AQUEOUS DISPERSIONS OF AMINO-FUNCTIONALIZED ORGANOPOLYSILOXANES PRE-CROSSLINKED WITH OXALATOPOLYETHERS

Abstract

An aqueous dispersion includes precrosslinked organopolysiloxanes, emulsifiers, and water. The precrosslinked organopolysiloxanes include units of the formula R.sub.2SiO.sub.2/2 (I), and on average at least one structural unit of the formula SiR.sup.1O.sub.2/2—Y—SiR.sup.1O.sub.2/2 (III) where Y is a divalent radical of the formula —R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3—C(O)—C(O)—NR.sup.3—Z—NR.sup.3—C(O)—C(O)—NR.sup.3—[R.sup.4—NR.sup.3—].sub.nR.sup.2—.

Claims

1-13. (canceled)

14. An aqueous dispersion comprising (1) precrosslinked organopolysiloxanes which comprise units of the formula
R.sub.2SiO.sub.2/2  (I), and on average at least one structural unit of the formula
SiR.sup.1O.sub.2/2—Y—SiR.sup.1O.sub.2/2  (III) where Y is a divalent radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3—C(O)—C(O)—NR.sup.3—Z—NR.sup.3—C(O)—C(O)—NR.sup.3—[R.sup.4—NR.sup.3—].sub.nR.sup.2— Z is identical or different and is a divalent organic radical containing a polyoxyalkylene group, R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, R.sup.1 may be identical or different and is a radical R or a radical —O—R.sup.7, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 1 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, R.sup.5 is identical or different and is a C.sub.1-C.sub.10 alkylene radical, R.sup.6 is a C.sub.1-C.sub.10 alkylene radical, R.sup.7 may be identical or different and is hydrogen or a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, n is 0, 1, 2, 3 or 4 and m is an integer and is on average 1 to 80, (2) emulsifiers, and (3) water.

15. The aqueous dispersion as claimed in claim 14, wherein the precrosslinked organopolysiloxanes (1) comprise structural units of the formula
R.sup.1ASiO.sub.2/2  (II) where A may be identical or different and is a radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3.sub.2 where R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, R.sup.1 may be identical or different and is a radical R or a radical —O—R.sup.7, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 1 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, and n is 0, 1, 2, 3 or 4.

16. The aqueous dispersion as claimed in claim 14, wherein the precrosslinked organopolysiloxanes (1) are selected from the group of the formulae ##STR00006## and mixtures thereof, where R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, Y is a divalent radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3—C(O)—C(O)—NR.sup.3—Z—NR.sup.3—C(O)—C(O)—NR.sup.3—[R.sup.4—NR.sup.3—].sub.nR.sup.2— Z is identical or different and is a divalent organic radical containing a polyoxyalkylene group, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 1 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, R.sup.7 may be identical or different and is hydrogen or a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, A may be identical or different and is a radical of the formula
—R.sub.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3.sub.2, e is 0 or 1, j is 0 or an integer between 1 and 15, k is at least 1 and at most 15, and l is at least 40 and at most 1000.

17. The aqueous dispersion as claimed in claim 14, characterized in that following the removal of the water, the precrosslinked organopolysiloxanes form elastomeric films.

18. A precrosslinked organopolysiloxane (1) which comprises units of the formula
R.sub.2SiO.sub.2/2  (I), and on average at least one structural unit of the formula
SiR.sup.1O.sub.2/2—Y—SiR.sup.1O.sub.2/2  (III) where Y is a divalent radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3—C(O)—C(O)—NR.sup.3—Z—NR.sup.3—C(O)—C(O)—NR.sup.3—[R.sup.4—NR.sup.3—].sub.nR.sup.2— Z is identical or different and is a divalent organic radical containing a polyoxyalkylene group, R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, R.sup.1 may be identical or different and is a radical R or a radical —O—R.sup.7, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, R.sup.5 is identical or different and is a C.sub.1-C.sub.10 alkylene radical, R.sup.6 is a C.sub.1-C.sub.10 alkylene radical, R.sup.7 may be identical or different and is hydrogen or a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, n is 0, 1,2,3 or 4, and m is an integer and is on average 1 to 80.

19. A process for producing the aqueous dispersions of precrosslinked organopolysiloxanes (1), wherein organopolysiloxanes (4) which comprise units of the formula
R.sub.2SiO.sub.2/2  (I), and on average at least one structural unit of the formula
R.sup.1ASiO.sub.2/2  (II) where R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, R.sup.1 may be identical or different and is a radical R or a radical —O—R.sup.7, A may be identical or different and is a radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3.sub.2, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 1 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, R.sup.7 may be identical or different and is hydrogen or a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, and n is 0, 1, 2, 3 or 4, are reacted with oxalamidoester-terminated polyethers (5) of the formula (V) ##STR00007## where Z is identical or different and is a divalent organic radical containing a polyoxyalkylene group, and R.sup.8 is identical or different and is a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, in the presence of emulsifiers (2) and water (3).

20. The process as claimed in claim 19, wherein organopolysiloxanes (4) used comprise those selected from the group of the formulae
[ARSiO.sub.2/2].sub.j[R.sub.2SiO.sub.2/2].sub.l[R.sub.3-e(OR.sup.7).sub.eSiO.sub.1/2].sub.2  (VIa),
[A(OR.sup.1)SiO.sub.2/2].sub.j[R.sub.2SiO.sub.2/2].sub.l[R.sub.3-e(OR.sup.7).sub.eSiO.sub.1/2].sub.2  (VIb), and mixtures thereof, where R may be identical or different and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, R.sup.1 may be identical or different and is a radical R or a radical —O—R.sup.7, A may be identical or different and is a radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.nNR.sup.3.sub.2, R.sup.2 is an SiC-bonded, divalent linear or branched hydrocarbon radical having 1 to 18 carbon atoms, R.sup.3 is a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, R.sup.4 is a divalent hydrocarbon radical having 1 to 6 carbon atoms, R.sup.7 may be identical or different and is hydrogen or a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms, and n is 0, 1, 2, 3 or 4 are reacted with oxalamidoester-terminated polyethers (5) of the formula (V) e is 0 or 1, j is 0 or an integer between 1 and 15, and l is at least 40 and at most 1000.

21. A composition for treating substrates comprising the aqueous dispersions of claim 14.

22. The composition as claimed in claim 21, wherein the substrates are fibrous.

23. The composition as claimed in claim 22, characterized in that the fibrous substrates are textiles.

24. The use of the composition as claimed in claim 21 for treating substrates.

25. The use as claimed in claim 24, wherein the composition is used for cleaning and caring for substrates.

26. The use as claimed in claim 24, wherein the substrates are fibrous substrates.

27. The use as claimed in claim 26, wherein the fibrous substrates are textiles.

28. A composition for treating substrates, comprising the aqueous dispersions of precrosslinked organopolysiloxanes of claim 18.

29. A composition for treating substrates, comprising the aqueous dispersions produced as claimed in claim 19.

Description

Example 1: Oxalamidoester-Terminated Polyether A

[0247] In a 1 I round-bottom flask, 200 g of α,ω-diamino-terminated polyether, purchasable under the trade name Jeffamine® ED-600 (from Huntsman Corporation), are devolatilized, for the removal of water traces and volatile constituents, for 2 h on a rotary evaporator with oil heating bath under a reduced pressure of 0.1 mbar and at 100° C. heating bath temperature. The dewatered Jeffamine® ED-600 possesses an amine number of 3.3 meq/g (MG=606 g/mol). 243 g of diethyl oxalate (1.66 mol) from Sigma-Aldrich (St. Louis, Missouri/USA) are admixed slowly dropwise, under N.sub.2 protective gas and with intense stirring, with 100 g of the dewatered Jeffamine ED-600 (0.33 mol of NH.sub.2), so that the reaction mixture does not heat up above 50° C. This is followed by further stirring at room temperature for 1 h. The excess diethyl oxalate is distilled off subsequently on a rotary evaporator under reduced pressure (1 mbar) at a bath temperature of 90° C. This gives 222.3 g of a clear yellowish liquid.

Example 2: Oxalamidoester-Terminated Polyether B

[0248] 883 g of diethyl oxalate (6.04 mol) from Sigma-Aldrich (St. Louis, Missouri/USA) are admixed slowly dropwise, under N.sub.2 protective gas and with intense stirring, with 100 g (1.14 mol of NH.sub.2) of 3,3′-ethylenedioxybis(propylamine) (MW=176 g/mol), purchasable under the tradename Jeffamine® EDR-176 (from Huntsman Corporation), so that the reaction mixture does not heat up above 50° C. This is followed by further stirring at room temperature for 1 h. The excess diethyl oxalate is distilled off subsequently on a rotary evaporator under reduced pressure (1 mbar) at a bath temperature of 90° C. This gives a clear light-brown liquid.

Example 3: Oxalamidoester-Terminated Polyether C

[0249] In a 1 I round-bottom flask, 250 g of α,ω-diamino-terminated polyether, purchasable under the trade name Jeffamine® D-2000 (from Huntsman Corporation), are devolatilized, for the removal of water traces and volatile constituents, for 2 h on a rotary evaporator with oil heating bath under a reduced pressure of 0.1 mbar and at 100° C. heating bath temperature. The dewatered Jeffamine® D-2000 possesses an amine number of 1.015 meq/g (MG=1970 g/mol).

[0250] 296.66 g of diethyl oxalate (2.03 mol) from Sigma-Aldrich (St. Louis, Missouri/USA) are admixed slowly dropwise, under N.sub.2 protective gas and with intense stirring, with 200 g (0.20 mol of NH.sub.2) of dewatered Jeffamine® D-2000, so that the reaction mixture does not heat up above 50° C. This is followed by further stirring at room temperature for 1 h. The excess diethyl oxalate is distilled off subsequently on a rotary evaporator under reduced pressure (1 mbar) at a bath temperature of 90° C. This gives a clear light-brown liquid.

(Comparative) Example 4: Emulsion CE1 of an Amino-Functionalized Polydimethylsiloxane (Noninventive)

[0251] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) at 5000 rpm is used to premix 1.6 g of an 80% aqueous solution of isotridecyl decaethoxylate, purchasable under the trade name Lutensol TO 10 (from BASF), 5.8 g of isotridecyl pentaethoxylate, purchasable under the trade name Lutensol TO 5 (from BASF), 2.5 g of fully demineralized water and 0.3 g of 80% acetic acid. This premix is admixed in four portions with 14.8 g of a hydroxy/methoxy-terminated copolymer, conditioned at 40° C., composed of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, having an amine number of 0.30 mequ/g and a viscosity of 800-1800 mm.sup.2/s (25.0° C.; capillary number IIIc), with each portion being incorporated and homogenized in 2 minutes with shearing at 5000 rpm. Slow dilution is carried out with 70.0 g of fully demineralized water in portions at 4000 rpm to give the desired emulsion. Addition of 0.9 g of 2-phenoxyethanol, purchasable under the trade name S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG), and 4.0 g of 86% glycerol is followed by homogenization at 4000 rpm for a further 2 minutes. This gives a transparent to opalescent, colorless microemulsion of low viscosity with a solids content of 27% and a pH of 5.5. The emulsion remains stable and homogeneous even in storage.

(Comparative) Example 5: Emulsion CE2 of an Amino-Functionalized Polydimethylsiloxane (Noninventive)

[0252] An LDV 1 dissolver from PC Laborsystem is used to prepare an emulsion CE2 from 6.5 g of isotridecyl pentethoxylate, purchasable under the tradename Lutensol TO 5 (from BASF), 20.0 g of a copolymer of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, having an amine number of 0.13 mequ/g and a viscosity of 3900 mm.sup.2/s (25.0° C.; capillary no. IV), 2.9 g of glycerol, 0.12 g of 80% acetic acid, 0.19 g of N-morpholinomethyltriethoxysilane and 70 g of water, this emulsion having a particle size D(50) of 28 nm (at a photon count rate of 286 kcps). Incorporated into this emulsion by mixing is 0.13 g of 2-phenoxyethanol, purchasable under the tradename S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG).

(Comparative) Example 6: Emulsion CE3 of an Amino-Functionalized Polydimethylsiloxane (Noninventive)

[0253] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to premix 6.0 g of C11-15 Pareth-7 (ethoxylated secondary alcohol, 7 ethylene oxide units), purchasable under the tradename Tergitol 15-S-7 (from Dow), and 1.9 g of hot, fully demineralized water. Weighed out into this premix are 1.0 g of lauryl ethoxylate-9 (ethoxylated primary alcohol, 9 ethylene oxide units), purchasable under the tradename Sympatens AL/090 (from KLK Kolb), 3.0 g of melted isotridecyl dodecaethoxylate, purchasable under the tradename Lutensol TO 12 (from BASF), and 1.9 g more of hot, fully demineralized water, and the mixture is homogenized at 5000 rpm for 2 minutes. Subsequently 2.3 g of 86% glycerol are metered in and the mixture is homogenized at 5000 rpm for a further 2 minutes. Added to this mixture are 20.0 g of a hydroxy/methoxy-terminated copolymer of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, having an amine number of 0.25 mequ/g and a viscosity of 1500-2100 mm.sup.2/s (25.0° C.; capillary no. IIIc) in three portions, with homogenization in each case for 2 minutes with shearing at 5000 rpm. Addition of 0.9 g of 2-phenoxyethanol, purchasable under the tradename S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG), and 0.4 g of 80% acetic acid is followed by homogenization at 5000 rpm for a further 2 minutes. Slow dilution takes place with 62.6 g of fully demineralized water in portions of 4000 rpm to give the desired emulsion.

[0254] This gives a transparent to opalescent, colorless microemulsion of low viscosity with a solids content of 33% and a pH of 5.0.

Example 7: Emulsion E4 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0255] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 99.26 g of the emulsion CE1 with 0.74 g of oxalamidoester-terminated polyether A (˜5 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a transparent to slightly hazy, colorless to minimally yellowish, emulsion E4 of low viscosity with a solids content of 28% and a pH of 5.0.

[0256] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a pronounced, whitish, elastic, soft film which adheres well to aluminum and is not tacky on the surface.

Example 8: Emulsion E5 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0257] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 99.70 g of the emulsion CE1 with 0.30 g of oxalamidoester-terminated polyether B (˜2 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a transparent to slightly hazy, colorless to minimally yellowish, emulsion E5 of low viscosity with a solids content of 27% and a pH of 5.0.

[0258] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a pronounced, whitish, elastic, soft film which adheres well to aluminum and is not tacky on the surface.

Example 9: Emulsion E6 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0259] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 98.52 g of the emulsion CE1 with 1.48 g of oxalamidoester-terminated polyether C (˜10 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a hazy, colorless to minimally yellowish, emulsion E6 of low viscosity with a solids content of 28% and a pH of 5.0.

[0260] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a whitish, elastic, soft film which adheres well to aluminum and is not tacky on the surface.

Example 10: Emulsion E7 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0261] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 97.00 g of the emulsion CE3 with 3.00 g of oxalamidoester-terminated polyether A (˜15 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a slightly hazy, minimally yellowish, emulsion E7 of low viscosity with a solids content of 35% and a pH of 4.5.

[0262] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a whitish, elastic, soft film which adheres well to aluminum and is not tacky on the surface.

Example 11: Emulsion E8 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0263] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 99.20 g of the emulsion CE3 with 0.80 g of oxalamidoester-terminated polyether B (˜4 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a transparent, minimally yellowish, emulsion E8 of low viscosity with a solids content of 34% and a pH of 4.5.

[0264] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a pronounced, whitish, elastic, soft film which adheres well to aluminum and is not tacky on the surface.

Example 12: Emulsion E9 of an Amino-Functionalized Polydimethylsiloxane Crosslinked with an Oxalamidoester-Terminated Polyether

[0265] An Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA) is used at 5000 rpm to homogenize 96.00 g of the emulsion CE3 with 4.00 g of oxalamidoester-terminated polyether C (˜20 wt % based on amino-functionalized polydimethylsiloxane) over the course of a minute. This gives a hazy, minimally yellowish, emulsion E9 of low viscosity with a solids content of 36% and a pH of 4.5.

[0266] After a drying time of 1-3 days at 25° C., evaporation of the emulsion gives a whitish, elastic, very soft film which adheres well to aluminum and is not tacky on the surface.

(Comparative) Example 13: Emulsion CE10 of a Linear Oxalamidoester-Polyether-Bridged Polydimethylsiloxane

[0267] Emulsion CE10 is produced in analogy to example 1 of WO 2019/114953 A1:

[0268] A 500 ml 3-neck flask with thermocouple, KPG stirrer and reflux condenser was charged with 100 g (20 mmol) of a linear oxamidoester-terminated silicone oil (5065 g/mol). Added at 22° C. over the course of 10 minutes with stirring were 3.74 g (20 mmol) of TA 187 (═N.sup.1-(3-(dimethylamino)propyl)-N.sup.3,N.sup.3-dimethylpropane-1,3-diamine, purchasable from SIGMA-ALDRICH, MERCK, Darmstadt, Germany) and subsequently 6.6 g (10 mmol) of JEFFAMINE® ED-600 (available from Huntsman Performance Products, Everslaan 45, B-3078 Everberg, Belgium). This was followed by stirring for 30 minutes more. Thereafter the reaction product was freed from the resultant alcohol at 40° C. under a pressure of 20 hPa. This gave 107 g of an opaque oligomeric product. 21.2 g of the product obtained are mixed in 4.7 g of diethylene glycol monobutyl ether (available from Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) and 4.1 g of tridecyl alcohol ethoxylate (available as LUTENSOL® TO from BASF SE, Ludwigshafen) and then slowly diluted with 70.0 g of water and adjusted to a pH of 4.5 with 80% acetic acid.

Example 14

[0269] The degree of crosslinking was determined using the following emulsions described in table 1. The emulsions here are poured into aluminum trays, and the appearance of the emulsions was evaluated following the removal of the water.

TABLE-US-00002 TABLE 1 Crosslinking experiments C1 to C9 Emulsions Film formation C1 *) after 1 day: p, o; no film containing CE1 C2 *) after 1 day: p, o; no film containing CE3 C3 *) after 1 day: p, o; no film containing CE10 C4 **) after 1 day: e, s; film containing E4 C5 **) after 1 day: e, s; film containing E5 C6 **) after 1 day: pc, p; incipient film-forming containing E6 after 3 days: e, s; film C7 **) after 1 day: g-e; film containing E7 after 3 days: e, s; film C8 **) after 1 day: g-e; film containing E8 after 3 days: e, s; film C9 **) after 1 day: p, no film containing E9 after 3 days: pc-g-e; incipient film-forming after 1 week: g-e; film Key: pc = partly crosslinked; e = elastic; g = gellike; o = oily; P = pasty; s = soft. *) not inventive; **) inventive

Example 15: Determination of the Crease Recovery Angle

[0270] The performance tests relating to the determination of the crease recovery angle took place using the following aqueous formulations described in table 2. The amount of polyoxysiloxane-containing emulsions is selected such that the polysiloxane content (except for the blank value F1) is always the same.

TABLE-US-00003 TABLE 2 Aqueous formulations F1 to F8 Polyoxysiloxane- Formulations containing emulsion Water F1 (blank value) — 100.0 g  F2 *) 10.8 g CE2 89.2 g F3 **) 10.8 g E4 89.2 g F4 **) 10.8 g E5 89.2 g F5 **) 10.8 g E6 89.2 g F6 **) 8.0 g E7 92.0 g F7 **) 8.0 g E8 92.0 g F8 **) 8.0 g E9 92.0 g *) noninventive **) inventive

[0271] The formulations (both inventive and noninventive) are produced by simple mixing of the constituents (with the aid of an IKA Eurostar Power basic agitator mechanism with paddle stirrer).

[0272] For assessment of the desired effects in terms of the crease recovery angle:

[0273] Textile strips 2×5 cm are taken from a wfk 10 A cotton test fabric (100% cotton with around 170 g/m.sup.2 basis weight) from wfk-Testgewebe, this fabric having been washed twice with a commercial heavy-duty powder detergent at 90° C.

[0274] The aqueous formulations F1 to F8 (see table 2) are sprayed onto the textile strips using a trigger spray. The mass of the formulations F1 to F8 applied by spraying is selected such that it is the same as the mass of the textile strip. The textile strips are dried overnight on the line, conditioned for 24 hours in a conditioning chamber at 23° C./60% humidity, and then ironed with an iron on “cottons” setting.

[0275] The crease recovery angle is determined by the method of DIN 53 890/1972:

[0276] Each textile strip is folded over in transverse direction, so that the length of the sample flank to be laid over is 10 mm. An aluminum foil 0.15 mm in thickness is placed under the sample flank to be laid over, in order to prevent the fibers adhering. The sample is covered with a microscope slide and weighted down with a 1000 g weight such that the weight rests on the overlaid sample flank only. The weighting time is 30 min.

[0277] After the weight on the microscope slide has been removed, the gradually increasing crease recovery angle is determined after 5 and 30 min on both sides of the angle flank, using a protractor.

[0278] At least ten samples should be prepared and measured for each textile. The measurement results reported are the averages from the respective determinations.

TABLE-US-00004 TABLE 3 Determination of the crease recovery angle on wfk 10 A cotton test fabric Crease recovery angle after spray application and drying Formulations After 5 min F1 (blank value) 42.4° ± 1.7° F2 *) 66.6° ± 2.4° F3 **) 75.6° ± 2.9° F4 **) 72.6° ± 2.0° F5 **) 69.0° ± 1.8° F6 **) 70.4° ± 2.1° F7 **) 69.8° ± 1.1° F8 **) 80.8° ± 2.7° *) contains noninventive emulsion containing an uncrosslinked amino- functional polydiorganosiloxane **) contains inventive emulsion containing a crosslinked hydrophilic polydiorganosiloxane

[0279] The modification of the textiles with the formulations F3 to F8, containing the inventive emulsions E4 to E9, results in a significant increase in crease recovery angle relative to a textile sprayed only with water (blank value F1).

[0280] The comparison with formulation F2 as well, which contains the noninventive emulsion CE2 of an uncrosslinked amino-functionalized polydimethylsiloxane, shows that the inventive formulations F3 to F8, particularly the formulations F3 and F8, exhibit an increased crease recovery angle.

[0281] Consequently a significantly reduced propensity to creasing than is provided by the prior art is achieved when using the emulsions of the invention in textile products whose function is to reduce or suppress creasing in textiles, such as clothing.

Example 16: Droplet Absorption Time

[0282] The performance tests relating to the determination of the droplet absorption time took place using the aqueous formulations F2 to F5 described in table 2 (example 15).

[0283] A wfk 10 A cotton test fabric from wfk-Testgewebe is modified in accordance with the method as described in example 15.

[0284] One droplet of deionized water was placed from a height of 4 cm onto the stretched fabric surface of the textile thus modified, after drying, and a determination was made of the time for the water droplet to have been absorbed by the fabric. Five determinations were conducted, and the average was formed.

TABLE-US-00005 TABLE 4 Determination of the droplet absorption time on wfk 10 A cotton test fabric Droplet absorption time on wfk 10 A cotton test fabric after spray application Absorption time Formulations in seconds F2 (noninventive) 32 ± 2 F3 (inventive) 14 ± 3 F4 (inventive) 21 ± 3 F5 (inventive) 17 ± 2

[0285] The modification of the cotton test fabric with the formulations F3 to F5 containing the inventive emulsions E4 to E6 leads to a significantly reduced droplet absorption time on cotton test fabric, relative to the modification with the formulation F2 containing the noninventive emulsion CE2 of an uncrosslinked amino-functionalized polydimethylsiloxane. As a result, significantly better water absorption is achieved for the textile than in the prior art.

Example 17: Soft Hand in Application as a Fabric Softener Ingredient

[0286] The performance tests relating to the determination of the crease recovery angle took place using the following aqueous formulations described in table 5.

TABLE-US-00006 TABLE 5 Aqueous formulations F9 to F13 Polyoxysiloxane- Cationic Formulations containing emulsion surfactant ***) Water F9 *) — 4.0 g 36.0 g F10 **) 1.4 g E4 2.4 g 36.2 g F11 **) 1.4 g E5 2.40 g 36.2 g F12 **) 1.4 g E6 2.40 g 36.2 g F13 *) 1.4 g VE1 2.40 g 36.2 g *) noninventive **) inventive ***) N,N-bis[ethyl(tallowate)]-N-(2-hydroxyethyl)-N-methylammonium methylsulfate (90% ethanolic solution), purchasable under the tradename Stepantex ® VK90 (from Stepan)

[0287] To assess the desired effects in terms of soft hand, six terry hand towels made of cotton fabric were washed together with around 2 kg of ballast fabric in a MIELE Softronic W 1935 WPS EcoLine household washing machine using the boil/color wash program at 40° C. and spun at 1200 rpm. The washing surfactant metered in here was 65 g of an ECE-2 test laundry detergent powder from WFK. After the wash cycle, the formulation F9 to F13 (pre-diluted in 1 liter of tap water of 16° dH [German hardness]) is added via the detergent drawer. Lastly the material was dried for at least 12 hours in a conditioning chamber at 23° C. and 60% atmospheric humidity on the line.

[0288] Determination of the Soft Hand (Hand Evaluation)

[0289] Because the soft hand of textiles is greatly subject to the subjective perception of the testers, the boundary conditions only, but not the evaluation, can be standardized. In order to ensure reproducibility nevertheless, the modified specimens were assessed for their soft hand and ranked. For this purpose, 10 testers awarded 1 to n marks, depending on the number n of specimens tested, where n marks were rewarded for the softest specimen and 1 mark for the specimen modified with the lowest softness. The unmodified reference specimen received 0 marks. The evaluation of the hand of a specimen is computed accordingly as the average of the points apportioned to that specimen respectively.

TABLE-US-00007 TABLE 6 Soft hand assessment on terry cloth Soft hand assessment on terry cloth (basis weight: 500 g/m.sup.2) after washing machine treatment and drying Formulations Soft hand F9 (noninventive) +++ F10 (inventive) ++ F11 (inventive) ++ F12 (inventive) +++ F13 (noninventive) + +++ excellent softness, ++ very soft, + soft, ∘ hard

[0290] The modification of the textile with the inventive formulations F10 to F12 leads to a significantly improved soft hand relative to the prior-art formulation F13 (containing emulsion CE1 of an uncrosslinked amino-functionalized diorganopolysiloxane), which has a lower soft hand.

[0291] The combination of cationic surfactant and, in particular, of the inventive emulsion in formulation F12 leads, further, to a soft hand which is otherwise attainable only with a significantly increased cationic surfactant content, as in formulation F9. This leads to a reduced use of raw materials, which represents a distinct improvement on the prior art both environmentally and economically.