ZWITTERIONIC POLYSILOXANES

Abstract

The present invention relates to polysiloxanes having zwitterionic groups, their preparation, compositions comprising such polysiloxanes and the use of these polysiloxanes or compositions for treating substrates.

Claims

1. A polysiloxane of general formula A ##STR00050## wherein R.sup.1 is independently of each other methyl, ##STR00051## with the proviso that in formula A at least one R.sup.1 corresponds to one of formulae II-V, R.sup.2 is independently of each other ##STR00052## R.sup.3 is independently of each other ##STR00053## or a zwitterionic group selected from ##STR00054## with the proviso that at least one R.sup.3 in formula A is a zwitterionic group, R.sup.4 is independently of each other an unbranched or branched C.sub.1-7-alkylene, preferably an unbranched C.sub.1-5-alkylene, particularly preferably (CH.sub.2).sub.2, R.sup.5 is independently of each other a branched or unbranched C.sub.1-18-alkyl, preferably an unbranched C.sub.1-8-alkyl, particularly preferably methyl, R.sup.6 is independently of each other an unbranched C.sub.2-s-alkylene, preferably (CH.sub.2).sub.2 or (CH.sub.2).sub.3, R.sup.7 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably (CH.sub.2).sub.2 or methylene, R.sup.8 is independently H or OH, R.sup.9 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably methylene, R.sup.11 is independently of each other ##STR00055## R.sup.12 is independently of each other ##STR00056## R.sup.13 is independently of each other an aliphatic or cyclic C.sub.1-18-alkylene or arylene, in each case optionally substituted by C.sub.1-8-alkyl or benzyl, preferably unbranched C.sub.1-8-alkylene, in particular (CH.sub.2).sub.4, (CH.sub.2).sub.6, ##STR00057## n is an integer from 20-2,000, preferably 40-1,000, particularly preferably 40-180, and m is 0 or an integer greater than 0, preferably 0 or 1-2,000, more preferably 0 or 1-55.

2. The polysiloxane according to claim 1, wherein 0-99.9%, preferably 50-99.9%, more preferably 80-99.9% and particularly preferably 90-99.9% or 0-99.999%, preferably 50-99.999%, more preferably 80-99.999% and particularly preferably 90-99.999% of the R.sup.1 substituents are methyl.

3. The polysiloxane according to claim 1, wherein the two terminal R.sup.1 substituents are methyl and at least one lateral R.sup.1 substituent corresponds to one of the formulae II-V, or all lateral R.sup.1 substituents are methyl and the two terminal R.sup.1 substituents are selected from formulae II-V.

4. The polysiloxane according to claim 1, wherein all R.sup.1 substituents are selected from methyl and formula II, and/or wherein R.sup.2 is ##STR00058## and/or wherein R.sup.11 is ##STR00059## is and/or wherein R.sup.12 corresponds to one of formulae XIII or XIV.

5. The polysiloxane according to claim 1, wherein 10-100%, preferably 40-99.9%, more preferably 50-95% and most preferably 60-80% of R.sup.3 in formula A are zwitterionic groups, and/or all zwitterionic groups are present as formula VIa or all zwitterionic groups are present as formula VIb.

6. The polysiloxane according to claim 1, having the general formula I ##STR00060## wherein R.sup.1 is independently of each other methyl, ##STR00061## with the proviso that in formula I at least one R.sup.1 corresponds to one of formulae II-V, R.sup.2 is independently of each other ##STR00062## R.sup.3 is independently of each other ##STR00063## or a zwitterionic group selected from ##STR00064## with the proviso that at least one R.sup.3 in formula I is a zwitterionic group, R.sup.4 is independently of each other an unbranched or branched C.sub.1-7-alkylene, preferably an unbranched C.sub.1-5-alkylene, particularly preferably (CH.sub.2).sub.2, R.sup.5 is independently of each other a branched or unbranched C.sub.1-18-alkyl, preferably an unbranched C.sub.1-8-alkyl, particularly preferably methyl, R.sup.6 is independently of each other an unbranched C.sub.2-s-alkylene, preferably (CH.sub.2).sub.2 or (CH.sub.2).sub.3, R.sup.7 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably (CH.sub.2).sub.2 or methylene, R.sup.3 is independently H or OH, R.sup.9 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably methylene, and n is an integer from 20-2,000, preferably 40-1,000, particularly preferably 40-180.

7. A process for the preparation of the polysiloxane according to claim 1, comprising the steps of (a) providing a polysiloxane of the general formula VII ##STR00065## wherein R.sup.10 is independently of each other methyl, ##STR00066## with the proviso that in formula VII at least one R.sup.10 corresponds to one of formulae VIII-XI, (b) optionally reacting the polysiloxane of the general formula VII with a diisocyanate of the formula OCNR.sup.13NCO, and (c) reacting the polysiloxane of the formula VII or the polysiloxane adduct obtained after step (b) with a reactant selected from a peroxide and/or a compound of the general formula XII ##STR00067## wherein X is a halogen, in particular Cl or Br, and wherein the peroxide is preferably hydrogen peroxide (H.sub.2O.sub.2), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peroxyacetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and/or barium peroxide and particularly preferably hydrogen peroxide (H.sub.2O.sub.2), wherein the molar ratio between reactant and the tertiary amino groups in the polysiloxane of formula VII or in the polysiloxane adduct obtained after step (b) is preferably 0.1:1-1:1, more preferably 0.4:1-0.999:1, more preferably 0.5:1-0.95:1 and most preferably 0.6:1-0.8:1.

8. The process according to claim 7, wherein in step b) the molar ratio of the isocyanate groups of the diisocyanate of the general formula OCNR.sup.13NCO to the isocyanate-reactive hydroxy groups of the polysiloxane of the general formula VII is from 0.1:1-1:1, more preferably from 0.4:1-0.999:1, particularly preferably from 0.5:1-0.95:1 and most preferably from 0.6:1-0.9:1, and/or wherein in step b) the diisocyanate of the general formula OCNR.sup.13NCO is selected from the group consisting of toluene-2,4-diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), higher-chain homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate and/or isophorone diisocyanate.

9. Process according to claim 7, wherein in step c) the reaction is carried out in a solvent which preferably comprises water and/or at least one organic solvent, and/or wherein step b) is carried out using a solvent or in the absence of a solvent, and/or wherein step b) and/or step c) is carried out at 15-150 C., more preferably at 20-105 C., even more preferably at 25-95 C., even more preferably at 40-90 C. and particularly preferably at 70-85 C.

10. A composition comprising (i) the polysiloxane according to claim 1 and (ii) a solvent, in particular water and/or an organic solvent, which is preferably from the group of mono- and polyfunctional alcohols and/or their ether compounds and/or their ester compounds, (iii) optionally at least one anionic, cationic, non-ionic or amphoteric emulsifier, preferably at least one non-ionic emulsifier, particularly preferably ethoxylated products of aliphatic alcohols, wherein the emulsifier (iii) is present preferably with 2-100 wt. %, more preferably with 10-80 wt. %, particularly preferably with 20-70 wt. %, based on component (i), and/or (iv) optionally at least one additive, for example a dilutant, glycerol, urea and/or at least one acid and/or at least one softening agent, preferably an organomodified polysiloxane, wherein the composition preferably contains 0.005-99.9% by weight, more preferably 5-99% by weight, particularly preferably 10-90% by weight of component (i), based on its total mass.

11. The composition according to claim 10, which is present as an emulsion, preferably as an o/w emulsion.

12. A process comprising using the polysiloxane according to claim 1 for treating a substrate, in particular for finishing a textile substrate, wherein the textile substrate is preferably a woven fabric, knitted fabric, non-woven fabric, fibre and/or leather and particularly preferably contains natural and/or synthetic fibres, or as an additive in paint, glaze, lacquer and/or car care formulations.

13. The process according to claim 12, wherein the polysiloxane is used for improving the soft handle of the textile substrate, and/or for improving the wetting, spreading and/or levelling properties of paint, glaze, lacquer and/or car care formulations.

14. A substrate, in particular textile substrate, which is treated with a polysiloxane according to claim 1, wherein the textile substrate preferably contains 0.04-2.4 wt. %, particularly preferably 0.08-1.2 wt. % of polysiloxanes based on its total mass.

15. A process for treating a substrate comprising the steps of (i) providing a substrate, (ii) applying the polysiloxane according to claim 1 to the substrate, and (iii) optionally treating the substrate obtained after step (ii) at an elevated temperature, preferably to remove water, in particular at a temperature of 110-150 C., wherein step (ii) is preferably carried out by foulard, spraying, brushing, dipping, padding and/or by exhaust.

Description

EXAMPLES

Example 1 (not According to the Invention)

[0174] According to EP 0 294 642 A2, Example 3, 56.8 g (200 mmol) of lauryl (dimethylaminopropyl) amide were mixed with 80.0 g of H.sub.2O and 12.0 g (200 mmol) of glacial acetic acid were added at 20 C. After 30 min, the reaction was heated to 50 C. and 590 g (100 mmol) of an epoxysiloxane with an epoxide content of 0.338 mol/kg and an average chain length of 75 was dropwise added. After addition of 200 ml isopropanol, stirring was continued for 6 h under reflux. The H.sub.2O/isopropanol mixture was distilled off at 100 C. and 0.2 bar. 140 g of butyl diglycol were added, yielding a slightly yellow organopolysiloxane.

Example 2 (According to the Invention)

[0175] 500 g of a laterally SiH-modified poly(dimethylsiloxane-co-methylhydrosiloxane)s with 0.089 wt. % Si-bound hydrogen (corresponding to 443 mmol SiH) and an average chain length of 75 were added within 60 minutes to a solution of 28.3 mg Karstedt catalyst in 65.7 g (575 mmol) allyl glycidyl ether, which had previously been tempered to 135 C. After removal of the excess allyl glycidyl ether by distillation, 44.4 g (443 mmol) of N-methylpiperazine was slowly added at 135 C. to give a clear, slightly yellowish organopolysiloxane (intermediate A).

[0176] 76.5 g of the intermediate A obtained (corresponding to 114 mmol tert. nitrogen) was heated to 35 C. together with 14.0 g butyl diglycol. At this temperature, 6.46 g (57.0 mmol) of a 30% aqueous hydrogen peroxide solution was added with stirring. After the end of the exotherm reaction, stirring was continued for 6 h at 75 C., whereby a slightly yellowish organopolysiloxane was obtained.

Example 3 (According to the Invention)

[0177] 76.5 g of the intermediate A from Example 2 (corresponding to 114 mmol tert. nitrogen) was heated to 35 C. together with 8.50 g of butyl diglycol. At this temperature, 12.9 g (114 mmol) of a 30% aqueous hydrogen peroxide solution was added with stirring. After the end of the exotherm reaction, stirring was continued for 6 h at 75 C. to give a slightly yellowish organopolysiloxane.

Example 4 (According to the Invention)

[0178] 500 g of an ,-dihydrogenpolydimethylsiloxane with 0.035 wt. % Si-bonded hydrogen (corresponding to 176 mmol SiH) and an average chain length of 75 were added within 60 min to a solution of 26.3 mg Karstedt catalyst in 26.1 g (229 mmol) allyl glycidyl ether, which was previously tempered to 135 C. After removal of the excess allyl glycidyl ether by distillation, 33.0 g (176 mmol) of bis[3-(dimethylamino)propyl]amine was slowly added at 135 C. to give a yellowish organopolysiloxane (Intermediate B).

[0179] 76.5 g of intermediate B (corresponding to 48.7 mmol tert. nitrogen) was heated to 35 C. together with 13.0 g butyl diglycol. At this temperature, 5.52 g (48.7 mmol) of a 30% aqueous hydrogen peroxide solution was added with stirring. After the end of the exotherm reaction, stirring was continued for 6 h at 75 C., whereby a slightly yellowish organopolysiloxane was obtained.

Example 5 (According to the Invention)

[0180] 7.04 g (74.5 mmol) chloroacetic acid was dissolved in 5.00 g H.sub.2O, 10.0 g butylglycol. To this solution, 5.96 g (74.5 mmol) of 50% sodium hydroxide solution was added with stirring. After stirring for 15 min, 100 g of the intermediate A from example 2 (corresponding to 149 mmol tert. nitrogen) was added and the mixture was stirred for 4 h at 75 C., yielding a slightly yellowish organopolysiloxane.

Example 6 (According to the Invention)

[0181] 5.41 g (57.3 mmol) of chloroacetic acid was dissolved in 6.00 g of H.sub.2O, 12.0 g of butylglycol. To this solution, 4.58 g (57.3 mmol) of 50% sodium hydroxide solution was added with stirring. After stirring for 15 min, 100 g of the intermediate B from example 4 (corresponding to 63.6 mmol tert. nitrogen) was added and the mixture was stirred for 4 h at 75 C., yielding a slightly yellowish organopolysiloxane.

Example 7 (According to the Invention)

[0182] 500 g of an ,-dihydrogenpolydimethylsiloxane with 0.035 wt. % Si-bonded hydrogen (corresponding to 176 mmol SiH) and an average chain length of 75 were added within 60 min to a solution of 26.3 mg Karstedt catalyst in 26.1 g (229 mmol) allyl glycidyl ether, which was previously tempered to 135 C. After removal of the excess allyl glycidyl ether by distillation, 33.0 g (176 mmol) of bis[3-(dimethylamino)propyl]amine was slowly added at 135 C. The catalyst was then cooled to 50 C. It was then cooled to 50 C., 896 mg of 1,4-diazabicyclo[2.2.2]octane and 38.1 g (172 mmol) of isophorone diisocyanate were added and the mixture was stirred at 70 C. until no NCO band was visible in the IR spectrum, yielding a yellowish organopolysiloxane (polysiloxane adduct C).

[0183] 75.1 g of the polysiloxane adduct C (corresponding to 46.6 mmol tert. nitrogen) was heated to 75 C. together with 5.00 g H.sub.2O, 10.0 g butyl glycol, 2.64 g (28.0 mmol) chloroacetic acid and 2.24 g (28.0 mmol) 50% sodium hydroxide solution. The mixture was stirred at 75 C. for 4 h, yielding a slightly yellowish organopolysiloxane.

Emulsion Examples

General Emulsification Instructions:

[0184] The specified amount of emulsifier was added to the organopolysiloxane to be emulsified at room temperature and stirred using a wall-mounted anchor stirrer until a homogeneous mixture was obtained. H.sub.2O was added to this mixture in portions and stirred until the entire portion of water was absorbed.

TABLE-US-00001 Emulsion Emulsion Emulsion Emulsion Emulsion Emulsion Emulsion E1 E2 E3 E4 E5 E6 E7 Component quantity quantity quantity quantity quantity quantity quantity Organopolysiloxane 20.0% from example 1 Organopolysiloxane 20.0% from example 2 Organopolysiloxane 20.0% from example 3 Organopolysiloxane 20.0% from example 4 Organopolysiloxane 20.0% from example 5 Organopolysiloxane 20.0% from example 6 Organopolysiloxane 20.0% from example 7 Isotridecyl alcohol + 8.5% 8.5% 8.5% 8.5% 8.5% 8.5% 8.5% 6 EO H.sub.2O 71.5% 71.5% 71.5% 71.5% 71.5% 71.5% 71.5%

Application Examples

Soft Grip Assessment Sections of cotton terry cloth that had not been optically brightened were finished with an aqueous liquor containing 20 g/l of the emulsions prepared according to the examples, adjusted to pH 5 with 60% acetic acid, in a Mathis Labomat for 20 minutes at 40 C. and at a liquor ratio of 1:10. The excess liquor was then squeezed out with a laboratory padder at 3 bar, followed by drying at 140 C. for 2 minutes. The circulation speed was 45 rpm.

[0185] The grip character of the test fabrics treated with the emulsions was then assessed. This is subject to individually different, subjective criteria. Nevertheless, in order to obtain meaningful results, an assessment by at least 5 test persons is required. The results were analysed using statistical methods, with grade 1 representing the softest, most pleasant grip and grade 3 the hardest, least soft and most unpleasant grip within the test series.

TABLE-US-00002 Assessment Emulsion example E1 2.8 (not according to the invention) Emulsion example E2 1.2 Emulsion example E3 2.0 Emulsion example E4 2.2 Emulsion example E5 1.3 Emulsion example E6 1.7 Emulsion example E7 1.1

Hydrophilicity

[0186] The hydrophilicity of the cotton terry fabric finished for soft handle evaluation was assessed according to the TEGEWA drop test (Melliand Textilberichte 68 (1987), 581-583).

TABLE-US-00003 Soaking time [s] Emulsion example E1 2 (not according to the invention) Emulsion example E2 1.5 Emulsion example E3 1 Emulsion example E4 0.5 Emulsion example E5 1.5 Emulsion example E6 1 Emulsion example E7 1

Anion Stability

[0187] 100 ml of the emulsion to be tested was prepared in water at a concentration of 40 g/I in each of two beakers. 100 ml of a solution of 4 g/L VEROLAN NEW (organic dispersant with polyacrylates and alkyl phosphonate, anion-active) are added to the first beaker. In the second beaker, 100 ml of a solution of 12 g/L RUCO-BLANC AMA (whitener, stilbene derivative, anion-active) was added. The liquors were adjusted to pH 5 with 60% acetic acid.

[0188] The evaluation was carried out after six hours of standing time, according to the following grading: [0189] 1 liquor is clear [0190] 2 liquor is cloudy or slightly cloudy [0191] 3 The liquor is flocculent or has a sediment that can be stirred back in (does not flocculate again within 1 minute) [0192] 4 Large flake formation or sediment that can no longer be stirred in [0193] 5 Oily deposits on the surface of the liquor or beaker

[0194] The test is deemed to have been passed if the assessment is no worse than 3.

TABLE-US-00004 Assessment after 6 hours* Emulsion example E1 5/4 (not according to the invention) Emulsion example E2 3/3 Emulsion example E3 2/1 Emulsion example E4 3/2 Emulsion example E5 2/2 Emulsion example E6 2/2 Emulsion example E7 2/1 *The left-hand value of the assessment refers to the stability in the presence of VEROLAN NEW, the right-hand value to the stability in the presence of RUCO-BLANC AMA.

Thermal Yellowing

[0195] Sections of a bleached, not optically brightened cotton modal knitted fabric were impregnated with an aqueous liquor containing 20 g/l of the emulsions prepared according to the examples and 0.5 g/I 60% acetic acid on a lab foulard with a wet absorption of 80%, dried at 120 C. for 2 minutes and then heat-set at 170 C. for 2 minutes. The whiteness of the samples was then measured according to Ganz (Applied Optics 15 (1976) 9, 2039-2058) on the texflash 2000 whiteness measuring device from datacolor international (Switzerland).

TABLE-US-00005 Whiteness according to Ganz Unfinished textile 231 Emulsion example E1 231 Emulsion example E2 229 Emulsion example E3 230 Emulsion example E4 232 Emulsion example E5 230 Emulsion example E6 232 Emulsion example E7 231

[0196] The preparations according to the invention do not cause yellowing of the textile substrate. The degree of whiteness of the substrates treated with the preparations according to the invention corresponds to that of the untreated textile.

Phenolic Yellowing

[0197] Sections of a bleached, not optically brightened cotton modal knitted fabric were impregnated with an aqueous liquor containing 40 g/l of the emulsions prepared according to the examples and 0.5 g/l of 60% acetic acid on a lab foulard with a wet absorption of 80% and then dried at 120 C. for 2 minutes. The yellowing was then assessed using the sandwich test (DIN EN ISO 105-X18).

[0198] Each test sample and the control fabric are placed individually between a folded test paper between two glass plates in a horizontal stack. The stack of plates, test papers, test samples and control tissue is then packed airtight and incubated in a heating cabinet at 50 C. for 16 hours.

[0199] After opening the package, possible colour changes are immediately evaluated using the grey scale on a scale of 1-5 in accordance with ISO 105-A01.

[0200] The higher the value on the grey scale, the less yellowed the textile is:

TABLE-US-00006 Assessment Emulsion example E1 3-4 (not according to the invention) Emulsion example E2 4 Emulsion example E3 4-5 Emulsion example E4 4-5 Emulsion example E5 4 Emulsion example E6 4-5 Emulsion example E7 4-5

Jet Stability

[0201] In a beaker, 400 mL of liquor containing 4 g/I sodium sulphate and 5 g/L of the emulsion to be tested in water was adjusted to pH 4.5 with 60% acetic acid. The aqueous liquor was then heated to 40 C. and stirred for twenty minutes at this temperature with an inclined blade stirrer at two thousand rounds per minute. At the end of this time, the stirrer was switched off and the liquid was assessed for separation after a rest period of one hour. This test is intended to simulate the mechanical forces of a jet process in the presence of textile auxiliaries remaining on the textile from previous finishing steps.

TABLE-US-00007 Result Emulsion example E1 Silicone deposits on the edge (not according to the invention) and surface Emulsion example E2 Cloudy liquor, no deposits Emulsion example E3 Slightly cloudy liquor, no deposits Emulsion example E4 Slightly cloudy liquor, no deposits Emulsion example E5 Cloudy liquor, no deposits Emulsion example E6 Slightly cloudy liquor, no deposits Emulsion example E7 Slightly cloudy liquor, no deposits

[0202] The following items summarise the invention: [0203] 1. A polysiloxane of the general formula A

##STR00032## wherein [0204] R.sup.1 is independently of each other [0205] methyl,

##STR00033## with the proviso that in formula A at least one R.sup.1 corresponds to one of the formulae II-V, [0206] R.sup.2 is independently of each other

##STR00034## [0207] R.sup.3 is independently of each other

##STR00035## or a zwitterionic group selected from

##STR00036## with the proviso that at least one R.sup.3 in formula A is a zwitterionic group, [0208] R.sup.4 is independently of each other an unbranched or branched C.sub.1-7-alkylene, preferably an unbranched C.sub.1-5-alkylene, particularly preferably (CH.sub.2).sub.2, [0209] R.sup.5 is independently of each other a branched or unbranched C.sub.1-18-alkyl, preferably an unbranched C.sub.1-8-alkyl, particularly preferably methyl, [0210] R.sup.6 is independently of each other an unbranched C.sub.2-s-alkylene, preferably [0211] (CH.sub.2).sub.2 or (CH.sub.2).sub.3, [0212] R.sup.7 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably (CH.sub.2).sub.2 or methylene, [0213] R.sup.3 is independently H or OH, [0214] R.sup.9 is independently of each other is an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably methylene, [0215] R.sup.11 is independently of each other

##STR00037## R.sup.12 is independently of each other

##STR00038## [0216] R.sup.13 is independently of each other an aliphatic or cyclic C.sub.1-18-alkylene or arylene, in each case optionally substituted by C.sub.1-8-alkyl or benzyl, preferably unbranched C.sub.1-8-alkylene, in particular (CH.sub.2).sub.4, (CH.sub.2).sub.6,

##STR00039## n is an integer from 20-2,000, preferably 40-1,000, particularly preferably 40-180, and [0217] m is 0 or an integer greater than 0, preferably 0 or 1-2,000, particularly preferably 0 or 1-55. [0218] 2. Polysiloxane according to item 1, wherein 0-99.9%, preferably 50-99.9%, more preferably 80-99.9% and particularly preferably 90-99.9% or 0-99.999%, preferably 50-99.999%, more preferably 80-99.999% and particularly preferably 90-99.999% of the R.sup.1 substituents are methyl. [0219] 3. Polysiloxane according to any of the preceding items, wherein the two terminal R.sup.1-substituents are methyl and at least one lateral R.sup.1-substituent corresponds to one of the formulae II-V. [0220] 4. Polysiloxane according to any of items 1-2, wherein all lateral R.sup.1-substituents are methyl and the two terminal R.sup.1-substituents are selected from formulae II-V. [0221] 5. Polysiloxane according to any of the preceding items, wherein all R.sup.1-substituents are selected from methyl and formula II. [0222] 6. Polysiloxane according to any of the preceding items, wherein 10-100%, preferably 40-99.9%, more preferably 50-95% and most preferably 60-80% of R.sup.3 in formula A are zwitterionic groups. [0223] 7. Polysiloxane according to any of the preceding items, wherein all zwitterionic groups are present as formula VIa. [0224] 8. Polysiloxane according to any of items 1-6, wherein all zwitterionic groups are present as formula VIb. [0225] 9. Polysiloxane according to any of the preceding items, wherein R.sup.2 is preferably

##STR00040##

[0226] 10. Polysiloxane according to any of the preceding items, wherein R.sup.11 is

##STR00041## [0227] 11. Polysiloxane according to item 10, wherein R.sup.12 corresponds to one of the formulae XIII or XIV. [0228] 12. Polysiloxane according to any of the preceding items, wherein essentially all, in particular 90-99.999%, of the lateral R.sup.1-substituents are methyl if m is greater than 0. [0229] 13. Polysiloxane according to any of items 1-9, having the general formula I

##STR00042## wherein [0230] R.sup.1 is independently of each other [0231] methyl,

##STR00043## with the proviso that in formula I at least one R.sup.1 corresponds to one of formulae II-V, [0232] R.sup.2 is independently of each other

##STR00044## R.sup.3 is independently of each other

##STR00045## or a zwitterionic group selected from

##STR00046## with the proviso that at least one R.sup.3 in formula I is a zwitterionic group, [0233] R.sup.4 is independently of each other an unbranched or branched C.sub.1-7-alkylene, preferably an unbranched C.sub.1-5-alkylene, particularly preferably (CH.sub.2).sub.2, [0234] R.sup.5 is independently of each other a branched or unbranched C.sub.1-18-alkyl, preferably an unbranched C.sub.1-8-alkyl, particularly preferably methyl, [0235] R.sup.6 is independently of each other an unbranched C.sub.2-s-alkylene, preferably (CH.sub.2).sub.2 or (CH.sub.2).sub.3, [0236] R.sup.7 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably (CH.sub.2).sub.2 or methylene, [0237] R.sup.3 is independently H or OH, [0238] R.sup.9 is independently of each other an unbranched or branched C.sub.1-18-alkylene, preferably an unbranched C.sub.1-8-alkylene, particularly preferably methylene, and [0239] n is an integer from 20-2,000, preferably 40-1,000, particularly preferably 40-180. [0240] 14. A process for the preparation of polysiloxanes according to any of the preceding items, comprising [0241] (a) providing a polysiloxane of the general formula VII

##STR00047## wherein [0242] R.sup.10 is independently of each other [0243] methyl,

##STR00048## [0244] with the proviso that in formula VII at least one R.sup.10 corresponds to one of formulae VIII-XI, [0245] (b) optionally reacting the polysiloxane of the general formula VII with a diisocyanate of the formula OCNR.sup.13NCO, and [0246] (c) reacting the polysiloxane of the formula VII or the polysiloxane adduct obtained after step (b) with a reactant selected from a peroxide and/or a compound of the general formula XII

##STR00049## wherein X is a halogen, in particular Cl or Br, [0247] and wherein the peroxide is preferably hydrogen peroxide (H.sub.2O.sub.2), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peroxyacetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and/or barium peroxide and particularly preferably hydrogen peroxide (H.sub.2O.sub.2). [0248] 15. Process according to item 14, wherein the molar ratio between reactant and the tertiary amino groups in the polysiloxane of formula VII or in the polysiloxane adduct obtained after step (b) is 0.1:1-1:1, preferably 0.4:1-0.999:1, more preferably 0.5:1-0.95:1 and most preferably 0.6:1-0.8:1. [0249] 16. Process according to item 14 or 15, wherein in step b) the molar ratio of the isocyanate groups of the diisocyanate of the general formula OCNR.sup.13NCO to the isocyanate-reactive hydroxy groups of the polysiloxane of the general formula VII is from 0.1:1-1:1, more preferably from 0.4:1-0.999:1, particularly preferably from 0.5:1-0.95:1 and most preferably from 0.6:1-0.9:1. [0250] 17. Process according to any of items 14-16, wherein in step b) the diisocyanate of the general formula OCNR.sup.13NCO is selected from the group consisting of toluene-2,4-diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), higher-chain homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate and/or isophorone diisocyanate. [0251] 18. Process according to any of items 14-17, wherein in step b) and/or c) the reaction is carried out at 15-150 C., preferably at 20-105 C., more preferably at 25-95 C., even more preferably at 40-90 C. and particularly preferably at 70-85 C. [0252] 19. Process according to any of items 14-18, wherein step b) is carried out using a solvent or in the absence of a solvent, preferably in the absence of a solvent. [0253] 20. Process according to any of items 14-19, wherein step b) is carried out using a catalyst, in particular based on a tertiary amine, a bismuth compound and/or an organotin compound. [0254] 21. Process according to one of items 14-20, wherein the course of the reaction in step b) is monitored titrimetrically or by IR spectroscopy. [0255] 22. The process according to any of items 14-21, wherein the reaction in step c) is carried out in a solvent preferably comprising water and/or at least one organic solvent. [0256] 23. A composition comprising [0257] (i) at least one polysiloxane according to any of items 1-13 and [0258] (ii) a solvent, in particular water and/or an organic solvent. [0259] 24. Composition according to item 23, wherein the composition contains 0.005-99.9% by weight, preferably 5-99% by weight, particularly preferably 10-90% by weight of component (i), based on its total mass. [0260] 25. Composition according to any of items 23-24, further comprising [0261] (iii) at least one anionic, cationic, non-ionic or amphoteric emulsifier, preferably at least one nonionic emulsifier, particularly preferably ethoxylated products of aliphatic alcohols. [0262] 26. Composition according to item 25, wherein the emulsifier (iii) is present with 2-100 wt. %, preferably with 10-80 wt. %, particularly preferably with 20-70 wt. %. based on component (i) [0263] 27. Composition according to any of items 23-26, wherein the organic solvent is preferably from the group of mono- and polyfunctional alcohols and/or their ether compounds and/or their ester compounds. [0264] 28. Composition according to any of items 23-27, further comprising [0265] (iv) at least one additive, for example a dilutant, glycerol, urea and/or at least one acid and/or at least one softening agent, preferably an organomodified polysiloxane. [0266] 29. Composition according to any of items 23-28, which is present as an emulsion, preferably as an o/w emulsion. [0267] 30. A use of a polysiloxane according to any of items 1-13 or a composition according to any of items 23-29 for treating a substrate, in particular for finishing a textile substrate, or as an additive in paint, glaze, lacquer and/or car care formulations. [0268] 31. Use according to item 30, wherein the textile substrate is a fabric, knitted fabric, nonwoven, fibre and/or leather. [0269] 32. Use according to any of items 30-31, wherein the textile substrate contains natural fibres, in particular cotton and/or wool, and/or synthetic fibres, in particular viscose, polyester, polyamide and/or polyacrylonitrile. [0270] 33. Use according to any of the items 30-32 for improving the soft handle of the textile substrate. [0271] 34. Use according to item 30 for improving the wetting, spreading and/or levelling properties of paint, glaze, lacquer and/or car care formulations. [0272] 35. A substrate, in particular textile substrate, which is treated with polysiloxanes according to any of items 1-13. [0273] 36. Substrate according to item 35, which contains 0.04-2.4% by weight, preferably 0.08-1.2% by weight, of polysiloxanes based on the total mass of the textile substrate. [0274] 37. A process for treating a substrate comprising the steps of [0275] (iii) providing a substrate, [0276] (iv) applying the polysiloxane according to any of items 1-13 or a composition according to any of items 23-29 to the substrate, and [0277] (v) optionally treating the substrate obtained after step (ii) at elevated temperature. [0278] 38. Process for treating a substrate according to item 37, wherein step (ii) is carried out by foulard, spraying, brushing, dipping, padding and/or by exhaust. [0279] 39. Process for treating a substrate according to any of items 37-38, wherein in step (iii) water is removed, preferably at a temperature of 110-150 C.