PREPARATION AS WATER REPELLING AGENTS

Abstract

The invention relates to preparations comprising a polyurethane and/or polyurea and a copolymer as well as their use as hydrophobing agents,

Claims

1. Preparation (Z), comprising (1) at least one conversion product (S) obtainable by reacting at least one compound (A) of the formula ##STR00022## and/or ##STR00023## wherein R.sup.1 is XYZ or Z with X(CH.sub.2).sub.n, Y ##STR00024## or, ##STR00025## Z(CH.sub.2).sub.mCH.sub.3, R.sup.2is ##STR00026## R.sup.3 is XYZ, Z or YZ, with the provision that in the case of the meaning of YZ n is replaced by n in residue R.sup.2, R.sup.4 is XYZ or (CH.sub.2).sub.nH, B.sup.1 VWZ or Z, with V(CH.sub.2).sub.n or ##STR00027## W ##STR00028## B.sup.2 is (CH.sub.2).sub.nNH.sub.2, or ##STR00029## B.sup.3 is VWZ, Z or ##STR00030## B.sup.4 is VWZ or ##STR00031## Q is (CH.sub.2).sub.n and n, n, n, and m are each independently an integer, wherein n=0-2, n=0-4, n=1-4, N=0-4 and m=8-30, preferably 10-26, more preferably 10-22, with at least one unblocked or at least partially blocked di-, tri- or polyisocyanate (IC), wherein the proportion of free isocyanate (NCO) groups in the polyisocyanate (IC) is between. 1.8 and 10 per mole, (2) at least one copolymer (C) comprising at least one building block of the formula ##STR00032## wherein ##STR00033## and/or ##STR00034## and/or ##STR00035## wherein R.sup.5 is H or CH.sub.3, R.sup.6 is a C.sub.12-C.sub.40 hydrocarbon residue, R.sup.7 is a linear or branched aliphatic C.sub.1-C.sub.8 hydrocarbon residue, U is O or NH, R.sup.8 is ##STR00036## or CH.sub.2(CH.sub.2).sub.pOH, and k and p are each independently an integer wherein k=1-5 and p=0-10, (3) optionally at least one unblocked or at least partially blocked di-, tri or polyisocyanate (IC), (4) optionally water and/or at least one organic solvent and (5) optionally at least one surface-active substance.

2. The preparation (Z) according to claim 1, wherein the latter is free from fluorine compounds,

3. The preparation (Z) according to claim 1, wherein the component (1) accounts for 10-90 wt. %, preferably 20-80 wt. %, more preferably 25-65 wt. % relative to the total preparation (Z).

4. The preparation (Z) according to claim 1, wherein the component (2) accounts for 10-90 wt. %, preferably 20-80 wt. %, more preferably 30-70 wt. % relative to the total preparation (Z).

5. The preparation (Z) according to claim 1, wherein the component (3) accounts for 0-50 wt. %, preferably 5-35 wt. %, more preferably 10-25 wt. % relative to the total preparation (Z).

6. The preparation (Z) according to claim 1, wherein the component (4) accounts for 20-99.9 wt. %, preferably 40-99.8 wt. %, more preferably 50-99 wt. % relative to the total preparation (Z).

7. The preparation (Z) according to claim 1, wherein the component (5) accounts for 0-20 wt. %, preferably 1-20 wt. %, more preferably 2-15 wt. %, relative to the total amount of components (1), (2) and optionally (3) and/or optionally (5).

8. The preparation (Z) according to claim 1 wherein the component (2) contains 30-90 mol-%, preferably 40-85 mol-%, more preferably 50-80 mol-%, of the building block M(1),

9. The preparation (Z) according to claim 1, wherein the component (2) contains 5-65 mol %, preferably 10-55 mol %, more preferably 16-49 mol %, of the building block M(2).

10. The preparation (Z) according to claim 1, wherein the component (2) contains 0.1-8 mol %, preferably 0.5-5 mol %, more preferably 1-4 mol %, of the building block M(3).

11. The preparation (Z) according to claim 1, wherein the component (2) contains 30-90 mol % of the building block M(1), 5-65 mol % of the building block, M(2) and 0.1-5 mol % of the building block M(3).

12. The preparation (Z) according to claim 1, wherein for the conversion 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.

13. The preparation (Z) according to claim 12, wherein the isocyanate-reactive groups are hydroxy groups and/or primary amino groups.

14. The preparation (Z) according to claim 1, wherein the compound (A) is hydrophobic.

15. The preparation (Z) according to claim 1, wherein the isocyanate (IC) is selected from the group consisting of 2,4-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), higher chain homologues of the 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 mixtures of MDI and polymer MDI, and derivatives thereof.

16. The preparation (Z) according to claim 1, wherein the organic solvent according to component (4) is selected from esters, e.g. ethyl acetate, n-propylacetate, isopropylacetate, n-butyl acetate, isobutyl acetate or amylacetate, ketones, e.g. acetone, methyl ethyl ketone and saturated hydrocarbons, such as n-hexane, n-heptane or n-octane.

17. The preparation (Z) according to claim 1, wherein component (5) is selected from anionic, cationic and non-ionic surfactants.

18. The preparation (Z) according to claim 1 further comprising at least one conversion product (CD1) obtainable by the following steps a) Providing at least one di-, tri- or polyisocyanate (IC), b) Reacting (IC) with at least one organic compound (O) which contains at least one isocyanate-reactive group, wherein the molar ratio of isocyanate groups to isocyanate-reactive groups is adjusted to 10:1 to 3:2, preferably 4:1 to 2:1, and c) Carbodiimidizing the products present after step b) with a catalyst at temperatures of 25-150 C., preferably 40-100 C.

19. The preparation (Z) according to claim 1, comprising at least one conversion product (CDI) obtainable by the following steps a) Providing at least one di-, tri- or polyisocyanate (IC), b) Carbodiimidizing of (IC) with a catalyst at temperatures of 25-150 C., preferably of 40-100 C.; and c) Reacting the products present after step b) with at least one organic compound (O) which contains at least one isocyanate-reactive group, wherein the molar ratio of isocyanate groups to isocyanate-reactive groups is adjusted to a ratio of 1:1.

20. The preparation (Z) according to claim 18, wherein the organic compound (O) is selected from the group consisting of monoamine, monoalcohol, diamine, diol, polyamine and polyol, preferably monoamine, monoalcohol, diamine and diol.

21. The preparation (Z) according to claim 18, wherein the organic compound (O) is selected from the group consisting of R.sup.9OH, R.sup.9NH.sub.2, HOR.sup.10OH and H.sub.2NR.sup.10NH.sub.2, wherein R.sup.9 is a saturated or unsaturated hydrocarbon residue having 12-40 carbon atoms, which may optionally contain at least one group selected from COO, CO, CONH and O and is optionally substituted with at least one polyalkylene oxide, cationic, anionic and/or amphoteric group, and R.sup.10 is a saturated or unsaturated hydrocarbon group residue having 12-40 carbon atoms which may optionally contain at least one group selected from COO, CO, CONH and O and is optionally substituted with at least one polyalkylene oxide, cationic, anionic and/or amphoteric group.

22. The preparation (Z) according to claim 21, wherein the cationic group is selected from an ammonium group.

23. The preparation (Z) according to claim 21, wherein the anionic group is selected from carboxylate, sulfonate and/or phosphate.

24. The preparation (Z) according to claim 21, wherein the amphoteric group is selected from a betaine and/or stab betaine.

25. The preparation (Z) according to claim 20, wherein the monoalcohol is selected from cetyl alcohol, stearyl alcohol, behenyl alcohol, glycerin distearate, glycerin dibehenate, pentaerythritol tristearate, sorbitan tristearate, triethanolamine distearate and mixtures thereof.

26. The preparation (Z) according to claim 20, wherein the monoamine is selected from stearylamine, distearylamine, conversion products of diethanolamine with fatty acids, and mixtures thereof.

27. The preparation (Z) according to claim 20, wherein the diamine is selected from dimer fatty acid diamines.

28. The preparation (Z) according to claim 20, wherein the diol is selected from dimer fatty acid diols.

29. The preparation (Z) according to claim 18, wherein the catalyst for carbodiimidizing is selected from phospholene oxides, in particular 3-methyl-1-phenyl-2-phospholenoxide, 1-methyl-3-phospholenoxide, 1-methyl-2-phospholenoxide, 1,3-dimethyl-2-phospholenoxide and 1,3-dimethyl-3-phospholenoxide, and mercury compounds.

30. The preparation (Z) according to claim 18, wherein the conversion product (CDI) is 1-50 wt. %, preferably 5-35 wt. % relative to the total preparation.

31. The use of a preparation (Z) according to claim 1 as hydrophobing agent.

32. The use of the preparation (Z) according to claim 31 as a hydrophobing agent on fabrics, in particular textile substrates, paper, leather and mineral fabrics.

33. The use of the preparation (Z) according to claim 31 as additive in paints, varnishes or plasters.

34. A method for hydrophobizing substrates, comprising applying the preparation (Z) according to claim 1 to a substrate, preferably a fabric, more preferably a textile substrate, paper, leather or mineral substrate.

35. The method according to claim 34, wherein the application is by spraying, dipping, impregnating, painting or sponge application.

36. The method according to claim 34, wherein the preparation (Z) is applied to a textile substrate by forced application or by the exhaust method.

37. The method according to claim 34, wherein the preparation (Z) is applied to an already washed textile substrate.

Description

EXAMPLES

[0156] Fabric Finishing, Water Repellency

[0157] The following examples explain the invention. The finishes were applied to textile fabrics on a type LFV 350/2 RFA (Benz, Switzerland) laboratory padder with subsequent drying and hot treatment on a type TKF 15/M 350 (Benz, Switzerland) laboratory tensioning frame. The liquor absorption was determined by weighing out the finished test samples before and after application.

[0158] The modified substrates were tested in a standard climate (20 C., 65% relative humidity) 24 hours after conditioning. The coating quantities and the conditions of the hot treatment are listed in Tables 3a and 3b.

[0159] The water repellency was tested on the textile fabrics both by spray test according to the AATCC Standard Test Method 22 and by the much more differentiated Bundesmann test according to DIN 53 888. The test according to the AATCC Standard Test Method 22 is performed by spraying distilled water under controlled conditions onto the textile substrate to be tested and then visually comparing the wetting pattern to images of an evaluation standard listed in the test method. The numerical values specified refer to the appearance of the surface after water spraying and have the following meanings:

TABLE-US-00001 100 = no water droplets adhering or wetting of the upper surface 90 = isolated adherence of water droplets or wetting of the upper surface 80 = wetting of the upper surface at the water impact points 70 = Partial wetting of the entire upper surface 50 = Complete wetting of the entire upper surface 0 = Complete wetting of the entire upper and lower surface (wetting through).

[0160] In the Bundesmann test according to DIN 53 888, the textile substrate to be tested is exposed to the effect of a defined artificial rain and the amount of water absorbed after a certain period is determined as a percentage (marked as water absorption in Tables 3a and 3b). Furthermore, the water beading effect designated as beading effect in Tables 3a and 3b is used for the evaluation. This is evaluated by visual comparison of the irrigated test samples with images listed in the DIN standard according to 5 grades, which are designated as follows: [0161] Grade 5=small droplets roll off vividly [0162] Grade 4=formation of larger droplets [0163] Grade 3=droplets get stuck on the test sample in places [0164] Grade 2=test sample partially wetted [0165] Grade 1=test sample is wetted or perfused over the entire surface.

[0166] The test samples were washed at 60 C. and dried in accordance with EN ISO 6330:2000 in order to test the resistance of the finished textile fabrics to washing processes.

[0167] Determination of Breathability Migration Test

[0168] A laminate consisting of an untreated polyester outer fabric and a breathable Sympatex membrane is finished with the preparation according to the invention. The preparation is applied to one side of the stretched laminate using pump spray on the polyester outer fabric. The application and coating quantities can be found in Table 3c.

[0169] Water vapor permeability is measured in accordance with AS 1099 Method B2. A laminate finished with the hydrophobing agent is stretched over a cup filled with potassium acetate. This is placed bottom-up with the stretched side on a wet fleece and the amount of water absorbed by the hygroscopic salt through the membrane is measured. Thus, the breathability value in g/24 h/m.sup.2 is obtained.

[0170] Thermal Storage TestMigration Test

[0171] The treated laminates (Table 3c) are stored in the oven at 60 C. for one week. The breathability is then determined, and the loss of breathability as compared to the original values is calculated as a percentage (%). The aim is to minimize the loss as far as possible.

[0172] DelaminationAdhesion

[0173] PES fabric samples finished with the padding process Table 4 are laminated together with the corresponding adhesive nonwoven in a sandwich-like manner. For this purpose, the adhesive nonwoven is laid between 2 finished fabric samples and the structure is pressed with a thermal printing press from the company Wagner (model: Motifprint Printstar) for 30 seconds at a pressure of 2.5 bar at 135 C. To test adhesion, test specimens measuring 305 cm are then punched out. The adhesion is measured analogous to DIN 54310 with a Zwick testing machine. The value is given as the separating force. The higher the separating force, the higher the adhesion.

[0174] The following commercially available products were used: [0175] Ruco-Guard WEB: Solids content: 25%, aqueous emulsion of a butanone oxime blocked aromatic polyisocyanate; Rudolf GmbH [0176] Ruco-Guard AFB6 conc.: Solids content: 27%, aqueous emulsion of an oleophobing and hydrophobing agent based on a fluorocarbon polymer containing 2-perfluorohexypethyl methacrylate, Rudolf GmbH [0177] Freepell 1225: Solids content: 25%, aqueous emulsion of a paraffin wax and a fatty acid-modified melamine resin, Emerald Performance Materials [0178] Phobotex APK: Solids content: 25%, aqueous emulsion of a paraffin wax and a fatty acid aluminium salt, Huntsman [0179] Xiameter MEM-0075: Solids content: 60%, aqueous emulsion of a reactive methylhydrogen polysiloxane, Xiameter [0180] Lutensol ON 110: Isodecanol 11 EO; BASF [0181] Arquad 2C75: Dicocosdimethylammonium chloride, Akzo Nobel [0182] Ethoquat HT25: Stearyl-N,N-polyoxyethylene methylammonium chloride, Akzo Nobel

Examples for the Production of Component (1)

[0183] Compound (A)

[0184] General Manufacturing Instruction for Compounds of Formula (Al) and/or (All)

[0185] The starting materials (a1, a2 or a3) and (b1) listed in Table 1 are melted under inert gas and stirring in the quantities in grams listed in Table 1 in a suitably dimensioned three-neck flask equipped with distillation cooler, controllable stirrer and internal thermometer The mixture is then heated to the final temperature (T) specified in Table 1 and stirred until no more conversion water is distilled off and the acid number (AN) specified in Table 1 is reached. If necessary, 0.1% sulphuric acid can be added as a catalyst in the esterification reactions. The amidation reactions do not require the addition of a catalyst. The resulting condensation product is poured out and after cooling processed into flakes.

[0186] Compound (A)

[0187] Special Manufacturing Instructions for Compounds (A) of Formula (Al) and/or (All) Using Alkyl Isocyanates (b2) and Further Processing to Conversion Product (S)

[0188] The compounds (a1) and (b2) listed in Table 1 in grams are presented in isopropyl acetate (solvent (SO)) in a suitably dimensioned three-necked flask equipped with reflux cooler, adjustable stirrer, internal thermometer and dropping funnel. Then 0.05% 1,4-diazabicylo(2,2,2)octane as catalyst, based on the total amount of components, is added and the mixture is stirred at 8 C. until no more NCO band is visible in the IR spectrum. Then the amount in grams of component (IC) specified in Table 1 is added to the mixture to prepare the conversion product (S) and stirring is continued at 50 C. until no more NCO band is visible in the IR spectrum.

[0189] Conversion Products (S) (=component (1)):

[0190] General Manufacturing Instruction for Conversion Products (S) From a Compound (A) and Unblocked or Partially Blocked Di- , Tri- or Polyisocyanates (IC)

[0191] The compounds (A) and the components (IC) listed in Table 1 are presented in isopropyl acetate (SO) in the quantities in grams listed in Table 1 in a suitably dimensioned three-necked flask equipped with reflux condenser, adjustable stirrer, internal thermometer and dropping funnel. Then 0.05% 1,4-diazabicylo(2,2,2)octane as catalyst, based on the total amount of components, is added and the mixture is stirred at 65 C. until no more NCO band is visible in the IR spectrum.

[0192] Special Manufacturing Instruction for the Conversion Products (S) (=component 1) Used in Emulsions (E) 3 and 8

[0193] A conversion product (S) is used to prepare the emulsions (E) 3 in accordance with Table 1, during the preparation of which (conversion of component (A) with the isocyanate (IC) the quantity in grams of dimethylaminoethanol indicated in Table 1 is added. A conversion product (S) is used to prepare the emulsions (E) 8 in accordance with Table 1, during the preparation of which (conversion of component (A) with the isocyanate (IC)) the quantity in grams of bisoctadecylamine indicated in Table 1 is added.

[0194] Emulsions (E):

[0195] General Manufacturing Instruction for Emulsions (E) from the Conversion Products (S) (=component (1))

[0196] Oily phase: In a suitably sized beaker, the quantities in grams of conversion product (S) given in Table 1, present in the above isopropyl acetate, are presented and heated to 65-70 C. while stirring until a clear homogeneous solution is obtained. The conversion product (S) to be used may have to be melted at 65-70 C. before use to obtain a homogeneous product.

[0197] Aquoous phase: In a suitably dimensioned beaker the quantities in grams of component (5) given in Table 1 are dissolved in the indicated quantity of water at 65 C. Both phases are stirred under a high-speed stirrer to form a coarse pre-emulsion and then homogenized at 65 C. in a high-pressure homogenizing machine at 300-500 bar until an average particle size of between 0.1 and 10 micrometers is achieved. The solvent (SO) is then removed by azeotropic distillation on the rotary evaporator in a vacuum. If necessary, the pH value of the emulsion obtained is adjusted to 5-7 with 60% acetic acid, the white emulsion obtained is filtered through a 20-micrometer filter and adjusted to a solids content of 25% with water.

Examples for the Production of Component (2)

[0198] Acrylic acid 2-[[(octadecylamine)carbonyl)oxy]ethyl ester is produced analogously to example 2 in EP0448399B1.

[0199] Copolymer Emulsion (CE(2)

[0200] 62.7 g (0.150 mol) acrylic acid 2-[[(octadecylamine)carbonyl)oxy]ethyl ester, 11.1 g (0.078 mol) isobutyl methacrylate and 1.5 g (0.015 mol) glycidyl methacrylate are mixed together with 20 g dipropylene glycol and heated to 80 C. In parallel, a solution of 0.25 g Ethoquad HT 25, 1.0 g Arquad 2C75 and 7.7 g Lutensol ON 110 in 145 g water is prepared at 80 C. in a separate vessel. The aqueous and the organic phase are then mixed with an Ultra-Turrax under strong stirring and then homogenized with an ultrasonic homogenizer for 3 min until a finely divided emulsion is formed. The pre-emulsion is transferred to a three-necked flask. After repeated inerting with nitrogen, 0.18 g lauryl mercaptan is added to the pre-emulsion. Polymerization is started by adding 1.05 g 2,2-azobis[2-(2-imidazolin-2-yl)propane)dihydrochloride at about 80 C. Stir for a further 4 h at 80 C. to obtain a white emulsion with a solids content of approx. 32%.

[0201] Molar ratio in mol [%]: Monomer M(1): Monomer M(2): Monomer M(3)=e.g. 63:32:5

[0202] Copolymer Emulsion (CE(2))

[0203] 265.2 g (0.75 mol) stearyl methacrylate, 29.5 g (0.21 mol) tert-butyl methacrylate and 2.63 g (0.012 mol) glycidyl methacrylate and 2.63 g (0.02 mol) 2-hydroxyethyl methacrylate are mixed with 79.5 g dipropylene glycol and heated to 60 C. In parallel, a solution of 1.0 g Ethoquad HT 25, 4.0 g Arquad 2C75 and 30.8 g Lutensol ON 110 in 600 g water is prepared at 60 C. in a separate vessel. The aqueous and the organic phase are then mixed with an Ultra-Turrax under strong stirring and then homogenized with an ultrasonic homogenizer for 3 min until a finely divided emulsion is formed. The pre-emulsion is transferred to a three-necked flask. After repeated inerting with nitrogen, 0.72 g lauryl mercaptan is added to the pre-emulsion. Polymerization is started by adding 4.2 g 2,2-azobis(2-amidinopropane) dihydrochloride at approx. 60 C. Stir for a further 4 h at 60 C. to obtain a white emulsion with a solids content of approx. 32%.

[0204] Molar ratio in mol [%]: Monomer M(1): Monomer M(2): Monomer M(3)=e.g. 76:21:3

[0205] Copolymer Emulsion (CE(3))

[0206] 275.0 g (0.67 mol) behenyl methacrylate, 19.0 g (0.096 mol) 2-ethylhexyl methacrylate and 2.63 g (0.012 mol) glycidyl methacrylate are mixed together with 79.5 g dipropylene glycol and heated to 60 C. In parallel, a solution of 5.0 g Ethoquad HT 25 and 30.8 g Lutensol ON 110 in 600 g water is prepared at 60 C. in a separate vessel. The aqueous and the organic phase are then mixed with an Ultra-Turrax under strong stirring and then homogenized with an ultrasonic homogenizer for 3 min until a finely divided emulsion is formed. The pre-emulsion is transferred to a three-necked flask. After repeated inerting with nitrogen, 0.72 g lauryl mercaptan is added to the pre-evulsion. Polymerization is started by adding 4.2 g 2.2-azobis(2-amidinopropane) dihydrochloride at approx. 60 C. Stir for a further 4 h at 60 C. to obtain a white emulsion with a solids content of approx. 32%.

[0207] Molar ratio in mol [%]: Monomer M(1): Monomer M(2): Monomer M(3)=e.g. 86:12:2

[0208] Copolymer Emulsion (CE(4))

[0209] 265.0 g (0.67 mol) behenyl acrylate, 25.0 g (0.18 mol) tert-butyl methacrylate, 2.63 g (0.02 mol) 2-hydroxyethyl methacrylate and 2.63 g (0.012 mol) glycidyl methacrylate are mixed with 79.5 g dipropylene glycol and heated to 60 C. In parallel, a solution of 5.0 g Ethoquad HT 25 and 30.8 g Lutensol ON 110 in 600 g water is prepared at 60 C. in a separate vessel. The aqueous and the organic phase are then mixed with an Ultra-Turrax under strong stirring and then homogenized with an ultrasonic homogenizer for 3 min until a finely divided emulsion is formed. The pre-emulsion is transferred to a three-necked flask. After repeated inerting with nitrogen, 0.72 g lauryl mercaptan is added to the pre-emulsion. Polymerization is started by adding 4.2 g 2.2-azobis(2-amidinopropane) dihydrochloride at approx. 60 C. Stir for a further 4 h at 60 C. to obtain a white emulsion with a solids content of approx. 32%.

[0210] Molar ratio in mol [%]: Monomer M(1) Monomer M(2): Monomer M(3)=e.g. 76:20:4

[0211] Preparation of the Conversion Product ((CDI) 1)

[0212] In a suitably dimensioned three-necked flask equipped with reflux cooler, adjustable stirrer and internal thermometer 174 g (1 mol) toluene diisocyanate (mixture 2,4-isomer:2,6-isomer 80:20) are dissolved in 309 g methyl ethyl ketone. Then 135 g (0.5 mol) stearyl alcohol are added in portions, while the mixture is slowly heated to about 80 C. After 1 h stirring, the free NCO content is determined. If the stearyl alcohol has completely converted, 0.7 g LUBIO Polykat 2 (phospholenoxide derivative) is added and the carbodiimidization reaction is started. The reaction mixture is heated for 9 h at 80 C. until no more NCO band is visible in the IR spectrum.

[0213] 1.73 g Ethoquad HT 25, 0.65 g Arquad 2 C 75 and 1.29 g Lutensol ON 110 are dissolved in 346 g water at 65 C. in a suitably dimensioned beaker.

[0214] The aqueous phase and 200 g of the reaction mixture is then stirred with a high-speed stirrer to form a coarse pre-emulsion and subsequently homogenized at 65 C. in a high-pressure homogenizer at 300-500 bar until an average particle size between 0.1 and 10 micrometers is achieved. The solvent is then removed by distillation on a rotary evaporator in a vacuum. If necessary, the pH value of the emulsion obtained is adjusted to 5-7 with 60% acetic acid, the white emulsion obtained is filtered through a 20-micrometer filter and adjusted to a solids content of 20% with water.

[0215] Preparation of the Conversion Product ((CDI) 2)

[0216] In a suitably dimensioned three-necked flask equipped with reflux cooler, adjustable stirrer and internal thermometer 174 g (1 mol) toluene diisocyanate (mixture 2,4-isomer:2,6-isomer 80:20) are dissolved in 328 g methyl ethyl ketone. Then 82 g (0.25 mol) behenyl alcohol and 71 g (0.13 mol Pripol 23 (dimer fatty acid diol) are added in portions, while the mixture is slowly heated to about 80 C. After 1 h stirring, the free NCO content is determined. If the two alcohols have been completely converted, 0.7 g LU810 Polykat 2 (phospholene oxide derivative) is added and the carbodiimidization reaction is started. The reaction mixture is heated for 9 h at 80 C. until no more NCO band is visible in the IR spectrum.

[0217] 0.73 g Ethoquad NT 25, 1.65 g Arquad 2 C 75 and 1.29 g Lutensol ON 110 are dissolved in 346 g water at 65 C. in a suitably dimensioned beaker.

[0218] The aqueous phase and 200 g of the reaction mixture is then stirred with a high-speed stirrer to form a coarse pre-emulsion and subsequently homogenized at 65 C. in a high-pressure homogenizer at 300-500 bar until an average particle size between 0.1 and 10 micrometers is achieved. The solvent is then removed by distillation on a rotary evaporator in a vacuum. If necessary, the pH value of the emulsion obtained is adjusted to 5-7 with 60% acetic acid, the white emulsion obtained is filtered through a 20-micrometer filter and adjusted to a solids content of 20% with water.

[0219] Preparation of the Preparations (Z) According to the Invention

[0220] The emulsions (E) listed in Table 1, containing components (1) and (5), are mixed with component (2). Where appropriate, components (3) and (4) (water) and, where appropriate, (CDI) are added in the weight ratios stated, resulting in the preparations (Z) stated in Tables 2a and 5. Table 2b lists non-inventive hydrophobing agents which are used unchanged in the application examples,

Finishing Examples

[0221] Application of Water-Based Preparations (Z) on Textile Fabrics:

[0222] Finishing conditions and test results are given in Tables 3a, 3b, 3c, 4, 6, 7, 8 and 9.

TABLE-US-00002 TABLE 1 (according to the invention): Preparation of component (1) and its emulsions (E); quantities in grams Materials 1 2 3 4 5 6 7 8 Compound (a) (a1) glycerol 92.1 92.1 92.1 (A) (a2) triethanolamine 149.0 149.0 (a3) bis(aminoethyl)amine 103.0 103.0 103.0 lauric acid 400.0 (b) (b1) palmitic acid 512.0 512.0 stearic acid 568.0 behenic acid 680.0 680.0 (b2) stearyl isocyanate 591.0 591.0 final temperature (T) in C. 90 160 160 165 160 165 90 160 acid number (AN) <5 <5 <10 <5 <5 <5 Conversion product compound (A) 123.0 156.0 156.0 141.0 134.0 113.0 128.0 113.0 (S) = bis(octadecyl)amine 10.4 Component (1) dimethylaminoethanol 5.4 isocyanate (IC) 2,4-toluylene 56.3 64.7 47.3 41.0 diisocyanate/ trimethylol- propanurethane with 13.5 wt. % NCO hexamethylene 53.1 41.4 50.5 35.7 diisocyanate trimer with 21.7 wt. % NCO solvent (SO) isopropyl acetate 179 209 203 206 184 160 164 164 Emulsion (E) conversion product (S) 100.0 152.0 152.0 124.0 124.0 113.0 113.0 113.0 containing component (5) Ethoquad HT 25 0.25 0.53 0.53 0.31 0.31 0.40 0.40 0.40 components emulsifier (Em) Disponil A 1080 2.15 4.30 4.30 2.68 2.68 2.71 2.71 2.71 (1) and (5) Arquad 2C75 1.86 3.96 3.96 2.77 2.77 2.86 2.86 2.86 water 261 456 456 306 306 341 341 341 acetic acid 60% 0.30 0.50 0.50 0.40 0.40 0.40 0.40 0.40

TABLE-US-00003 TABLE 2a Mixing ratios of the preparation (Z) according to the invention Parts by weight [%] Parts by weight [%] Copolymer emulsion (CE) Parts by weight [%] emulsion (E) containing containing components Component (3) RUCO- Parts by weight [%] components (1) and (5) (2) and (5) GUARD WEB Water Preparation (Z) 45 of (E) 1 45 of (CE) 1 10 1 (according to the invention) 45 of (E) 1 45 of (CE) 1 10 2 (according to the invention) 45 of (E) 2 45 of (CE) 1 10 3 (according to the invention) 45 of (E) 2 45 of (CE) 1 10 4 (according to the invention) 45 of (E) 3 45 of (CE) 2 10 5 (according to the invention) 45 of (E) 3 45 of (CE) 2 10 6 (according to the invention) 45 of (E) 4 45 of (CE) 2 10 7 (according to the invention) 45 of (E) 4 45 of (CE) 2 10 8 (according to the invention) 45 of (E) 5 45 of (CE) 3 10 9 (according to the invention) 45 of (E) 5 45 of (CE) 3 10 10 (according to the invention) 45 of (E) 6 45 of (CE) 3 10 11 (according to the invention) 45 of (E) 6 45 of (CE) 3 10 12 (according to the invention) 45 of (E) 7 45 of (CE) 4 10 13 (according to the invention) 45 of (E) 7 45 of (CE) 4 10 14 (according to the invention) 45 of (E) 8 45 of (CE) 4 10 15 (according to the invention) 45 of (E) 8 45 of (CE) 4 10 16 (according to the invention)

TABLE-US-00004 TABLE 2b non-Inventive Preparations (Z) Products Preparation (Z) RUCO-GUARD AFB6 conc 17 (non-inventive) Frepell 1225 18 (non-inventive) Phobotex APK 19 (non-inventive) Xiameter MEM-0075 20 (non-inventive)

TABLE-US-00005 TABLE 3a Forced application to cotton poplin, 155 g/m.sup.2; finishing results Application amount of preparation (Z) 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 2a/2b 1 2 3 4 5 6 7 8 9 10 11 Original AATCC Standard 100 100 100 100 100 100 100 100 100 100 100 Test Method 22 DIN 53 888 4 5 4 4 3 4 4 5 2 3 4 beading effect DIN 53 888 20 14 22 26 24 23 20 16 28 25 21 water absorption After 10 AATCC Standard 90 90 90 90 90 90 90 30 80 80 90 60 C.- Test Method 22 washing * Preparation (Z) according according to the invention non-inventive to Tab. 2a/2b 12 13 14 15 16 17 18 19 20 Original AATCC Standard 100 100 100 100 100 100 90 90 100 Test Method 22 DIN 53 888 5 4 5 2 3 5 1 2 1 beading effect DIN 53 888 16 22 15 31 26 12 41 35 38 water absorption After 10 AATCC Standard 90 90 90 80 80 90 70 70 70 60 C.- Test Method 22 washing * * = according to EN ISO 6330:2000; tumble drying (70 C.)

TABLE-US-00006 TABLE 3b Forced application on PES fabric, 75 g/m.sup.2; Finishing results Application amount of preparation (Z) 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 2a/2b 1 2 3 4 5 6 7 8 9 10 11 Original AATCC Standard 100 100 100 100 100 100 100 100 100 100 100 Test Method 22 DIN 53 888 5 5 4 5 4 5 5 5 4 4 5 beading effect DIN 58 888 15 11 19 14 19 12 14 12 21 18 14 water absorption in % After 10 AATCC Standard 100 100 90 100 90 100 100 100 90 100 90 60 C.- Test Method 22 washing * Preparation (Z) according according to the invention non-inventive to Tab. 2a/2b 12 13 14 15 16 17 18 19 20 Original AATCC Standard 100 100 100 100 100 100 90 90 100 Test Method 22 DIN 53 888 5 5 5 4 4 5 2 2 3 beading effect DIN 58 888 13 13 11 21 20 10 29 32 26 water absorption in % After 10 AATCC Standard 100 100 100 90 100 100 70 70 80 60 C.- Test Method 22 washing * * = according to EN ISO 6330:2000; tumble drying (70 C.)

TABLE-US-00007 TABLE 3c Spray application on polyester fabric, laminated on one side with polyester film, 125 g/m.sup.2 Finishing result and breathability (g/m.sup.2/24 h) before and after storage Application amount of preparation (Z) 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 2a/2b 1 2 3 4 5 6 7 8 9 10 11 Original AATCC 100 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 breathability 7856 8512 9246 8632 7985 8647 9254 7968 8347 8047 7583 JIS L 1099 Method B2 7 d, 60 C. AATCC 100 100 100 100 100 100 100 100 100 100 100 Standard Test Method 22 breathability 7653 8045 8268 7871 7654 8207 8635 7057 8197 7640 7045 JIS L 1099 Method B2 decrease 3% 5% 11% 9% 4% 5% 7% 11% 2% 5% 7% in % Preparation (Z) according according to the invention non-inventive to Tab. 2a/2b 12 13 14 15 16 17 18 19 20 Original AATCC 100 100 100 100 100 100 90 90 100 Standard Test Method 22 breathability 9224 8547 8145 9158 8025 7941 9784 3226 8032 JIS L 1099 Method B2 7 d, 60 C. AATCC 100 100 100 100 100 100 90 80 100 Standard Test Method 22 breathability 8067 7952 7421 8547 7057 7819 1099 2488 7354 JIS L 1099 Method B2 decrease 13% 7% 9% 7% 12% 2% 89% 23% 8% in %

TABLE-US-00008 TABLE 4 Forced application on PES fabric, 75 g/m.sup.2 subsequent adhesion tests with adhesive fleece Application amount of preparation (Z) 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Pressing with adhesive fleece: 20 seconds 120 C. 2.5 bar Preparation (Z) according to Tab. according to the invention non-inventive 2a/2b 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Force according 9.5 10.1 9.6 8.9 9.1 11.2 8.1 9.0 9.7 10.2 9.8 9.1 11.1 9.8 9.5 8.8 6.0 5.2 4.6 0.8 to DIN 54310* *Separating force Clamping length 200 mm Pre-measurement path length 20 mm Test speed 230 mm Measuring distance 230 mm

TABLE-US-00009 TABLE 5 Mixing ratios of the preparations (Z) according to the invention Parts by weight [%] Parts by weight [%] Copolymer emulsion (CE) emulsion (E) containing containing components Parts by weight Parts by weight components (1) and (5) (2) and (5) [%] (CDI) [%] Water Preparation (Z) 45 of (E) 1 45 of (CE) 1 10 (CDI) 1 21 (according to the invention) 45 of (E) 2 45 of (CE) 1 10 (CDI) 2 22 (according to the invention)

TABLE-US-00010 TABLE 6 Forced application to cotton poplin, 155 g/m.sup.2, Finishing results Application amount of preparation (Z): 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 5 21 22 Original AATCC Standard Test 100 100 Method 22 DIN 53 888 beading effect 5 5 DIN 53 388 17 16 water absorption in % After 10 AATCC Standard Test 90 90 60 C. Method 22 washing* *= according to EN ISO 6330:2000; tumble drying (70 C.)

TABLE-US-00011 TABLE 7 Forced application on PES fabric, 75 g/m.sup.2 Finishing results Application amount of preparation (Z): 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 5 21 22 Original AATCC Standard Test 100 100 Method 22 DIN 53 888 beading effect 5 5 DIN 53 888 12 11 water absorption in % After 10 AATCC Standard Test 100 100 60 C. Method 22 washing* *= according to EN ISO 6330:2000; tumble drying (70 C.)

TABLE-US-00012 TABLE 8 Spray application on polyester fabric, laminated on one side with polyester film, 125 g/m.sup.2 Finishing results and breathability (g/m.sup.2/24 h) before and after storage Application amount of preparation (Z): 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Preparation (Z) according according to the invention to Tab. 5 21 22 Original AATCC Standard Test 100 100 Method 22 Breathability JIS L 8432 8158 1099 Method B2 7 d, 60 C. AATCC Standard Test 100 100 Method 22 Breathability JIS L 8015 7796 1099 Method B2 decrease in % 5% 4%

TABLE-US-00013 TABLE 9 Forced application on PES fabric, 75 g/m.sup.2, then adhesion tests with adhesive fleece Application amount of preparation (Z): 40 g/l in water Liquor absorption: 80% Drying and condensation: 2 minutes at 170 C. Pressing with adhesive fleece: 20 seconds 120 C. 2.5 bar Preparation (Z) according according to the invention to Tab. 5 21 22 Force according to DIN 54310 * 9.0 8.5 * Separating force Clamping length 200 mm Pre-measurement path length 20 mm Test speed 230 mm Measuring distance 230 mm