unblocked or at least partially blocked polyisocyanate (IC), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mole, and wherein the formulation is free of fluorine compounds. (2) At least one organopolysiloxane according to any one of claims 1-8, (3) Optionally at least one unblocked or at least partially blocked polyisocyanate (IC). (4) Optionally at least one water or organic solvent, and (5) Optionally at least one emulsifier.

12. The formulation according to claim 11, wherein component (1) accounts for 10-90% by weight relative to the total mass of components (1) and (2), and / or component (2) accounts for 10-90% by weight relative to the total mass of components (1) and (2), and / or component (3) accounts for 0-50% by weight relative to the total mass of components (1), (2) and (3), and / or component (5) accounts for 0-25% by weight relative to the total mass of components (1), (2), optionally (3) and (5).

13. The formulation according to claim 11 is in the form of an aqueous dispersion, wherein the solid content of the dispersion is 10-40% by weight.

14. The formulation of claim 11, wherein the polyisocyanate (IC) is selected from the group consisting of: 2,4-toluene 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 trimer, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, isophorone diisocyanate trimer, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate and dimer diisocyanate.

15. The formulation according to claim 11, wherein, for the reaction product (S), the molar ratio of the free isocyanate (NCO) group in the polyisocyanate (IC) to the isocyanate-reactive group in the compound (A) is set to 1.1 to 1:1.3, wherein the isocyanate-reactive group is a hydroxyl, primary and / or secondary amino group.

16. The organopolysiloxane according to any one of claims 1-8 or the formulation according to any one of claims 11-15, as a hydrophobic agent on textile substrates, paper, leather and mineral planar structures, and as an additive in dyes, paints or plaster.

17. A method for hydrophobicating a substrate, comprising applying the formulation of any one of claims 11-15 or the organopolysiloxane of any one of claims 1-8 to a textile substrate, paper, leather or mineral substrate.

18. The method of claim 17, wherein the application is performed by means of spraying, dipping, impregnation, scraping, or application by a sponge.

19. The method according to claim 17 or 18, wherein the formulation is applied to the textile substrate by means of forced application or by absorption.

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