Siloxanes for treating textiles and for use in cleaning and care formulations

Abstract

Specific siloxanes, compositions containing these specific siloxanes, and processes for preparation thereof, are useful for treatment of fabrics, in cleaning and care formulations for the household and for industrial purposes, and in cosmetic, pharmaceutical and dermatological compositions, especially in cosmetic cleansing and care formulations, hair treatment products and hair aftertreatment products, and for cleaning and care of hard surfaces, preferably for cleaning and care of motor vehicles, especially as additive in drying aids for carwash facilities.

Claims

1: A siloxane (A) of formula (I):
M.sup.1.sub.a1M.sup.2.sub.a2M.sup.3.sub.a3M.sup.4.sub.a4D.sup.1.sub.b1D.sup.2.sub.b2D.sup.3.sub.b3T.sup.1.sub.c1T.sup.4.sub.c4Q.sub.dFormula(I), with M.sup.1=[R.sup.1.sub.3SiO.sub.1/2]; M.sup.2=[R.sup.2R.sup.1.sub.2SiO.sub.1/2]; M.sup.3=[R.sup.3R.sup.1.sub.2SiO.sub.1/2]; M.sup.4=[R.sup.4R.sup.1.sub.2SiO.sub.1/2]; D.sup.1=[R.sup.1.sub.2SiO.sub.2/2]; D.sup.2=[R.sup.1R.sup.2SiO.sub.2/2]; D.sup.3=[R.sup.1R.sup.3SiO.sub.3/2]; T.sup.1=[R.sup.1SiO.sub.3/2]; T.sup.4=[R.sup.4SiO.sub.3/2]; Q=[SiO.sub.4/2]; a1=0 to 32; a2=0 to 32; a3=0 to 32; a4=0 to 6; b1=1 to 1000; b2=0 to 10; b3=0 to 10; c1=0 to 10; c4=0 to 5; d=0 to 10; R.sup.1=each independently identical or different hydrocarbon radicals; R.sup.2=R.sup.21-R.sup.22; R.sup.21=each independently identical or different divalent hydrocarbon radicals having at least one hydroxyl group and optionally further oxygen atoms; R.sup.22=each independently identical or different radicals of formula (II) ##STR00028## R.sup.3=R.sup.31-R.sup.32; R.sup.31=R.sup.21; R.sup.32=each independently identical or different radicals of formula (III) ##STR00029## R.sup.4=each independently identical or different alkoxy groups or acyloxy groups; R.sup.7=each independently identical or different divalent radicals selected from the group consisting of O and NR.sup.10; R.sup.8=each independently identical or different radicals selected from the group consisting of hydrocarbon radicals; R.sup.9=each independently identical or different radicals selected from the group consisting of hydrogen and hydrogen radicals; R.sup.10=each independently identical or different radicals selected from the group consisting of hydrogen, C(O)R.sup.9, and hydrocarbon radicals; R.sup.11=each independently identical or different radicals selected from the group consisting of hydrocarbon radicals having at least one hydroxyl group; A.sup.m-=each independently identical or different anions selected from inorganic or organic anions of acids H.sub.mA, and derivatives thereof, m=1 to 3; and x=2 to 18; wherein conditions (i) and (ii) are applicable:
a2+b21; and(i)
a3+b31.(ii)

2: The siloxane (A) according to claim 1, wherein in addition, either condition (iii) or condition (iv) is applicable:
a1=a4=b2=b3=c1=c4=d=0 and
a2=a3=1; or(iii)
b2=b3=0,
c1+c4+d1, and
a2+a3+a43.(iv)

3: A composition, comprising: at least one siloxane (A) according to claim 1.

4: The composition according to claim 3, wherein the composition additionally comprises: at least one siloxane selected from the group consisting of siloxane (B) and siloxane (C), wherein: the siloxane (B) is a siloxane that differs from the siloxane (A) at least in that conditions (v) and (vi) are applicable rather than the conditions (i) to (ii):
a2=b2=0, and(v)
a3+b32; and(vi) the siloxane (C) is a siloxane that differs from the siloxane (A) at least in that conditions (vii) and (viii) are applicable rather than conditions (i) and (ii):
a3=b3=0, and(vii)
a2+b22.(viii)

5: The composition according to claim 4, wherein a. a proportion by mass of the at least one siloxane (A) based on the total mass of the siloxanes is from 20% to 70%; and/or b. a proportion by mass of the siloxane (B) based on the total mass of the siloxanes is from 0% to 15%; and/or c. a proportion by mass of the siloxane (C) based on the total mass of the siloxanes is from 3% to 80%.

6: The composition according to claim 3, wherein the composition comprises amide amines, wherein a proportion by mass of the amide amines based on the total mass of the at least one siloxane (A) is less than 1%.

7: A process for preparation of the siloxane (A) according to claim 1 or of a composition comprising the siloxane (A), the process comprising: reacting at least one epoxy-functional siloxane having at least two epoxy groups with at least one tertiary amine selected from the group consisting of amide amines and ester amines, and at least one tertiary amine selected from the group consisting of dialkanolamines, to form quaternary ammonium groups.

8: The process according to claim 7, wherein at least one epoxy-functional siloxane is prepared by hydrosilylation of at least one olefinically unsaturated epoxide with at least one SiH-functional siloxane of formula (V)
M.sup.1.sub.a1M.sup.5.sub.a5D.sup.1.sub.b1D.sup.5.sub.b5T.sup.1.sub.c1T.sup.4.sub.c4Q.sub.dFormula (V), with M.sup.5=[R.sup.1.sub.2SiHO.sub.1/2], D.sup.5=[R.sup.1SiHO.sub.2/2], a5=0 to 32; b5=0 to 10; where M.sup.1, D.sup.1, T.sup.1, T.sup.4, Q, a1, b1, c1, c4, d, and R.sup.1 are as defined in formula (I).

9: The process according to claim 7, wherein the at least one epoxy-functional siloxane is a siloxane of the formula (VI)
M.sup.1.sub.a1M.sup.6.sub.a5D.sup.1.sub.b1D.sup.6.sub.b5T.sup.1.sub.c1T.sup.4.sub.c4Q.sub.dFormula (VI), with M.sup.6=[R.sup.13R.sup.1.sub.2SiO.sub.1/2], D.sup.6=[R.sup.13R.sup.1SiO.sub.2/2], a5=0 to 32, b5=0 to 10, R.sup.13=each independently identical or different organic epoxy radicals wherein M.sup.1, D.sup.1, T.sup.1, T.sup.4, Q, a1, b1, c1, c4, d, and R.sup.1 are as defined in formula (I).

10: The process according to claim 7, wherein a residual content of the at least one tertiary amine selected from the group consisting of amide amines and ester amines after the reaction, as a proportion by mass based on the total mass of the composition, is less than 1%.

11: The process according to claim 7, wherein the at least one tertiary amine selected from the group consisting of amide amines and ester amines is a tertiary amine of formula (VII) ##STR00030## wherein R.sup.8, R.sup.7, R.sup.9 and x are as defined in formula (II).

12: The process according to claim 7, wherein the at least one tertiary amine selected from the group consisting of dialkanolamines is a tertiary amine of formula (VIII) ##STR00031## wherein R.sup.8 and R.sup.11 are as defined in formula (III).

13: A composition obtainable by the process according to claim 7.

14: A composition, comprising: water, and at least one siloxane (A) according to claim 1 or a composition comprising the at least one siloxane (A).

15: A method, comprising: a) treating two-dimensional structures; b) producing cleaning and care formulations for the household and for industrial purposes; c) producing cosmetic, pharmaceutical, and dermatological compositions; and/or d) cleaning hard surfaces, with the siloxane (A) according to claim 1.

16: The siloxane (A) according to claim 1, wherein a1=0 to 12; a2=1 to 3; a3=1 to 2; a4=0; b1=10 to 400; b2=0; b3=0; c1=0 to 4; c4=0; d=0 to 4; R.sup.1=alkyl radicals having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms, wherein the alkyl radicals are linear, branched, saturated, or unsaturated; R.sup.21=each independently identical or different divalent radicals selected from the group consisting of ##STR00032## R.sup.4=each independently identical or different groups, selected from the group consisting of acetoxy groups, methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, tert-butoxy groups, and alkoxy groups derived from glycol radicals; R.sup.5=each independently identical or different radicals selected from the group consisting of hydrogen and hydrocarbon radicals; R.sup.6=each independently identical or different divalent hydrocarbon radicals optionally containing ether groups; R.sup.7=each independently identical or different divalent radicals NR.sup.10; R.sup.8=each independently identical or different radicals selected from the group consisting of linear, branched, saturated, or unsaturated alkyl radicals having 1 to 12 carbon atoms; R.sup.9=each independently identical or different radicals selected from the group consisting of alkyl radicals having 12 to 24 carbon atoms, wherein the hydrocarbon radicals or alkyl radicals are linear, branched, substituted, unsubstituted, saturated, or unsaturated; R.sup.10=each independently identical or different radicals selected from the group consisting of alkyl radicals having 1 to 6 carbon atoms, wherein the hydrocarbon radicals or alkyl radicals are linear, branched, substituted, unsubstituted, saturated, or unsaturated; R.sup.11=each independently identical or different radicals selected from the group consisting of alkyl radicals having at least one hydroxyl group and 1 to 6 carbon atoms, wherein the alkyl radicals are linear, branched, saturated, or unsaturated, and radicals of the formula (IV) ##STR00033## R.sup.12=each independently identical or different radicals selected from the group consisting of hydrocarbon radicals; m=1; v=0 to 30; w=0 to 30; x=3; and y=2 to 18.

17: The Siloxane (A) according to claim 16, wherein R.sup.1=methyl, ethyl, propyl, or phenyl; R.sup.21=each independently identical or different divalent radicals selected from the group consisting of ##STR00034## R.sup.5=each independently identical or different radicals selected from the group consisting of alkyl radicals having 1 to 6 carbon atoms, wherein the alkyl radicals are linear, branched, saturated, or unsaturated; R.sup.6=each independently identical or different divalent hydrocarbon radicals optionally containing ether groups, having 1 to 6 carbon atoms; R.sup.8=each independently identical or different radicals selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl; R.sup.9=each independently identical or different radicals selected from the group consisting of alkyl radicals having 16 to 22 carbon atoms, wherein the hydrocarbon radicals or alkyl radicals are linear, unsubstituted, and saturated; R.sup.10=hydrogen; R.sup.11=2-hydroxyethyl and/or 2-hydroxypropyl; R.sup.12=each independently identical or different radicals selected from the group consisting of alkyl radicals having 1 to 6 carbon atoms, wherein the alkyl radicals are linear, branched, saturated, or unsaturated; m=1; v=1 to 3; w=0 to 10; and y=3, wherein for R.sup.4, the glycol radicals, if present, are selected from the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, pentylene glycol, and butyldiglycol.

18: The siloxane (A) according to claim 2, wherein for condition (iv), a22, a31,and a4=0.

19: The composition according to claim 4, wherein the siloxane (B) is a siloxane that differs from the siloxane (A) precisely in that the conditions (v) and (vi) are applicable rather than the conditions (i) to (ii), and wherein the siloxane (C) is a siloxane that differs from the siloxane (A) precisely in that the conditions (vii) and (viii) are applicable rather than the conditions (i) and (ii).

20: The composition according to claim 5, wherein a. the proportion by mass of the at least one siloxane (A) based on the total mass of the siloxanes is from 30% to 50%; and/or b. the proportion by mass of the at least one siloxane (B) based on the total mass of the siloxanes is from 1% to 10%; and/or c. the proportion by mass of the at least one siloxane (C) based on the total mass of the siloxanes is from 10% to 50%.

Description

EXAMPLES

General Methods

Nuclear Spin Resonance Spectroscopy (NMR Spectroscopy)

[0379] The siloxanes can be characterized with the aid of .sup.1H NMR and .sup.29Si NMR spectroscopy. These methods, especially taking account of the multiplicity of the couplings, are familiar to the person skilled in the art.

[0380] The conversion of the epoxy groups (epoxy conversion) can be determined with the aid of .sup.1H NMR spectroscopy.

Gel Permeation Chromatography (GPC):

[0381] GPC measurements for determination of the polydispersity and weight-average molar masses Mw are conducted under the following measurement conditions: Column combination SDV 1000/10 000 (length 55 cm), temperature 35 C., THF as mobile phase, flow rate 0.35 ml/min, sample concentration 10 g/l, RI detector, evaluation of the polymers against polystyrene standard (162 2 520 000 g/mol).

High-performance liquid Chromatography (HPLC):

[0382] To determine the concentration of amide amines (Tegoamid S18, Tegoamid D5040, Tegoamid PKFC), reverse-phase HPLC is conducted with gradient conditions. An RP-C18 column (Inertsil ODS-3, GL Science) is used as stationary phase. Acetonitrile and dilute sulfuric acid are employed as binary eluent system. Detection is effected by UV detector at a wavelength of 210 nm. The external standard used for the calibration is specific amide amines that are used in the respective synthesis of the siloxane/silicone quat. The residual content is reported in percent by weight based on the corresponding composition.

Gas Chromatography:

[0383] The proportion by mass of cyclic siloxanes, especially octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), can be determined with the aid of a gas chromatography method (GC method) in which the substances are separated according to their boiling point and detected by means of a thermal conductivity detector. This is done by analysing an aliquot of the sample to be examined without further dilution by means of GC. This is conducted in a gas chromatograph equipped with a spilt/splitless injector, a capillary column and a thermal conductivity detector, under the following conditions: [0384] Injector: 290 C., split 40 ml [0385] Injection volume: 1 l [0386] Column: 5 m*0.32 mm HP5 1 m [0387] Carrier gas: helium, const. flow, 2 ml/min [0388] Temperature program: 1 minute at 80 C., then 80 C.-300 C. at 30 C./min, then conditioning at 300 C. for 10 minutes. [0389] Detector: TCD at 320 C. [0390] Make-up gas 6 m/min [0391] Reference gas 18 ml/min

[0392] The cyclic siloxanes are separated according to their boiling point. The proportion by mass of the individual substances is determined as the percentage of the peak areas determined for the respective substance by comparison with the total area of all substances detected (area % method).

Viscosity:

[0393] Viscosity is measured with a Brookfield R/S-CPS Plus rheometer using the RP75 measurement plate at 25 C. The test method is described in DIN 53019 (DIN 53019-1:12008-09, DIN 53019-2:2001-02 and DIN 53019-3:2008-09).

General Synthesis Method:

[0394] The quaternized siloxanes (also referred to here as active ingredients or silicone quats) are prepared in the manner known to the person skilled in the art, as described in the prior art, for example in publications DE 102010000993 A1 and DE 3802622 A1. The preparation is effected in three stages. In the first stage the SiH-functional siloxanes are prepared. In the second stage the SiH-functional siloxanes prepared are used to prepare epoxy-functional siloxanes by means of hydrosilylation. In the third stage the epoxy-functional siloxanes obtained are reacted with tertiary amines under acid catalysis as follows:

1st StagePreparation of SiH-Functional Siloxanes:

Linear Terminal SiH Siloxanes:

[0395] An inertized 500 ml three-neck flask with a precision glass stirrer, reflux condenser and internal thermometer was initially charged with the respective amounts (cf. Table 1) of decamethylcyclopentasiloxane (D5) and ,-dihydropolydimethylsiloxane (,-dihydro-PDMS) having an SiH value of 2.97 mmol/g, and 0.25 g of trifluoromethanesulfonic acid was added while stirring. After stirring at 40 C. for 6 h, 5 g of sodium hydrogencarbonate were added and the mixture was stirred for 2 h. After filtration, transparent, fluid, colourless products were obtained.

[0396] Starting weights and further details of the preparation of the SiH-functional siloxanes can be found in Table 1.

TABLE-US-00001 TABLE 1 Starting weights and further details of the preparation of the SiH-functional siloxanes of formula (V) ,-dihydro- SiH siloxane a5 b1 R.sup.1 PDMS D5 SH1 2 48 methyl 45.5 g 204.5 g SH2 2 78 methyl 28.5 g 221.5 g SH4 2 18 methyl 114.6 g 135.4 g SH5 2 28 methyl 76.2 g 173.8 g

Branched SiH Siloxane (SH3):

[0397] The preparation was effected as disclosed in document EP 2176319 B1.

[0398] 44.2 g (0.248 mol) of methyltriethoxysilane, 125.3 g of an ,-dihydropolydimethylsiloxane having a hydrogen content of 2.97 mmol SiH/g and 1352.5 g of decamethylcyclopentasiloxane were initially charged in a four-neck flask equipped with a precision glass stirrer, an internal thermometer, a dropping funnel and a distillation system while stirring at room temperature, 1.5 g of trifluoromethanesulfonic acid were added and the mixture was stirred for 30 minutes. A mixture of 13.4 g of deionized water and 20 ml of methanol was added dropwise while stirring within a further 30 minutes, and the mixture was stirred for a further 30 minutes. The reaction mixture was heated to 40 C. for 1 hour and then distilled in a waterjet-pump vacuum of about 50 mbar at 40 C. for 1 hour. After neutralization with 30.4 g of sodium hydrogencarbonate and filtration, 152 g of Lewatit K 2821, a predried sulfonic acid cation exchange resin, were added, and the mixture was stirred at 40 C. for 4 hours and filtered. This gave a clear, colourless liquid.

2nd StagePreparation of Epoxy-Functional Siloxanes:

[0399] An inertized 500 ml three-neck flask with precision glass stirrer, Internal thermometer and reflux condenser was initially charged with the respective amounts of SiH siloxane and allyl glycidyl ether (AGE) (cf. Table 2) and heated up to 70 C. while stirring. 0.13 g of Karstedt catalyst (0.1% Pt) was added with a syringe and the mixture was stirred at 80 C. for a further 2 h, if required with counter-cooling of the initial exothermicity. After distillation at 120 C. and 1 mbar for 3 h, a transparent, pale beige, fluid product of viscosity 135 mPa*s was obtained. The hydrosilylation reaction was brought to full conversion in relation to the hydrogen content of the SiH-functional siloxanes. In the context of the present invention, full conversion is understood to mean that more than 99% of the SiH functions were converted. Detection is effected in a manner familiar to the person skilled in the art by gas-volumetric means after alkaline breakdown.

[0400] Starting weights and further details of the preparation of the epoxy-functional siloxanes can be found in Table 2.

TABLE-US-00002 TABLE 2 Starting weights and further details of the preparation of the epoxy-functional siloxanes of formula (VI) Epoxysiloxane a5 b1 c1 R.sup.1 SiH siloxane AGE SE1 2 48 0 methyl 231.4 g SH1 18.6 g SE2 2 78 0 methyl 238.1 g SH2 11.9 g SE3 6 316 4 methyl 241.1 g SH3 8.9 g SE4 2 18 0 methyl 208.0 g SH4 42.0 g SE5 2 28 0 methyl 220.4 g SH5 29.6 g

3rd StagePreparation of the Silicone Quats:

[0401] An inertized 500 ml three-neck flask with precision glass stirrer, dropping funnel, Internal thermometer and reflux condenser was initially charged with the respective amounts (cf. Table 3) of amide amine, alkanolamine and solvent, the respective amount of carboxylic acid was metered in and the mixture was stirred at room temperature for 1 hour. Subsequently, the respective epoxy-functional siloxane was added dropwise, and the mixture was heated to 80 C. and stirred for 12 to 16 hours until a conversion of epoxy groups (also referred to as epoxy conversion) of at least 90% had been attained. The conversion of the epoxy groups was determined by NMR spectroscopy. Optionally, the solvent was removed by distillation and exchanged by subsequent blending with another solvent, i.e. by dilution of the distillation residue obtained with another solvent.

[0402] The following raw materials were used in the preparation of the silicone quats: [0403] Amide1=3-N,N-dimethylaminopropylcocoamide, Tegoamid D 5040, Evonik [0404] Amide2=3-N,N-dimethylaminopropylstearamide, Tegoamid S 18, Evonik [0405] Amide3=3-N,N-dimethylaminopropylpalmitamide, Tegoamid PKFC, Evonik [0406] MDEA=N-methyldiethanolamine, 99%, Sigma-Aldrich [0407] MDIPA=N-methyldiisopropanolamine, BASF [0408] TEA=triethanolamine, 99%. Sigma-Aldrich [0409] DMAE=dimethylglycine (dimethylaminoacetic acid), >98%. Alfa-Aesar [0410] HOAc=acetic acid, p. A. Baker [0411] INA=isononanoic acid, 97%, Alfa-Aesar [0412] IPA=isopropanol, >99.9%, Sasol [0413] tBuOH=tert-butanol, ACS, Reag. Ph Eur, Merck [0414] DPG=dipropylene glycol, >=99%, Lyondell [0415] PG=1,2-propylene glycol, >=99%, Lyondell [0416] DMM=dipropylene glycol dimethyl ether, >94%, TCI Europe N.

[0417] Amide1 is prepared here by reaction of hydrogenated coconut fat with 3-aminopropyldiethylamine (DMAPA). The reaction leads to a chain length distribution of the fatty acid radical of the resulting amide amine from C8 to C18 with a maximum at C12.

[0418] The following epoxy-functional siloxanes were used in the preparation of the silicone quats:

TABLE-US-00003 TABLE 3 Epoxy-functional siloxanes of formula (VI) No. a1 a5 b1 b5 c1 c4 d R.sup.1 R.sup.12 SE1 0 2 48 0 0 0 0 methyl [00023] SE2 0 2 0 0 0 0 0 methyl [00024] SE3 0 6 316 0 4 0 0 methyl [00025] SE4 0 2 18 0 0 0 0 methyl [00026] SE5 0 2 28 0 0 0 0 methyl [00027]

[0419] Starting weights and further details of the preparation of the inventive siloxanes of formula (I) can be found in Tables 4and 5.

TABLE-US-00004 TABLE 4 Part 1: Starting weights and further details of the preparation of the inventive siloxanes of formula (I) (content figures in % by weight based on the overall composition) I1 I2 I3 I4 I5 I6 I7 SEI 860.2 g SE2 472.1 g 393.4 g 262.3 g 262.3 g 217.0 g SE3 297.7 g SE4 Amide1 109.1 g 39.3 g 21.8 g 21.8 g 17.5 g Amide2 39.6 g 21.0 g Amide3 MDEA 17.9 g 6.4 g 5.36 g 3.6 g 3.6 g 2.9 g 2.9 g MDIPA DMAE HOAc 30.9 g 11.1 g 9.3 g 6.2 g 4.9 g 4.9 g INA 16.3 g IPA 254.5 g 132.2 g 110.2 g 76 g 57.0 g DPG 73.5 g tBuOH DMM 13.0 g Distillation yes yes yes no yes no yes Blend yes yes yes no yes yes no Active 95% 80% 97.5% 80% 97.5% 80% 100% content.sup.1) Solvent 5% 20% 2.5% 20% 2.5% 15% PG DPG PG DPG PG DPG 5% DMM Epoxy 99% 97% 99% 97% 98% 87% 96% conversion Viscosity, 25 C., mPa*s 3960 1605 7414 1102 4731 851 n.d Residual amide amine content 0.4% 0.17% 0.35% 0.6% 0.4% .sup.0.3%

TABLE-US-00005 TABLE 4 Part 2: Starting weights and further details of the preparation of the inventive siloxanes of formula (I) (content figures in % by weight based on the overall composition) I8 I9 I10 I11 I12 I13 I14 SE1 SE2 189.8 g 419.7 g 419.7 g 288.5 g 472.1 g 239.9 g SE3 SE4 472.9 g Amide1 15.3 g 39.9 g 39.9 g 24.0 g Amide2 23.7 g 157.8 g Amide3 41.1 g MDEA 2.5 g 3.8 g 3.8 g 6.4 g 21.9 g MDIPA 4.0 g DMAE 3.4 g HOAc 4.3 g 9.9 g 9.9 g 4.8 g 11.1 g 5.6 g 37.4 g INA IPA 53 g 118 g 132.7 g 68.3 g 121.8 g DPG 67.9 g tBuOH 118 g 80.2 g DMM Distillation yes yes yes yes yes yes yes Blend yes yes yes yes yes yes yes Active 97.5% 97.5% 97.5% 97.5% 97.5% 80% 50% content.sup.1) Solvent 2.5% 2.5% 2.5% 2.5% 2.5% 20% 50% PG PG PG PG PG DPG PG Epoxy 99% 98% 96% 98% 99% 96% 100% conversion Viscosity, 25 C., mPa*s 8746 9104 8546 about 7544 1217 20000 Residual amide amine content 0.2% 0.6% 0.7% 0.8% 0.3% 0.1% .sup.0.8%

TABLE-US-00006 TABLE 4 Part 3: Starting weights and further details of the preparation of the inventive siloxanes of formula (I) (content figures in % by weight based on the overall composition) I15 I16 SE5 217.7 g 217.7 g Amide1 43.6 g Amide2 52.6 g MDEA 7.2 g 7.2 g HOAc 12.4 g 12.4 g IPA 70.2 g 72.5 g Distillation yes yes Blend yes yes Active 50% 50% content.sup.1) Solvent 50% PG 50% PG Epoxy 100% 98% conversion Viscosity, 705 616 25 C., mPa*s Residual 0.6% 0.6% amide amine content

TABLE-US-00007 TABLE 5 Starting weights and further details of the preparation of non-inventive siloxanes (content figures in % by weight based on the overall composition) V1 V2 V3 V4 SE1 860.2 g SE2 271.2 g 314.6 g 472.1 g SE3 Amide1 156 g 56.1 g Amide2 MDEA 14.3 g TEA 14.9 g HOAc 6.2 g 7.4 g 30.9 g 11.1 g INA IPA 73.0 g 254.5 g 132.2 g tBuOH 84.1 g Distillation yes yes yes yes Blend no yes yes yes Active content.sup.1) 97.5% 95% 97.5% Solvent 2.5% PG 5% PG 2.5% PG Epoxy conversion 0% 92.3% 98% 97% biphasic Viscosity, 25 C., 8429 4631 9114 mPa*s Residual amide 1.8% 1.4% amine content .sup.1)active content = proportion by mass of the siloxanes (active ingredients) based on the total mass of the composition

[0420] In the synthesis of inventive examples I1 to I14, mixtures of dialkanolamines and amide amines were used. In the case of comparative examples V1 and V2 by contrast, no amide amines but only alkanolamines were used, specifically a trialkanolamine in V1 and a dialkanolamine in V2. In the synthesis of comparative examples V3 and V4, again, exclusively amide amines and no alkanolamines were used. The non-inventive siloxane compositions V3 and V4 had a higher residual content of amide amine than the inventive siloxane compositions I1 to I14. In the case of V1 a phase separation was observed: no reaction of the epoxy-functional siloxane with the alkanolamine was detectable. In the case of V2, by contrast, epoxy conversion was observed. and so a reaction took place here. Since amide amines were not used either in V1 or V2, there is no need to state a residual content.

[0421] A non-inventive blend of 70 parts V4 with 30 parts V2 was prepared by stirring with a magnetic stirrer bar at room temperature in a sample bottle and subjected to HPLC analysis. The measurement of the residual amide amine content gave 0.8%, compared to the theoretical 0.9%. The inventive product 15 that was prepared by reaction of the same SE2 precursor with a mixture of 0.7 molar equivalent of Amide1 and 0.3 molar equivalent of MDEA based on 1 molar equivalent of epoxy groups has a residual amide amine content measured by HPLC of 0.4%. The solvent content of the mixture of V4 and V2 and in the case of 15 corresponded to 2.5% PG in a1 cases. This comparison shows that the inventive preparation of the novel mixed-functionality silicone quats and the compositions thereof achieves significantly lower residual amide amine contents than are achievable in comparison via the obvious blending.

Storage Stability Tests on the Silicone Quats:

[0422] Two 100 ml screwtop sample bottles in each case were each half-filled with the silicone quats I5. I6 and I7. One sample bottle was stored closed at room temperature (RT) and the respective second sample bottle was stored closed in a conventional laboratory drying cabinet from Binder at 50 C. After defined storage periods, the viscosity of the samples was determined at 25 C. and/or the content of cyclic siloxanes was checked by GC analysis. For better comparability and measurability, the 100% silicone quat 17, which had a high viscosity, was blended with 20% DPG to active content 80%. The results of the storage stability tests are summarized in Table 6.

TABLE-US-00008 TABLE 6 Results of the storage stability tests on the silicone quats (content figures in % by weight based on the overall composition) Storage Storage Viscosity at D4 content Sample period temperature 25 C. [mPa*s] [% by wt.] I5 0 week RT 4731 0.02 I5 4 weeks RT n.d 0.02 I5 12 weeks RT n.d 0.03 I5 4 weeks 50 C. n.d 0.06 I6 0 week RT 851 0.08 I6 4 weeks RT 1031 0.08 I6 12 weeks RT 1093 0.08 I7-80% 0 week RT 6396 0.09 I7-80% 4 weeks RT 5330 0.09 I7-80% 8 weeks RT 6001 0.09 I7-80% 12 weeks RT 6888 0.09

[0423] The storage tests show that there are no significant changes in viscosity and the silicone quats can still be metered efficiently even after prolonged storage time. In addition, the storage tests show that the new formation of cyclic siloxanes during the storage time is minimized, in that an increase in D4 of 0.05% by weight is detected. Sample 5, which was distilled particularly thoroughly, shows that the proportion of D4 is <0.1% by weight over a prolonged storage period. The content of D4 in the respective sample depends on the quality of distillation in the preparation and not on the storage time.

APPLICATION EXAMPLES

Materials Used:

[0424]

TABLE-US-00009 TABLE 7 Emulsifiers Emulsifiers Trade name C12-15 Pareth-7 / 9 / 12 Tomadol 25-7, Evonik Tomadol 25-9, Evonik Tomadol 25-12, Evonik Isotridecanol-6 / 8 / 12 Lutensol TO 6, BASF Lutensol TO 8, BASF Marlipal O13/120, BASF Laureth-6 / 12 Lutensol AO 6, BASF Marlipal 24/120, Sasol Sorbitan sesquioctanoate TEGO SQS 25, Evonik Methyldiisopropanolamine ester quat REWOQUAT CR 3099, Evonik

TABLE-US-00010 TABLE 8 Auxiliaries Further silicone compounds Trade name Alkyl/polyether-modified TEGOPREN 7008, Evonik silicone copolymer TEGOPREN 7009, Evonik

Fabric:

[0425] Textiles: cotton fabric (basis weight 205 g/m.sup.2, thickness: 400 m); polyester blend fabric (65% by weight of polyester and 35% by weight of cotton, basis weight 170 g/m.sup.2, thickness: 200 m); polyamide fabric (nylon-6,6, basis weight 65 g/m.sup.2. thickness: 50 m); all samples from WFK-Testgewebe GmbH (Christenfeld 10 41379 Brggen).

Formulation and Finishing:

Production of the Emulsions:

[0426] The synthesized siloxane compositions selected from I1 to I14 (based on mixtures of alkanolamine and amide amine), V2 (based on alkanolamine), V4 (based on amide amine) and V5 (Magnasoft DerMa NT as commercial comparative product) were initially charged and, if required. diluted further by addition of a glycol to the desired active content, i.e. the desired proportion by mass of active ingredient (siloxane). This was found to be advantageous since particularly good results were achieved when the active ingredients were converted further from a solvent, especially when they are used as mixtures with solvents having an active content of 80%. Thereafter, the mixtures RE1 to RE10 thus obtained were initially charged and the emulsifiers and any further auxiliaries and/or glycols were added. Then water was added gradually while stirring constantly with a propeller stirrer. The pH was adjusted to a pH of about 4 by subsequent addition of acetic acid. Stirring was continued until the mixture is homogeneous. In this way, the emulsions 11 to 126 and C1 to C5 were obtained.

Padding Method (Model: HVF, Mathis AG):

[0427] To test the respective emulsions, a liquor that contained 8 g/l of the appropriate emulsion in each case was applied to the above-described fabric, which was squeezed off to a wet pickup of about 70% to 80% by weight and dried. The values employed for pressure and speed can be found in Table 9. Padding application took place at room temperature.

TABLE-US-00011 TABLE 9 Pressures and roll speeds used in the padding method. Designation Pressure [bar] Speed [m/min] Cotton fabric 2.4-5.8 2 Polyester blend fabric 1.0-1.2 2 Polyamide fabric 1.0 1-2
Exhaust Process Starting from Solvent-Containing Formulations:

[0428] To test the active ingredients, the abovementioned fabrics were finished with a liquor that contained 20 g/l of the appropriate active ingredient in each case. A liquor ratio (fabric to liquor) of 1:15 was chosen. Solvents used are water, butyl acetate and ethyl acetate. The test fabric was treated in the liquor with continuous agitation on the reciprocating shaker (model: 3006, manufacturer GFL) for 30 min. After 30 min, the test fabric was removed from the bath, wrung out gently, shaken and dried. A blank was treated under the same conditions with demineralized water only.

Drying Method (LTE Lab Dryer, Mathis AG, Ventilator Speed 2000 Rpm):

[0429] The fabrics were dried at 105 C. (plus dwell time, i.e. the heating time of the textile fabric) for 2 min and then condensed at 160 C. to 180 C. (without dwell time) for 0.5 min to 1 min in order to fix the finish. The exact conditions are summarized in Table 10.

TABLE-US-00012 TABLE 10 Conditions for the drying process Drying Fixing [ C.] [min] [ C.] [min] Cotton fabric (exhaust) 105 2.0 160 1.0 Polyester blend fabric (exhaust) 105 2.0 180 0.5 Polyamide fabric (exhaust) 105 2.0 180 0.5 Cotton fabric (padding) 105 2.0 150 3.0 Polyester blend fabric (padding) 105 2.0 150 3.0 Polyamide fabric (padding) 105 2.0 150 3.0

Testing of the Finish:

Hand:

[0430] Hand is a fundamental quality parameter of a fabric. It can be described by, for example, smoothness, compressibility and stiffness. Normally, hand is determined by subjective assessment via manual testing. In addition, there are measuring instruments for the purpose that determine it objectively.

Assessment of Hand (Hand Test) Via Measuring Instruments (TSA Value/Handfeel):

[0431] A piece of textile fabric that has been cut to size, after prior conditioning (4 hours) at 25 C. and 50% relative air humidity, was inserted and clamped into the TSA (Tissue Soft Analyzer, from Emtec Electronic GmbH). The test instrument then determines individual values for softness, smoothness and stiffness of the textile fabric and uses these to ascertain the overall impression, the handfeel (HF). This TSA value (HF value) was ascertained by means of an algorithm specially designed for textiles by EMTEC. A higher HF value means a higher softness. The assessments are made in comparison to an analogous treatment without active ingredient.

Assessment of Hand (Hand Test) by Hand (Panel Test):

[0432] To assess hand, an experienced team of 10 specialists was assembled, who assessed the anonymized hand specimens, the abovementioned fabrics that had been finished with the emulsions, with the aid of a hand panel test on a scale of 1 to 5, with the mark 1 meaning very poor hand and the mark 5 very good hand. The result of the panel test is reported as the average of all assessments. For the hand specimens made of knitted fabric, an inconspicuously labelled untreated sample was additionally included.

Antistatic Properties:

[0433] Antistatic properties are measured in accordance with DIN 54345 T.1 (ring electrode) with measurement voltage 100 V (Tera-Ohm-Meter 6206 instrument). The finish with antistats reduces the electrical resistance on textile fabrics. The reduction in the resistance is a measure of antistatic efficacy.

[0434] The antistatic properties were determined using the following instruments and fabrics: [0435] Standard test fabric: polyester (100%, 30 A type from wfk/Krefeld) [0436] Washing machine for pretreatment and padding for finishing of the fabric [0437] Climate-controlled room (231 C., 50-60% r.h.) [0438] Tera-Ohm-Meter 6206 (from Eltex) [0439] 6216 test electrode (from Eltex) to DIN 54345 T.1

[0440] Prior to the measurement, the finished fabrics are stored in the climate-controlled room for one day in order to assure balanced moisture. 1015 cm pieces are placed onto a flat surface and the ring electrode is positioned thereon. The resistance of the different finishes is measured.

Application Results:

[0441] The synthesis products I3 to I12 and V2 and V4, and also a comparative product V5 which is customary on the market, if the active content was not already 80% by weight based on the composition, were brought to a homogeneous active content of 80% by addition of butyldiglycol (BDG). The mixtures RE1 to RE10 thus obtained are summarized in Table 8. These mixtures were used as described above to produce the emulsions I1 to I26 and C1 to C12. The compositions of the emulsions and the properties thereof are summarized in the tables which follow.

TABLE-US-00013 TABLE 11 Preliminary mixtures for the comparative performance testing RE8 RE1 RE2 RE4 RE5 RE6 RE7 RE3 RE9 RE10 Siloxane I3 I4 I8 I9 I10 I11 I12 V2 V4 V5 Additional solvent BDG BDG BDG BDG BDG BDG BDG BDG BDG

TABLE-US-00014 TABLE 12 Inventive emulsions and their properties (content figures in % by weight based on the overall composition) % I1 I2 I3 I4 I5 RE8 18.2 23.8 32.5 25 25 TEGOPREN 7008 5.6 TOMADOL 25-7 7.7 1.7 TOMADOL 25-9 2.5 1.5 TOMADOL 25-12 3.4 TEGO SQS 25 2.5 5.5 REWOQUAT 5.7 CR 3099 Butyldiglycol 8.6 10.0 Dipropylene 5.0 15.0 glycol Water 60.1 66.2 41.4 63.2 69.6 Acetic acid 0.3 0.3 0.3 Appearance clear milky white clear clear opaque solution solution solution Emulsion type micro- macro- micro- micro- micro- emulsion emulsion emulsion emulsion emulsion Property bulky bulky substantive cost- solvent- efficient reduced Hand test 39.2 38.8 38.4 37.6 37.2 (TSA value)

TABLE-US-00015 TABLE 13 Non-inventive emulsions and their properties (content figures in % by weight based on the overall composition) % C1 C2 C3 C4 C5 RE9 18.2 23.8 32.5 25 25 TEGOPREN 7008 5.6 TOMADOL 25-7 7.7 1.7 TOMADOL 25-9 2.5 1.5 TOMADOL 25-12 3.4 TEGO SQS 25 2.5 5.5 REWOQUAT 5.7 CR 3099 Butyldiglycol 8.6 10.0 Dipropylene 5.0 15.0 glycol Water 60.1 66.2 41.4 63.2 69.6 Acetic acid 0.3 0.3 0.3 Appearance clear milky white clear clear opaque solution solution solution Emulsion micro- macro- micro- micro- micro- type emulsion emulsion emulsion emulsion emulsion Property bulky bulky substantive cost-efficient solvent-reduced Hand test 37.4 37.0 37.3 36.5 36.3 (TSA value)

[0442] The inventive emulsions I1 to I5 from Table 12 differ from the corresponding non-inventive emulsions C1 to C5 from Table 13 only in the active ingredient used, with otherwise identical composition. The inventive emulsions by comparison with the non-inventive emulsions show distinctly improved TSA values (HF values, handfeel). The improved hand properties were confirmed in panel tests. As well as handfeel, good water absorption is also of relevance for wear comfort. Finishing with the inventive emulsions does not show any disadvantages here compared to finishing with emulsions based on prior art active ingredients. According to the material quality (thickness and weave type) and formulation, it is even possible to achieve better water absorption capacities or water retention capacities. Water absorption capacity or water retention capacity is additionally also affected by the choice of emulsifiers used.

TABLE-US-00016 TABLE 14 Inventive emulsions comprising auxiliaries for improvement of bulkiness and properties thereof (content figures in % by weight based on the overall composition) % I6 I7 I8 I9 I10 I11 RE0 20 20 20 RE1 20 20 20 TEGOPREN 4.0 4.0 7008 TEGOPREN 4.0 4.0 7009 Lutensol 1.5 1.5 1.5 1.5 1.5 1.5 TO 8 Butyldiglycol 10.0 10.0 10.0 10.0 10.0 10.0 Dipropylene 5.5 5.5 5.5 5.5 5.5 5.5 glycol Water 58.7 58.7 58.7 58.7 58.7 58.7 Acetic acid 0.3 0.3 0.3 0.3 0.3 0.3 Appearance clear clear separa- separa- clear clear solution solution tion tion solution solution Hand test 39.3 38.1 38.0 38.4 36.8 37.2 (TSA value) Panel test 5 4.3 4.3 4.3 3.8 4.0 (1-5; 5 = best mark)

[0443] Table 14 shows that the additional use of auxiliaries/additives for improving bulkiness (Tegopren 7008 and Tegopren 7009) can further improve the assessments of hand. This is equally true of assessments of hand that have been determined by means of measuring instruments (TSA value, handfeel) and by hand (panel test). The active ingredients according to the invention, In combination with an auxiliary/additive for improving bulkiness, show the best results when they have been converted from a solvent, especially when they have been used as mixtures with an active content of 80%. This finish is also impressive in an assessment of hand in a panel test.

TABLE-US-00017 TABLE 15 Emulsions with cost-optimized auxiliaries and their properties (content figures in % by weight based on the overall composition) % I12 C6 I13 I14 C7 I15 RE2 20.5 RE3 20.5 RE4 20.5 RES 20.5 RE9 20.5 RE6 20.5 Isotridecanol 1.5 1.5 1.5 1.5 1.5 1.5 8EO Butyldiglycol 10.0 10.0 10.0 10.0 10.0 10.0 Dipropylene 4.5 4.5 4.5 4.5 4.5 4.5 glycol Water 63.2 63.2 63.2 63.2 63.2 63.2 Acetic acid 0.3 0.3 0.3 0.3 0.3 0.3 Appearance clear separa- clear clear separa- clear solution tion solution solution tion solution Hand test 38.5 37.3 37.1 36.7 37.3 37.6 (TSA value)

[0444] Table 15 shows that, when cost-optimized auxiliaries are used, such as isotridecanol 8EO, very good assessments of hand are likewise achieved in the case of the emulsions according to the invention, without observation of phase separation.

TABLE-US-00018 TABLE 16 Inventive and non-inventive emulsions comprising additives for improvement of bulkiness and properties thereof (content figures in % by weight based on the overall composition) % I16 C8 I17 I18 C10 I19 RE2 18.5 RE3 18.5 RE4 18.5 RE5 18.5 RE9 18.5 RE6 18.5 TEGOPREN 5.6 5.6 5.6 5.6 5.6 5.6 7008 Rewopal 7.7 7.7 7.7 7.7 7.7 7.7 LA6 Butyldiglycol 5.0 5.0 5.0 5.0 5.0 5.0 Water 62.9 62.9 62.9 62.9 62.9 62.9 Acetic acid 0.3 0.3 0.3 0.3 0.3 0.3 Appearance clear separa- clear clear clear clear solution tion solution solution solution solution Hand test 38.3 37.9 37.3 38.2 37.4 37.3 (TSA value)

[0445] Table 16 shows the advantages of the emulsions according to the invention. The non-Inventive emulsion C8 shows good results in the hand test and no residual content of amide amines since it is based on an active ingredient (V2) that has been prepared solely from alkanolamines as tertiary amines. But emulsion C8 has the disadvantage that a phase separation is observed. Conversely, there is no phase separation in the case of non-inventive emulsion C10; instead, a clear solution is obtained. However, the assessment of hand here is much poorer. Since the emulsion is additionally based on an active ingredient (V4) that has been prepared solely from amide amines as tertiary amines, the residual content of amide amines is high. The compositions according to the invention lead to advantageous phase characteristics, a low residual content of amide amines, and a very good assessment of hand.

[0446] I12 and I16 show a particularity good assessment of hand as well as good formability.

TABLE-US-00019 TABLE 17 Inventive emulsions and their properties - effect on chain length of the fatty acid or of the alkoxylate (content figures in % by weight based on the overall composition) % I20 I21 I22 RE2 20.5 RE7 20.5 RE8 20.5 Lutensole TO 8 1.5 1.5 1.5 Dipropylene 4.5 4.5 4.5 glycol Butyldiglycol 10.0 10.0 10.0 Water 63.2 63.2 63.2 Acetic acid 0.3 0.3 0.3 Appearance clear clear clear solution solution solution Hand test 37.2 37.5 37.6 (TSA value)

[0447] Table 17 shows the effect of different fatty acid amides (I20: cocoyl, I21: palmityl, I22: stearyl). Irrespective of the choice of fatty acid amide, very good results are obtained in the hand test. In addition, it is found that the longer the alkyl chain length of the acid radical of the amide amine, the better the assessments in the hand test. This correlation was also confirmed in the panel test.

TABLE-US-00020 TABLE 18 Emulsions and their properties (content figures in % by weight based on the overall composition) % I23 C11 C12 RE8 20.5 RE9 20.5 RE10 20.5 Isotridecanol 10.5 10.5 10.5 6EO Isotridecanol 1.8 1.8 1.8 12EO Water 66.8 66.8 66.8 Acetic acid 0.4 0.4 0.4 Appearance clear clear clear solution solution solution Hand test 37.9 37.5 36.7 (TSA value) Panel test 4.8 4.5 4.0 (1-5; 5 = best)

[0448] The results in Table 18 show that the use of the active ingredients according to the invention leads to a better assessment of hand compared to non-inventive active ingredients, especially to commercially available active ingredients.

TABLE-US-00021 TABLE 19 Inventive emulsions comprising additives for improvement of bulkiness and properties thereof (content figures in % by weight based on the overall composition) % I24 I25 I26 RE2 20.5 RE7 20.5 RE8 20.5 TEGOPREN 7008 5.6 5.6 5.6 Dodecanol 6EO 7.7 7.7 7.7 Dipropylene glycol 3.3 3.3 3.3 Butyldiglycol 5.0 5.0 5.0 Water 63.5 63.5 63.5 Appearance clear clear clear solution solution solution Hand test (TSA value) 36.8 37.3 37.6

[0449] The results in Table 19 also make it clear that the use of siloxanes according to the invention leads to a better assessment of hand.

[0450] It should be emphasized that the use of the siloxanes according to the invention leads to a better assessment of hand, better phase characteristics and/or a lower amide amine content.

[0451] To test the antistatic properties, the silicone quats were diluted in demineralized water to an active content of 20% by weight and then applied to the polyester fabric by a padding operation by the method described above.

TABLE-US-00022 TABLE 20 Antistatic compositions (content figures in % by weight based on the overall composition) C13 I27 C14 C15 I28 Silicone quat 40% V6 .sup.2) 40% I14 .sup.3) 21% V7 .sup.4) 25% V8 .sup.5) 25% REB .sup.6) Water 60% 60% 79% 75% 75% Active content 20% 20% 20% 20% 20% Appearance clear opaque milky milky biphasic 2) Composition comprising a silicone quat prepared from Amide1 and SE4 (b1 = 18) 3) Composition comprising a silicone quat prepared from Amide2 and SE4 (b1 = 18) 4) Composition comprising a silicone quat prepared from Amide1 and SE2 (b1 = 78) 5) Composition comprising a silicone quat prepared from Amide1 and SE2 (b1 = 78) 6) Composition comprising a silicone quat prepared from Amide2 and SE2 (b1 = 78)

[0452] Comparison of I27 with C13 and of I28 with C14 and C15 shows that, given the same siloxane chain length, somewhat poorer solubility is observed in the case of the inventive compositions 127 and 128. When used as active antistatic and glidant ingredient, however, the somewhat poorer solubility reduces unwanted penetration of the product into the textile fibre matrix. The active antistatic ingredient remains on the surface to a greater degree than in the comparative examples and leads to a better gliding effect coupled with a similar antistatic effect. In order to compare the products, no further auxiliaries that are typically used in spinning preparations were used. In the case of 128, a phase separation was observed. For this reason, no antistatic measurements were conducted therefor.

TABLE-US-00023 TABLE 21 Antistatic properties Resistance in Resistance in Resistance in (0.01 g of sample/ (0.02 g of sample/ (0.03 g of sample/ 1 g of textile) 1 g of textile) 1 g of textile) C13 5.94E+08 4.75E+08 2.80E+07 I27 2.29E+09 1.37E+09 4.96E+08 C14 1.03E+10 2.81E+10 2.02E+10 C15 9.05E+10 3.83E+10 8.41E+09 I28 not determined not determined not determined Blank .sup.7) 4.13E+11 4.13E+11 4.13E+11 .sup.7) Value for the untreated polyester fabric

[0453] The samples comprising short-chain siloxanes C13 and 127 show an adequate antistatic effect. The antistatic properties of inventive example I27 are somewhat less than in the case of non-inventive example C13. This difference is acceptable and is more than compensated for by the better gliding effect and better hand of the inventive example. The inventive example has less of a tendency to penetrate into the fabric and hence improves the hand. Resistance is determined under the idealized boundary conditions that are to be observed according to the DIN cited. In industrial application, however, it is found that the antistatic finish in the case of C13 declines with time, whereas the antistatic properties of I27 remain largely unchanged. It is assumed that the elevated friction under real conditions leads to elevated penetration of the non-inventive sample into the textile, such that the antistatic finish declines with time. The product according to the invention, by contrast, has less of a tendency to penetrate and leads to a substantially constant finish under stress conditions that are customary in production.

Water-Thinnable Formulations for Automotive Care:

Materials Used:

[0454] Carspray 90 Di-(Oleyl carboxyethyl) Hydroxyethyl Methylammonium Methosulfate [0455] REWOCARE DOC diethylhexyl carbonate [0456] TEGO POLISH ADDITIV 5 decamethylcyclopentasiloxane, D5 [0457] REWOPAL MPG 40 tetraethylene monophenyl ether [0458] DPG dipropylene glycol [0459] TEGOPREN 6922 Quaternium 80 (silicone quat) [0460] REWOQUAT CR 3099 Di Oleic Acid Isopropylester Dimethylammonium Methosulfate [0461] Butyl Cellosolve 2-butylethanol [0462] REWOCARE OT isooctyl Tallowate

TABLE-US-00024 TABLE 22 Automotive care formulations (content figures in parts by weight) Formulation with Formulation Formulation Constituent benchmark with I15 with I16 Carspray 90 12 parts 12 parts 12 parts REWOCARE DOC 5 parts 5 parts 5 parts D5 2 parts 2 parts 2 parts REWOPAL MPG 40 6 parts 6 parts 6 parts DPG 8 parts 8 parts 8 parts TEGOPREN 6922 0.8 part I15 0.8 part I16 0.8 part Water 65.7 parts 65.7 parts 65.7 parts Acetic acid, conc. 0.5 part 0.5 part 0.5 part

TABLE-US-00025 TABLE 23 Automotive care formulations (content figures in parts by weight) Formulation Formulation Formulation Constituent with benchmark with I15 with I16 REWOQUAT CR 3099 10 parts 10 parts 10 parts REWOPAL MPG 40 8.6 parts 8.6 parts 8.6 parts Butyl Cellosolve 6.2 parts 6.2 parts 6.2 parts REWOCARE OT 8 parts 8 parts 8 parts D5 3 parts 3 parts 3 parts TEGOPREN 6922 0.8 part I15 0.8 part I16 0.8 part Water 62.9 parts 62.9 parts 62.9 parts Acetic acid, conc. 0.5 part 0.5 part 0.5 part

[0463] These automotive care formulations were tested for water thinnability by diluting 1 part automotive care formulation (see Tables 22 and 23) with 26 parts water. There must be no apparent cloudiness.

TABLE-US-00026 TABLE 24 Basis formulations for fabric softeners (without perfume, colour and other additives) (content figures in parts by weight) Formulation with Formulation Constituent benchmark with I3 SQ1 0.15 I3 0.15 part REWOQUAT WE 18 5.65 parts 5.65 parts Water 94.2 parts 94.2 parts