HYDROPHOBIZING AGENT HAVING A PERMANENT EFFECT

Abstract

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

Claims

1. Organopolysiloxane comprising at least one structural unit (i) and/or (vi): ##STR00026## wherein R.sup.6 independently comprises at least one C.sub.8-28 alkyl group, and at least one urea group, and R.sup.7 independently is selected from CH.sub.3, OH and a C.sub.1-5 alkoxy group.

2. The organopolysiloxane according to claim 1, wherein R.sup.6 comprises at least one C.sub.8-28 alkyl urea group ##STR00027##

3. The organopolysiloxane according to claim 1, wherein the organopolysiloxane further comprises at least one structural unit selected from ##STR00028## wherein R.sup.5 is a C.sub.8-28 alkyl group, R.sup.6 is independently selected from ##STR00029## R.sup.6 and R.sup.7 are as defined above.

4. The organopolysiloxane according to claim 1, wherein the molar portion of the structural unit (i) is in the range of 25-100 mol-%, and/or the molar portion of the structural unit (vi) is in the range of 25-100 mol-%, and/or the molar portion of the structural unit (ii) is in the range of 0-50 mol-%, and/or the molar portion of the structural unit (iii) is in the range of 0-40 mol-%, and/or the molar portion of the structural unit (iv) and/or (vii) is in the range of 0-20 mol-%, and/or the molar portion of the structural unit (v) is in the range of 0-50 mol-%.

5. Method for preparing an organopolysiloxane according to claim 1, comprising a) providing an organopolysiloxane and/or alkoxysilane having NCO-reactive primary and/or secondary amine groups, b) reacting the organopolysiloxane and/or alkoxysilane according to a) with C.sub.8-28 alkyl isocyanate; and c) optionally hydrolyzing/condensing the alkoxysilane obtained in b) to the organopolysiloxane.

6. The method according to claim 5, wherein the organopolysiloxane according to a) is obtained by equilibration in presence of or by hydrolysis/condensation of (C.sub.1-5-alkoxy)silanes having at least one NCO-reactive primary and/or secondary amine group, wherein the (C.sub.1-5-alkoxy)silane having at least one NCO-reactive primary and/or secondary amine group preferably has the structure ##STR00030## wherein R.sup.7 and R.sup.8 are as defined above.

7. Composition comprising (1) at least one reaction product (S) obtainable by reacting at least one compound (A) of ##STR00031## wherein R.sup.1=XYZ or Z, wherein ##STR00032## R.sup.3=XYZ, Z or YZ with the proviso that if R.sup.3=YZ, in R.sup.2, n is replaced by n, R.sup.4=XYZ or (CH.sub.2).sub.nH, B.sup.1=VWZ or Z, wherein ##STR00033## R.sup.s independently from each other is OH, YZ, ##STR00034## provided that at least one residue R.sup.s in formula (III) is an OH group, and n, n, n, n and m independently from each other is an integer, wherein n=0-2, n=0-4, n=1-4, n=0-4 and m=8-30, having at least one non-blocked or at least one partially blocked di-, tri- or polyisocyanate (IC), wherein the portion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mol wherein the preparation is free of fluorine compounds (2) at least one organopolysiloxane according to claim 1, (3) optionally at least one non-blocked or at least partially blocked di-, tri- or polyisocyanate (IC), (4) optionally at least one liquid medium, in particular water or an organic solvent, and (5) optionally at least one emulsifier.

8. The composition according to claim 7, wherein component (1) constitutes 10-90 wt %, based on the total mass of components (1) and (2) and/or component (2) constitutes 10-90 wt %, based on the total mass of components (1) and (2) and/or component (3) constitutes 0-50 wt %, based on the total mass of components (1), (2) and (3) and/or component (5) constitutes 0-25 wt %, based on the total mass of components (1), (2), optionally (3) and (5).

9. The composition according to claim 7 in the form of a dispersion, wherein the solids content of the dispersion is 10-40 wt %, preferably 15-30 wt %.

10. The composition according to claim 7, wherein the polyisocyanate (IC) is selected from the group consisting of 2,4-toluylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), higher chain homologues of diphenylmethane diisocyanate (polymer MDI), 4-methyl-cyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, and mixtures.

11. The composition (Z) according to claim 7, wherein for the reaction product (S) the molar ratio of free isocyanate (NCO) groups in the polyisocyanate (IC) to isocyanate-reactive groups in compound (A) is adjusted to 1:1 to 1:1.3, preferably 1 to 1.1, wherein the isocyanate-reactive groups are hydroxy groups, primary and/or secondary amino groups.

12. A method for providing the organopolysiloxane according to claim 1 as a hydrophobing agent on sheet materials or as an additive in paints, varnishes or plasters.

13. Method of hydrophobizing substrates without using fluorocarbon polymers, comprising applying the organopolysiloxane according to claim 1 to a substrate.

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

15. The method according to claim 13, wherein the preparation is applied to a textile substrate via forced application or by the exhaust method.

16. The organopolysiloxane according to claim 1, wherein the organopolysiloxane is fluorine-free and serves as a hydrophobizing agent for a textile substrate.

17. The organopolysiloxane according to claim 1, wherein the at least one C.sub.8-28 alkyl group is a C.sub.14-20 alkyl group or a C.sub.16-18 alkyl group.

18. The organopolysiloxane according to claim 2, wherein the at least one C.sub.8-28 alkyl group is a C.sub.14-20 alkyl urea-group or a C.sub.16-18 alkyl urea group.

19. The organopolysiloxane according to claim 2, wherein R.sup.6 is selected from ##STR00035## wherein R.sup.10 independently is H or R.sup.11, R.sup.11 independently is C(O)NHC.sub.8-28 alkyl provided that R.sup.6 comprises at least one R.sup.11, k is 2-4 or 2-3 and l is 2-4 or 2-3.

20. The method of hydrophobizing substrates according to claim 13, wherein the hydrophobizing agent is fluorine-free, the substrate is a textile substrate and the hydrophobizing of the substrate does not involve fluorocarbon polymers.

Description

EXAMPLES

[0143] The following examples illustrate the present invention. The application of the finishes on textile fabrics was carried out on a laboratory foulard of type LFV 350/2 RFA (company Benz, Switzerland) with subsequent drying and hot treatment on a laboratory stenter frame of type TKF 15/M 350 (company Benz, Switzerland). The liquor uptake was determined by weighing the finished test samples before and after application.

[0144] The hydrophobic effects were not tested immediately after application, but only after conditioning the substrates in a standard climate (ISO 139) for 24 hours, in order to level out influences on these properties due to overdrying. Application quantities as well as the conditions of the hot treatment are listed together with the phobic effects to be achieved in Tables 3a to 3c.

[0145] Water repellency was tested on the textile fabrics by means of a spray test according to AATCC Standard Test Method 22. The AATCC Standard Test Method 22 test is performed by spraying distilled water under controlled conditions onto the textile substrate to be tested and then visually comparing the wetting pattern to images of an evaluation standard listed in the test method. The numerical values given refer to the appearance of the surface after the water has been sprayed on and have the following meaning: [0146] 100=No adhesion of water droplets or wetting of the upper surface. [0147] 90=Isolated adhesion of water droplets or wetting of the upper surface [0148] 80=Wetting of the upper surface at the points of impact of the water [0149] 70=Partial wetting of the entire upper surface [0150] 50=Complete wetting of the entire upper surface [0151] 0=Complete wetting of the entire upper and lower surface (wetting)

[0152] In order to test the resistance of the finished fabrics to washing processes, the test samples were washed at 60 C. according to DIN EN ISO 6330:2013 and then dried according to drying method A or F (see Tab. 3a & 3c).

[0153] In order to examine the resistance of the hydrophobic finish to abrasion, the water repellency of the samples in the original condition was first determined by means of a spray test (AATCC Standard Test Method 22). Subsequently, the samples were subjected to abrasion testing in accordance with DIN EN ISO 12947-2. For this purpose, the respective samples were clamped in a Martindale test instrument and a knitted fabric with a load of 790 kg (corresponding to a nominal pressure of 12 kPa) was rubbed against the samples for 2000 cycles. After scrubbing, the hydrophobic effect of the samples was again determined by spray test (AATCC Standard Test Method 22) (see Table 3a).

[0154] In order to examine the influence of the hydrophobic agents on the flame retardant effect of special fibers, the test samples were tested according to DIN 4102, Part 1 (building material class B2: normally flammable building materials) (see Tab. 3b). For this purpose, the textile is stretched over the flame and it is observed whether the flame tip reaches the measuring mark at a height of 15 cm within 20 s or not (burning time of the flame: 15 s). This test is performed a total of five times each in the warp and weft directions of the textile.

[0155] The following commercially available products were used: [0156] Borchi Kat 24: versatile bismuth carboxylate catalyst, IMCD Deutschland GmbH [0157] RUCO-LINK XCR: solids content 25%, aqueous emulsion of an 3,5-dimethylpyrazole blocked polyisocyanates; Rudolf GmbH [0158] Ethoquad HAT/25: Polyoxyethylene(15)(hydrogenated tallow)methylammonium chloride, Julius Hoesch GmbH & Co. KG [0159] Disponil A 1080: fatty alcohol ethoxylate (C.sub.12/14, 10 EO), solids content 80%, BASF [0160] Arquad 2C.sub.75: Dicocosdimethylammonium chloride in isopropanol, solids content 75%, Julius Hoesch GmbH & Co. KG

Examples for the Preparation of Component (1)

[0161] Compound (A):

[0162] General Preparation Instruction for Compound (A) of Formula (I), (II), (Ill) and/or (IV)

[0163] In a suitably dimensioned three-necked flask equipped with a distillation condenser, adjustable stirrer and internal thermometer, the components (a1, a2 or a3) and (b1) listed in Tables 1a are melted in the quantities in grams indicated there under inert gas and with stirring. The mixture is then heated to the final temperature (T) indicated in Tables 1a and 1b and stirred further until no more reaction water is distilled off and the acid number (SZ) indicated in Tables 1a is reached. If necessary, 0.1% sulfuric acid can be added as a catalyst for the esterification reactions. In the amidation reactions, no addition of catalyst is necessary. The resulting condensation product is poured out and processed into flakes after cooling.

[0164] Compound (A):

[0165] Special Preparation Instructions for Compound (A) of the Formula (I) and/or (II) Using Alkyl Isocyanates (b2) and Further Processing to Obtain the Reaction Product (S)

[0166] In a suitably sized three-neck flask equipped with reflux condenser, controllable stirrer, internal thermometer and dropping funnel, the components (a1) and (b2) listed in Table 1a are added in grams to isopropyl acetate (solvent (LM)). Then, based on the total amount of components, 0.05% 1,4-diazabicylo(2,2,2)octane is added as catalyst and the mixture is stirred at 80 C. until no NCO band is visible in the IR spectrum.

[0167] Subsequently, the amounts in grams of component (IC) indicated in Table 1a are added to the mixture to prepare the reaction product (S) and stirring is continued at 80 C. until no NCO band can be detected in the IR spectrum.

[0168] Reaction Products (S) (=Component (1)):

[0169] General Preparation Instructions for Reaction Products (S) of a Compound (A) and Non-Blocked or Partially Blocked Di-, Tri- or Polyisocyanates (IC)

[0170] In a suitably dimensioned three-neck flask equipped with a reflux condenser, controllable stirrer, internal thermometer and dropping funnel, the components (A) indicated in Tables 1a and 1b and the components (IC) are added to isopropyl acetate (LM) in the amounts in grams indicated there. Then, based on the total amount of components, 0.05% of 1,4-diazabicylo(2,2,2)octane is added as catalyst and the mixture is stirred at 65 C. until no NCO band is visible in the IR spectrum.

[0171] Special Preparation Instructions for the Reaction Products (S) Used in Emulsions (E) 3 and 9

[0172] For the preparation of emulsion (E) 3 according to Table 1a, a reaction product (S) is used, in the preparation of which (reaction of compound (A) with isocyanate (IC)) the amount in grams of dimethylaminoethanol indicated in Table 1a is still added.

[0173] For the preparation of emulsion (E) 9 according to Table 1a, a reaction product (S) is used, in the preparation of which (reaction of compound (A) with the isocyanate (IC)) the amount in grams of bisoctadecylamine indicated in Table 1a is also added.

[0174] Emulsions (E):

[0175] General Preparation Instructions for Emulsions (E) from Component (1) or the Reaction Products (S) and Component (2)

[0176] Oily phase: The amounts in grams of reaction product (S), present in the above-mentioned isopropyl acetate, and component (2) given in Table 1a are placed in a suitably dimensioned beaker and heated to 65-70 C. with stirring until a clear, homogeneous solution is obtained. The reaction product (S) to be used may have to be melted at 65-70 C. before use to obtain a homogeneous product.

[0177] Aqueous phase: In a suitably sized beaker, dissolve the amounts in grams of emulsifier (Em) (=component (5)) indicated in Tables 1a in the indicated amount of water at 65 C.

[0178] The two phases are stirred under a high-speed stirrer to form a coarse pre-emulsion, which is then homogenized at 65 C. on the high-pressure homogenizer at 300-500 bar until an average particle size of between 0.1 and 10 micrometers is achieved. Subsequently, the solvent (LM) is removed on the rotary evaporator in vacuum by azeotropic distillation. If necessary, the pH of the obtained emulsion is adjusted to 5-7 with acetic acid 60%, the obtained white emulsion is filtered through a 20 micron filter and adjusted with water to a solids content of 25%.

Examples for the Preparation of Component (2) Organopolysiloxane (2-1)

[0179] 11.1 g (0.13 mol) of an amino group-containing organopolysiloxane (I) are mixed with 49.7 g of isopropyl acetate under nitrogen atmosphere. In this mixture, 0.06 g of Borchi catalyst is dissolved under stirring. Then 39.1 g (0.13 mol) of stearyl isocyanate is added in portions so that the exotherm can be well managed. After the exotherm has subsided, the reaction mixture is heated to 80 C. for another 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. 94.3 g of a compound is obtained which no longer contains protonatable basic nitrogen. The compound is used to prepare emulsions (E) 1, 4 & 7 in Table 1a.

[0180] Amino group-containing organopolysiloxane (I):

##STR00012##

[0181] Organopolysiloxane (2-2)

[0182] 12.4 g (0.13 mol) of an amino group-containing organopolysiloxane (II) are mixed with 49.0 g of isopropyl acetate under nitrogen atmosphere. In this mixture, 0.06 g of Borchi catalyst is dissolved under stirring. Then 38.5 g (0.130 mol) of stearyl isocyanate is added in portions so that the exotherm can be well managed. After the exotherm has subsided, the reaction mixture is heated to 80 C. for another 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. 92.8 g of a compound is obtained which no longer contains protonatable basic nitrogen. The compound is used to prepare emulsions (E) 2, 5 & 9 in Table 1a.

[0183] Amino group-containing organopolysiloxane (II):

##STR00013##

[0184] Organopolysiloxane (2-3)

[0185] 16.6 g (0.12 mol) of an amino group-containing organopolysiloxane (Ill) are mixed with 52.5 g of isopropyl acetate under nitrogen atmosphere. In this mixture, 0.07 g of Borchi catalyst is dissolved under stirring. Then 30.9 g (0.10 mol) of stearyl isocyanate is added in portions so that the exotherm can be well managed. After the exotherm has subsided, the reaction mixture is heated to 80 C. for another 2 h. When no more isocyanate is detectable (IR), the reaction mixture is cooled. 96.7 g of a compound containing 0.54 wt % protonatable basic nitrogen is obtained. The compound is used to prepare emulsions (E) 3, 6 & 8 in Table 1a.

[0186] Amino group-containing organopolysiloxane (Ill):

##STR00014##

[0187] Preparation of the Preparations (Z) According to the Present Invention

[0188] The emulsions (E) listed in Table 2a, containing components (1), (2) and (5), are optionally mixed with component (3) and optionally with water in the specified weight ratios to give the preparations (Z) listed in Table 2a.

[0189] The preparations Z 19-Z 20 (not according to the present invention) as described in Table 2b were prepared with emulsions from patents WO 2008/135208 A1 (composition according to example 5 of Table ha) instead of the emulsions with component (2) and are for comparison reasons only.

Finishing Examples

[0190] Application of Water-Based Preparations (Z) on Textile Fabrics:

[0191] Conditions of equipment and test results are shown in Tables 3a, 3b and 3c.

TABLE-US-00001 TABLE 1a (according to the present invention): Production of component (1) and component (2) as well as their emulsions (E) Quantities in grams Components 1 2 3 4 5 6 7 8 9 Compound (A) (a) (a1) Glycerol 81.0 81.0 81.0 (=precursor (a2) Triethanolamine 131.1 131.1 131.1 of (a) and (b) (a3) Bis(aminoethyl) 90.6 90.6 90.6 for reaction amine product(S)) (b) (b1) Lauric acid 352.0 Palmitic acid 450.6 450.6 Stearic acid 499.8 499.8 Behenic acid 598.4 598.4 (b2) Stearyl 520.1 520.1 isocyanate Final 90 160 160 165 165 160 165 90 160 temperature (T) in C. Acid number <5 <5 <10 <10 <5 <5 <5 (SZ) Reaction component (A) 108.2 137.3 137.3 124.1 124.1 117.9 99.4 112.6 99.4 Product (S) Bis (octadecyl) 9.2 (=comp. (1)) amine Dimethyl amino 4.8 ethanol Isocyanate (IC) 2,4- 49.5 56.9 39.4 36.1 Toluylendiisocyanate/ Trimethylol- propanurethane with 13.5 wt.-% NCO Hexamethylendiisocyanate 46.7 36.4 35.3 41.5 31.4 trimer having 21.7 wt.-% NCO Solvent (LM) Isopropylacetate 158 184 179 181 159 162 141 144 145 Emulsion (E) Reaction product (S) 88.0 133.8 133.8 109.1 109.1 109.1 99.4 99.4 99.4 comprising Cpomponent (2) Organopolysiloxane 29.0 35.2 50.2 components (1), Alkylurea- (2-1) (2), (4) and (5) functionalized Organopolysiloxane 66.9 35.2 50.2 organopolysiloxane (2-2) Organopolysiloxane 66.9 35.2 50.2 (2-3) Component (5) Ethoquad HT 25 0.2 0.5 0.5 0.3 0.3 0.3 0.4 0.4 0.4 emulsifier (Em) Disponil A 1080 1.9 3.8 3.8 2.4 2.4 2.4 2.4 2.4 2.4 Arquad 2C75 1.6 3.5 3.5 2.4 2.4 2.4 2.5 2.5 2.5 water (4) 229.7 401.3 401.3 269.3 269.3 269.3 300.1 300.1 300.1 Acetic acid 60% 0.3 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

TABLE-US-00002 TABLE 2a Mixing ratios of the preparations according to the invention (Z) Parts by weight Parts by of emulsion (E) weight of Parts containing component by components (1), (3) RUCO- weight (2), (4) and (5) LINK XCR water Preparation (Z) 80 of (E) 1 20 1 according to the present invention 80 of (E) 1 20 2 according to the present invention 80 of (E) 2 20 3 according to the present invention 80 of (E) 2 20 4 according to the present invention 80 of (E) 3 20 5 according to the present invention 80 of (E) 3 20 6 according to the present invention 80 of (E) 4 20 7 according to the present invention 80 of (E) 4 20 8 according to the present invention 80 of (E) 5 20 9 according to the present invention 80 of (E) 5 20 10 according to the present invention 80 of (E) 6 20 11 according to the present invention 80 of (E) 6 20 12 according to the present invention 80 of (E) 7 20 13 according to the present invention 80 of (E) 7 20 14 according to the present invention 80 of (E) 8 20 15 according to the present invention 80 of (E) 8 20 16 according to the present invention 80 of (E) 9 20 17 according to the present invention 80 of (E) 9 20 18 according to the present invention

TABLE-US-00003 TABLE 2b Preparations not according to the present invention (Z) Parts by weight of Parts component by (3) RUCO- weight Products LINK XCR water Preparation (Z) 80 Example 5 of 20 19 (not according to WO 2008/135208 A1 the invention) 80 Example 5 of 20 20 (not according to WO 2008/135208 A1 the invention)

TABLE-US-00004 TABLE 3a Forced application on polyester fabric, 105 g/m.sup.2 Finishing results Application quantity of preparation (Z): 30 g/l in water Liquor pick-up: 70% Drying and condensation: 2 minutes at 170 C. Preparation (Z) According to According to the present invention Tab. 2a/2b 1 2 3 4 5 6 7 8 9 10 Original AATCC 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 After 3 AATCC 100 100 100 90 100 100 100 100 100 100 60 C. Standard washes * Test Method 22 After 5 AATCC 90 90 90 100 90 100 90 90 90 100 60 C. Standard washes * Test Method 22 After 10 AATCC 90 90 80 90 90 90 90 90 80 90 60 C. Standard washes * Test Method 22 Abrasion AATCC 100 90 90 90 100 100 90 100 90 90 resistance ** Standard 2000 tours Test Method 22 Not according to Preparation (Z) the present According to According to the present invention invention Tab. 2a/2b 11 12 13 14 15 16 17 18 19 20 Original AATCC 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 After 3 AATCC 90 100 100 100 100 100 100 100 80 90 60 C. Standard washes * Test Method 22 After 5 AATCC 90 100 90 100 90 100 90 90 70 70 60 C. Standard washes * Test Method 22 After 10 AATCC 80 90 80 90 90 90 80 90 50 70 60 C. Standard washes * Test Method 22 Abrasion AATCC 100 100 100 90 80 90 90 100 70 80 resistance ** Standard 2000 tours Test Method 22 * according to EN ISO 6330: 2000; drying method A in standard climate standard climate (20 C., humidity 65%) (ISO 139) ** cf. description on p. 24 et seq.

TABLE-US-00005 TABLE 3b Forced application on Trevira CS fiber, 195 g/m.sup.2 Finishing results application quantity of preparation (Z): 30 g/l in water Liquor pick-up: 70% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according to According to the present invention table 2a/2b 1 2 3 4 5 Burning Fabric direction warp weft warp weft warp weft warp weft warp weft behavior Total burn time [s] 2 5 12 8 10 24 7 4 20 23 according Does the flame n n n n n y n n n n to DIN 4102, peak reach the Part 1* measuring mark before the end of the 20s? [y = yes/n = no] Preparation (Z) according to According to the present invention table 2a/2b 6 7 8 9 10 Burning Fabric direction warp weft warp weft warp weft warp weft warp weft behavior Total burn time [s] 28 18 13 22 3 5 8 12 27 20 according Does the flame y n n y n n n n y n to DIN 4102, peak reach the Part 1* measuring mark before the end of the 20s? [y = yes/n = no] Preparation (Z) according to According to the present invention table 2a/2b 11 12 13 14 15 Burning Fabric direction warp weft warp weft warp weft warp weft warp weft behavior Total burn time [s] 8 7 15 22 7 10 26 21 16 27 according Does the flame n n n n n n y n n y to DIN 4102, peak reach the Part 1* Measuring mark before the end of the 20s? [y = yes/n = no] Preparation (Z) Not according to according to According to the present invention the present invention table 2a/2b 16 17 18 19 20 Burning Fabric direction warp weft warp weft warp weft warp weft warp weft behavior Total burn time [s] 4 18 25 23 2 9 37 56 46 32 according Does the flame n n n n n n y y y n to DIN 4102, peak reach the Part 1* Measuring mark before the end of the 20s? [y = yes/n = no] *Building material class B2: normally flammable building materials

TABLE-US-00006 TABLE 3c Forced application on cotton, 175 g/m.sup.2 Finishing results Application quantity of preparation (Z): 40 g/l in water Liquor pick-up: 80% Preparation (Z) according to According to the present invention table 2a/2b 1 2 3 4 5 6 7 8 9 10 Original AATCC 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 After AATCC 90 100 100 100 100 100 90 100 90 100 5 Standard 60 C. Test washes * Method 22 After AATCC 90 90 80 90 80 90 90 90 90 90 10 Standard 60 C.- Test washes * Method 22 After AATCC 80 90 80 90 70 90 80 90 80 90 15 Standard 60 C. Test Washes * Method 22 Not according to Preparation (Z) the present according to According to the present invention invention table 2a/2b 11 12 13 14 15 16 17 18 19 20 Original AATCC 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 After AATCC 100 100 100 100 90 100 90 100 80 90 5 Standard 60 C. Test washes * Method 22 After AATCC 80 80 90 90 90 90 80 90 80 80 10 Standard 60 C.- Test washes * Method 22 After AATCC 70 80 80 90 90 90 80 80 50 70 15 Standard 60 C. Test Washes * Method 22 * according to EN ISO 6330: 2000; Drying method F (tumbler drying (70 C.))

[0192] The following items are comprised by the present invention: [0193] 1. Organopolysiloxane comprising at least one structural unit (i) and/or (vi):

##STR00015## [0194] wherein [0195] R.sup.6 independently comprises at least one C.sub.8-28 alkyl group, preferably C.sub.14-20 alkyl group, more preferably C.sub.16-18 alkyl group and at least one urea group, and [0196] R.sup.7 independently is selected from CH.sub.3, OH and a C.sub.1-5 alkoxy group. [0197] 2. Organopolysiloxane according to item 1, wherein [0198] R.sup.6 comprises at least one C.sub.8-28 alkyl urea group

##STR00016## [0199] more preferably one C.sub.14-20 alkyl urea group, more preferably a C.sub.16-18 alkyl urea group. [0200] 3. Organopolysiloxane according to item 1 or 2, wherein [0201] R.sup.6 is selected from

##STR00017## [0202] wherein [0203] R.sup.10 independently is H or R.sup.1, [0204] R.sup.11 independently is C(O)NHC.sub.8-28 alkyl provided that R.sup.6 comprises at least one R.sup.11, [0205] k is 2-4, preferably 2-3 and [0206] l is 2-4, preferably 2-3. [0207] 4. Organopolysiloxane according to any one of the preceding items, wherein the organopolysiloxane further comprises at least one structural unit selected from

##STR00018## [0208] wherein [0209] R.sup.5 independently is a C.sub.8-28 alkyl group, preferably C.sub.14-20 alkyl group, more preferably C.sub.16-18 alkyl group, [0210] R.sup.8 is independently selected from

##STR00019## [0211] R.sup.6 and R.sup.7 are as defined above. [0212] 5. Organopolysiloxane according to any one of the preceding items, wherein said organopolysiloxane is independently capped with end groups selected from

##STR00020## [0213] wherein [0214] R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are as defined above. [0215] 6. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (i) is in the range of 25-100 mol-%, preferably 50-100 mol-%. [0216] 7. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (vi) is in the range of 25-100 mol-%, preferably 50-100 mol-%. [0217] 8. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (ii) is in the range of 0-50 mol-%, preferably 0 30 mol-%. [0218] 9. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (iii) is in the range of 0-40 mol-%, preferably 0 20 mol-%. [0219] 10. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (iv) and/or (vii) is in the range of 0-20 mol-%, preferably 0-10 mol-%. [0220] 11. Organopolysiloxane according to any one of the preceding items, wherein the molar portion of the structural unit (v) is in the range of 0-50 mol-%, preferably 0 30 mol-%. [0221] 12. Organopolysiloxane according to any one of the preceding items, wherein the total basic nitrogen content as measured by titration is 0-3 wt %, preferably 0-1.5 wt %, more preferably 0.01-0.5 wt %. [0222] 13. Method for preparing an organopolysiloxane according to any one of items 1-13, comprising the steps of [0223] a) providing an organopolysiloxane and/or alkoxysilane having NCO-reactive primary and/or secondary amine groups, [0224] b) reacting the organopolysiloxane and/or alkoxysilane according to a) with C.sub.8-28 alkyl isocyanate; and [0225] c) optionally hydrolyzing/condensing the alkoxysilane obtained in step b) to the organopolysiloxane. [0226] 14. Method according to item 13, wherein the organopolysiloxane according to a) is obtained by equilibration in the presence of or by hydrolysis/condensation of (C.sub.1-5 alkoxy)silanes having at least one NCO-reactive primary and/or secondary amine group. [0227] 15. Method according to item 13, wherein the (C.sub.1-5 alkoxy)silane having at least one NCO-reactive primary and/or secondary amine group has the structure

##STR00021## [0228] wherein R.sup.7 and R.sup.8 are as defined above. [0229] 16. Method according to any one of items 14-15, wherein the equilibration is carried out in the presence of an organopolysiloxane comprising structural units (ii), (iii), and/or (v) in the presence of a catalyst and water. [0230] 17. Method according to any one of items 13-16, wherein step b) is preferably carried out in the presence of di-n-butyltin dilaurate, tin(II) octoate, dibutyltin diacetate, potassium octoate, zinc dilaurate, bismuth trilaurate or tertiary amines, such as 1,4-diazabicyclo[2,2,2]octane, dimethylcyclohexylamine, dimethylaminopropyldipropanolamine, pentamethyldipropylenetriamine, N-methylimidazole or N-ethylmorpholine, optionally at elevated temperature, e.g. 40 140 C. [0231] 18. Organopolysiloxane obtainable by a method according to any one of items 13-17. [0232] 19. Composition comprising [0233] (1) at least one reaction product (S) obtainable by reacting at least one compound (A) of

##STR00022## [0234] wherein R.sup.1=XYZ or Z, wherein

##STR00023## [0235] R.sup.3=XYZ, Z or YZ provided that in case of the meaning of YZ in the residue R.sup.2 n is replaced by n, [0236] R.sup.4=XYZ or (CH.sub.2).sub.nH, [0237] B.sup.1=VWZ or Z, wherein

##STR00024## [0238] R.sup.s independently from each other is OH, YZ,

##STR00025## [0239] provided that at least one residue R.sup.s in formula (III) is an OH group, and [0240] n, n, n, n and m independently from each other is an integer, wherein [0241] n=0-2, [0242] n=0-4, [0243] n=1-4, [0244] n=0-4 and [0245] m=8-30, preferably 12-26, more preferably 14-22, [0246] having at least one non-blocked or at least partially blocked di-, tri- or polyisocyanate (IC), wherein the portion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between 1.8 and 10 per mol. [0247] (2) at least one organopolysiloxane according to any one of items 1-12 or 18, (3) optionally at least one non-blocked or at least partially blocked di-, tri- or polyisocyanate (IC), [0248] (4) optionally at least one liquid medium, in particular water or an organic solvent, and [0249] (5) optionally at least one emulsifier. [0250] 20. Preparation according to item 19, wherein component (1) constitutes 10-90 wt %, preferably 20-80 wt %, more preferably 25-65 wt %, based on the total mass of components (1) and (2). [0251] 21. Preparation according to any one of items 19-20, wherein component (2) constitutes 10-90 wt %, preferably 20-80 wt %, more preferably 30-70 wt %, based on the total mass of components (1) and (2). [0252] 22. Preparation according to any one of items 19-21, wherein component (3) constitutes 0-50 wt %, preferably 1-35 wt %, more preferably 5-35 wt %, based on the total mass of components (1), (2) and (3). [0253] 23. Preparation according to any one of items 19-22, wherein component (5) constitutes 0-25 wt %, preferably 1-20 wt %, more preferably 2-15 wt %, based on the total mass of components (1), (2), optionally (3) and (5). [0254] 24. Preparation according to any one of items 19-23 in the form of a dispersion, preferably in the form of an aqueous dispersion. [0255] 25. Preparation according to any one of items 19-24, wherein the solids content of the dispersion is 10-40 wt %, preferably 15-30 wt %. [0256] 26. Preparation according to any one of items 19-25, wherein the polyisocyanate (IC) is selected from the group consisting of 2,4-toluylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), higher chain homologues of diphenylmethane diisocyanate (polymer MDI), 4-methyl-cyclohexane-1,3-diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dimer diisocyanate, and mixtures such as for example mixtures of MDI and polymeric MDI, and derivatives thereof. [0257] 27. Preparation (Z) according to any one of items 19-26, wherein for the reaction product (S) the molar ratio of free isocyanate (NCO) groups in the polyisocyanate (IC) to isocyanate-reactive groups in compound (A) is adjusted to 1:1 to 1:1.3, preferably 1 to 1.1. [0258] 28. Preparation (Z) according to item 27, wherein the isocyanate-reactive groups are hydroxy groups, primary and/or secondary amino groups. [0259] 29. Preparation (Z) according to any one of items 19-28, wherein the organic solvent according to component (4) is selected from esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate or amyl acetate, ketones, e.g. acetone, methyl ethyl ketone and saturated hydrocarbons, such as n-hexane, n-heptane or n-octane. [0260] 30. Preparation according to any one of items 19-29, wherein the emulsifier according to component (5) is selected from anionic, cationic and non-ionic surfactants. [0261] 31. Preparation according to any one of items 19-30, wherein the preparation is free of fluorine compounds. [0262] 32. Use of the organopolysiloxane according to any one of items 1-12 or 18 or of the preparation according to any one of items 19-31 as a hydrophobing agent. [0263] 33. Use according to item 32 as a hydrophobing agent on sheet materials, in particular textile substrates, paper, leather, and mineral sheet materials. [0264] 34. Use according to item 33 as an additive in paints, varnishes, or plasters. [0265] 35. Method of hydrophobizing substrates, comprising applying the preparation Z according to any one of items 19-31 or the organopolysiloxane according to any one of items 1-12 or 18 to a substrate, preferably a sheet material, more preferably a textile substrate, paper, leather or mineral substrate. [0266] 36. Method according to item 35, wherein the application is carried out by means of spraying, dipping, impregnating, brushing or by sponge application. [0267] 37. Method according to item 35 or 36, wherein the preparation is applied to a textile substrate by means of forced application or by the exhaust method.