Lipase-stable thickening agent

Abstract

The invention relates to novel compounds, to aqueous, in particular surfactant-containing formulations containing the novel compounds and to the use of the novel compounds as thickening agents of aqueous, in particular surfactant-containing formulations.

Claims

1. An aqueous formulation comprising a compound of formula (I) ##STR00005## wherein R.sup.1 and R.sup.2 of the compound of formula (I) are selected from one of the following groupings R.sup.1═H or 2-hydroxypropyl and R.sup.2=2-hydroxypropyl; R.sup.1═H or 2-aminoethyl and R.sup.2=2-aminoethyl; R.sup.1═H or N-(2-hydroxyethyl)aminoethyl and R.sup.2═N-(2-hydroxyethyl)aminoethyl; R.sup.1═H or 2-(2-hydroxyethoxy)ethyl and R.sup.2=2-(2-hydroxyethoxy)ethyl; R.sup.1=methyl or 2,3,4,5,6-pentahydroxyhexyl and R.sup.2=2,3,4,5,6-pentahydroxyhexyl; and R.sup.1═H or 2-(1-piperazinyl)ethyl and R.sup.2=2-(1-piperazinyl)ethyl.

2. The aqueous formulation of claim 1, wherein R.sup.1═H and R.sup.2═N-(2-hydroxyethyl)aminoethyl.

3. The aqueous formulation according to claim 1, wherein said aqueous formulation further comprises at least one surfactant.

4. The aqueous formulation according to claim 3, wherein the at least one surfactant is a mixture of at least one anionic surfactant and at least one nonionic surfactant.

5. The aqueous formulation according to claim 3, wherein the at least one surfactant is a biosurfactant selected from rhamnolipids, sophorolipids, trehalose- and other mycolic-acid-containing glycolipids, and also cellobiose and mannosylerythritol lipids.

6. The aqueous formulation according to claim 1, wherein said aqueous formulation further comprises at least one enzyme.

7. The aqueous formulation according to claim 1, wherein said at least one compound of formula (I) is present in an amount of from 0.1% by weight to 50% by weight, where the % by weight refers to the total formulation.

Description

(1) The following figures form part of the examples:

(2) FIG. 1: Rheology profile of a detergent formulation comprising N-(2-hydroxyethyl)-12-hydroxystearamide

(3) FIG. 2: Rheology profile of a detergent formulation comprising N-(2-hydroxypropyl-12-hydroxystearamide

(4) FIG. 3: Rheology profile of a detergent formulation comprising N-(2-hydroxypropyl)-12-hydroxystearamide (2)

(5) FIG. 4: Rheology profile of a detergent formulation comprising N-(2-aminoethyl)-12-hydroxystearamide

(6) FIG. 5: Rheology profile of a detergent formulation comprising N—(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide

(7) FIG. 6: Rheology profile of an aqueous formulation comprising N-(2,3,4,5,6-pentahydroxyhexyl)-12-hydroxystearamide

(8) FIG. 7: Rheology profile of a detergent formulation comprising hydrogenated castor oil

(9) FIG. 8: Lipase stability of a detergent formulation comprising N-(2-hydroxypropyl)-12-hydroxystearamide compared to hydrogenated castor oil after 60 minutes (8a) and after six days (8b).

EXAMPLES

Example 1: Synthesis of N-(2-hydroxyethyl)-12-hydroxystearamide

(10) 824 g (0.88 mol) of hydrogenated castor oil were admixed, at 90° C. and with stirring, with 161 g (2.64 mol) of 2-hydroxyethylamine and homogenized. This mixture was dried at a vacuum of 50 mbar and a temperature of 90-100° C. for 30 minutes. The vacuum was then broken with nitrogen and 10 g of a 30% strength by weight sodium methanolate solution in methanol were present. The reaction mixture was stirred for 3 hours at 110° C., reaction control taking place via the determination of the free 2-hydroxyethylamine (acid-base titration). 989 g of a N-(2-hydroxyethyl)-12-hydroxystearamide were obtained, the content of free 2-hydroxyethylamine was 1.2% by weight.

Example 2: Synthesis of N-(2-hydroxypropyl)-12-hydroxystearamide

(11) 374.2 g (0.40 mol) of hydrogenated castor oil were mixed as described under Example 1 with 90.1 g (1.2 mol) of 2-hydroxypropylamine and dried. 5 g of a 30% strength by weight sodium methanolate solution were added to this reaction mixture and stirring was carried out for 2.5 hours at 110° C. Reaction control was carried out via the determination of the free 2-hydroxypropylamine (acid-base titration). Here, the reaction mixture reacted to the point of a 2-hydroxypropylamine content of 0.8% by weight.

Example 3: Synthesis of N,N-di(2-hydroxyethyl)-12-hydroxystearamide

(12) 875.3 g (0.94 mol) of hydrogenated castor oil were mixed as described under Example 1 with 295.1 g (2.81 mol) of N,N-di(2-hydroxyethyl)amine. 15 g of a 30% strength by weight sodium methanolate solution were added to this reaction mixture and stirring was carried out for 3 hours at 110° C. The reaction control was carried out via the determination of the free N,N-(di-2-hydroxyethyl)amine. Here, the reaction mixture reacted as far as a N,N-di(2-hydroxyethyl)amine content of 4.0% by weight.

Example 4: Synthesis of N-(2-aminoethyl)-12-hydroxystearamide

(13) 561 g (0.6 mol) of hydrogenated castor oil were reacted as described under Example 1 with 541 g (9.0 mol) of 2-aminoethylamine and 14 g of a 30% strength by weight sodium methanolate solution. When amidation is complete, the excess ethylenediamine is distilled off at 160° C./20 mbar. The resulting amide has a residual content of 7.4% 2-aminoethylamine.

Example 5: Synthesis of N-2-(2-hydroxyethoxy)ethyl-12-hydroxystearamide

(14) 882.3 g (0.943 mol) of hydrogenated castor oil were reacted as described under Example 1 with 297.4 g (2.83 mol) of N-2-(2-hydroxyethoxy)ethylamine and 18 g of a 30% strength by weight sodium methanolate solution. Here, the reaction mixture reacted as far as a residual amine content of 4.6% by weight.

Example 6: Synthesis of N-(2,3,4,5,6-pentahydroxyhexyl)-12-hydroxystearamide

(15) 374 g (0.4 mol) of hydrogenated castor oil were reacted as described under Example 1 with 234.2 g (1.2 mol) of N-(2,3,4,5,6-pentahydroxyhexyl)amine and 9 g of a 30% strength by weight sodium methanolate solution. Here, the reaction mixture reacted as far as a residual amine content of 5% by weight.

Example 7: Synthesis of N—(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide

(16) 374.2 g (0.40 mol) of hydrogenated castor oil were initially introduced at 90° C. and dried for 30 min at a vacuum of 50 mbar. The vacuum was then broken with nitrogen, and 0.25 g of hypophosphorous acid (50% strength by weight in water) and 159.4 g (1.560 mol) of N,N-dimethyl-3-aminopropylamine were added. The reaction mixture was stirred for 3 h at 120° C. The reaction control was carried out by IR spectroscopy, the reaction being converted until the ester bands had completely disappeared. The temperature was then increased to 140° C. and the excess N,N-dimethyl-3-aminopropylamine was distilled off at a vacuum of 20 mbar. This gave 496 g of N—(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide.

Example 8: N-(2-Hydroxyethyl)-12-hydroxystearamide

(17) An aqueous composition of 3% by weight of N-(2-hydroxyethyl)-12-hydroxystearamide and 10% by weight of a linear alkylbenzenesulphonate neutralized with monoethanolamine was prepared and heated with stirring (magnetic stirrer core) to 80° C. until a homogeneous solution was present. The mixture was then slowly cooled to room temperature with stirring (cooling rate ˜2° C. per minute). 33% by weight of this mixture were incorporated into a detergent composition according to Table 1 such that a 1% strength by weight formulation of N-(2-hydroxyethyl)-12-hydroxystearamide was obtained:

(18) TABLE-US-00001 TABLE 1 % by Ingredient weight Linear alkylbenzenesulphonate 9.0 C12-14 fatty alcohol ethoxylate 4.5 C12-18 fatty acid 3.8 C12-14 dimethylamine oxide 1.5 Citric acid 1.5 1,2-Propanediol 3.8 Boric acid 0.4 Ethanol 1.1 Water to 100% Monoethanolamine to pH = 8.0

(19) The formulation has, as shown in FIG. 1, shear-thinning properties in the rheology test.

Example 9: N-(2-Hydroxypropyl)-12-hydroxystearamide

(20) An aqueous composition of 4% by weight of N-(2-hydroxypropyl)-12-hydroxystearamide and 19.1% by weight of a linear alkylbenzenesulphonate neutralized with monoethanolamine was produced and heated with stirring (magnetic stirrer core) to 80° C. until a homogeneous solution was present. The mixture was then cooled slowly with stirring to room temperature (cooling rate (˜2° C. per minute). 25% by weight of this mixture were incorporated into a detergent composition according to Table 1 such that a 1% strength by weight formulation of N-(2-hydroxypropyl)-12-hydroxystearamide was obtained. The formulation has, as shown in FIG. 2, shear-thinning properties in the rheology test.

(21) In an alternative procedure, N-(2-hydroxypropyl)-12-hydroxystearamide was incorporated directly into the example formulation according to Table 1 until an end concentration of 1.00% by weight was established. The formulation was heated with stirring (magnetic stirrer core) to 80° C. and cooled slowly with stirring to room temperature (cooling rate ˜2° C. per minute).

(22) Here too, the formulation has, as shown in FIG. 3, shear-thinning properties in the rheology test.

Example 10: N-(2-Aminoethyl)-12-hydroxystearamide

(23) 1.5% by weight of N-(2-aminoethyl)-12-hydroxystearamide were incorporated into the detergent formulation described in Table 1. The formulation was heated with stirring (magnetic stirrer core) to 80° C. and cooled slowly with stirring to room temperature (cooling rate ˜2° C. per minute). As shown in FIG. 4, the formulation has shear-thinning properties in the rheology test.

Example 11: N—(N,N-Dimethyl-3-aminopropyl)-12-hydroxystearamide

(24) An aqueous, hydrochloric solution (pH=1) of 3.5% by weight of N—(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide was prepared at room temperature with slow stirring (magnetic stirrer core). The detergent composition described in Table 1 was incorporated into this solution such that an end concentration of 2% by weight of N—(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide, based on the total formulation, was obtained. Then, the pH of the formulation was adjusted to pH=8 with monoethanolamines, during which a significant increase in the viscosity of the formulation could be observed. As shown in FIG. 5, the formulation has shear-thinning properties in the rheology test.

Example 12: N-(2,3,4,5,6-Pentahydroxyhexyl)-12-hydroxystearamide

(25) An aqueous composition of 2% by weight of N-(2,3,4,5,6-pentahydroxyhexyl)-12-hydroxystearamide was produced and heated with stirring (magnetic stirrer core) to 80° C. until a homogeneous solution was present. The mixture was then cooled slowly with stirring to room temperature (cooling rate (˜2° C. per minute). As shown in FIG. 6, the formulation has shear-thinning properties in the rheology test.

Example 13: Comparative Example: Hydrogenated Castor Oil

(26) An aqueous composition of 4% by weight of hydrogenated castor oil and 19.1% by weight of a linear alkylbenzenesulphonate neutralized with monoethanolamine was produced and heated with stirring (magnetic stirrer core) to 80° C. until a homogeneous solution was present. The mixture was then cooled slowly with stirring to room temperature (cooling rate (˜2° C. per minute).

(27) 20% by weight of this mixture were incorporated into a detergent composition according to Table 1 such that a 0.8% strength by weight formulation of hydrogenated castor oil was obtained. The formulation has, as shown in FIG. 7, shear-thinning properties in the rheology test.

Example 14: Lipase stability of N-(2-hydroxypropyl)-12-hydroxystearamide

(28) 1% by weight of lipase (lypozyme) was added to the first-mentioned example formulation of Example 2. The comparison formulation used was the formulation described in the comparative example to which 1% by weight of lipase was likewise added. The rheology behaviour of the formulations was recorded one hour and six days after mixing; as shown in FIGS. 8a and b, the thickening property of the hydrogenated castor oil breaks down completely after six days, whereas N-(2-hydroxypropyl)-12-hydroxystearamide retains its total activity.

Example 15: Thickening of a Biosurfactant Formulation

(29) The following formulations were prepared and their viscosities were measured using a Brookfield viscometer LVT, equipped with spindle 2, at 30 rpm and a temperature of 25° C.:

(30) SL=Sophorolipid from Ecover.

(31) LAS=MARLON ARL from Sasol, sodium (n-C10-C13-alkylbenzenesulphonate)

(32) TABLE-US-00002 LAS SL N-(2-Hydroxyethyl)-12-hydro- Viscosity [% by wt.] [% by wt.] xystearamide [% by wt.] [mPas] 4.5 4.5 0 25 4.5 4.5 1 1000 8.9 0.1 1 2500 8.1 0.9 1 3000 6.8 2.2 1 7500

(33) The results show that the compound according to the invention is able to thicken a biosurfactant formulation.

Example 16: Formulation Examples

(34) The formulation examples given in Tables 2 to 29 below show exemplary representatives of a large number of possible formulations according to the invention.

(35) If the preparation of the formulation requires the separate preparation and/or mixing of formulation constituents beforehand, this is referred to as multiphase preparation.

(36) If a two-phase preparation is required, the two phases are labelled as A and B in the tables given. In the case of three-phase processes, the three phases are labelled A, B and C. Unless stated otherwise, the data are data in % by weight.

(37) In the examples listed, the corresponding 12-hydroxystearamide is always incorporated into the end formulation at a temperature of 80° C.

(38) TABLE-US-00003 TABLE 2 Formulation Example 1, Shampoo, PEG- & sulphate-free REWOTERIC ® AMC, Evonik Goldschmidt GmbH, 32% 15.00 strength, (INCI:Sodium Cocoamphoacetate) REWOPOL ® SB F 12 P, Evonik Goldschmidt GmbH, 96% 3.80 strength, (INCI: Disodium Lauryl Sulfosuccinate) Perfume 0.30 Water 65.10 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength, 13.00 (INCI: Cocamidopropyl Betaine) ANTIL ® HS 60, Evonik Goldschmidt GmbH, (INCI: Cocamid- 1.00 opropyl Betaine; Glyceryl Laurate) Citric Acid, 30% strength q.s. Preservative 0.30 N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.5

(39) TABLE-US-00004 TABLE 3 Formulation Example 2, mild hair and body cleanser Plantacare ® 1200 UP, Cognis, 50% strength, 11.40 (INCI: Lauryl Glucoside) Plantacare ® 818 UP, Cognis, 51% strength, 5.60 (INCI: Coco Glucoside) Water 63.00 TEGOSOFT ® LSE 65 K SOFT, Evonik Goldschmidt GmbH, 1.50 (INCI: Sucrose Cocoate) TECO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength, 18.00 (INCI: Cocamidopropyl Betaine) Perfume, preservative q.s. Citric Acid, 30% q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 0.50

(40) TABLE-US-00005 TABLE 4 Formulation Example 3, moisturizing skin cleanser A TEXAPON ® NSO, Cognis, 28% strength, 30.00 (INCI: Sodium Laureth Sulfate) Perfume 0.30 B Water 54.80 TEGOCEL ® fluid, HPM, 4000, Evonik Goldschmidt, 1.20 GmbH, (INCI: Hydroxypropyl Methylcellulose) TEGO ® Betain C 60, Evonik Goldschmidt GmbH, 46% 8.10 strength, (INCI: Cocamidopropyl Betaine) TEGOSOFT ® APM, Evonik Goldschmidt GmbH, 1.00 (INCI: PPG-3 Myristyl Ether) TEGO ® Pearl N 300, Evonik Goldschmidt GmbH, 2.00 (INCI: Glycol Distearate; Laureth-4; Cocamidopropyl Betaine) REWODERM ® LI S 80, Evonik Goldschmidt GmbH, 1.00 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.60 Citric Acid, 30% strength q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(41) TABLE-US-00006 TABLE 5 Formulation Example 4, shower gel TAGAT ® CH 40, Evonik Goldschmidt GmbH, 2.50 (INCI: PEG-40 Hydrogenated Castor Oil) Perfume 0.30 TEXAPON ® NSO, Cognis, 28% strength, 42.90 (INCI: Sodium Laureth Sulfate) Water 39.30 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength, 10.70 (INCI: Cocamidopropyl Betaine) LACTIL ®, Evonik Goldschmidt GmbH, (INCI: Sodium Lactate; 1.00 Sodium PCA; Glycine; Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid) ANTIL ® 171, Evonik Goldschmidt GmbH 2.00 (INCI: PEG-18 Glyeryl Oleate/Cocoate) Preservative 0.30 N-(2-aminoethyl)-12-hydroxystearamide 1.00

(42) TABLE-US-00007 TABLE 6 Formulation Example 5, shower gel TEXAPON ® NSO, Cognis, 28% strength, 37.00 (INCI: Sodium Laureth Sulfate) Perfume 0.30 Water 42.00 REWOTERIC ® AMC, Evonik Goldschmidt GmbH, 32% 9.00 strength, (INCI: Sodium Cocoamphoacetate) TEGO ® Betain 810, Evonik Goldschmidt GmbH, strength, 7.60 (INCI: Capryl/Capramidopropyl Betaine) LACTIL ®, Evonik Goldschmidt GmbH, 1.00 (INCI: Sodium Lactate; Sodium PCA; Glycine; Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid) Citric Acid, 30% strength 1.30 REWODERM ® LI S 80, Evonik Goldschmidt GmbH, 0.50 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.30 N-(2-aminoethyl)-12-hydroxystearamide 1.00

(43) TABLE-US-00008 TABLE 7 Formulation Example 6, shampoo, PEG- & sulphate-free REWOTERIC ® AM C, Evonik Goldschmidt GmbH, 32% 15.00 strength, (INCI: Sodium Cocoamphoacetate) Plantapon ACG 50, Cognis (INCI: Disodium Cocoyl Glutamate) 3.80 Perfume 0.30 Water 66.30 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% 10.00 strength, (INCI: Cocamidopropyl Betaine) VARISOFT ® PATC, Evonik Goldschmidt (INCI: 2.30 Palmitamidopropyltrimonium Chloride) REWOMID ® SPA, Evonik Goldschmidt GmbH, 1.00 (INCI: Isostearamide MIPA) Preservative 0.30 Citric Acid, 30% strength q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(44) TABLE-US-00009 TABLE 8 Formulation Example 7, shower gel TEXAPON ® NSO, Cognis, 28% strength 15.00 (INCI: Sodium Laureth Sulfate) Perfume 0.30 PGFAC-S, Cognis (INCI: Sodium cocoyl hydrolyzed 1.50 wheat protein glutamate) REWOPOL SB CS 50 B, Evonik Goldschmidt GmbH, 40% 7.50 strength, (INCI: Disodium PEG-5 Lauryl Citrate Sulfosuccinate; Sodium Laureth Sulfate) Water 59.10 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% 9.00 strength, (INCI: Cocamidopropyl Betaine) TEGO ® Betain 810 Evonik Goldschmidt GmbH 38% strength, 4.00 (INCI: Capryl/Capramidopropyl Betaine) ANTIL ® 200, Evonik Goldschmidt GmbH, 1.80 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.30 N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.50

(45) TABLE-US-00010 TABLE 9 Formulation Example 8, shampoo, PEG- & sulphate-free A REWOTERIC ® AMC, Evonik Goldschmidt GmbH, 32% 20.00 strength, (INCI: Sodium Cocoamphoacetate) REWOPOL ® SB F 12 P, Evonik Goldschmidt, 96% strength, 5.90 (INCI: Disodium Lauryl Sulfosuccinate) B Water 65.90 Citric Acid, 30% strength 3.60 C ANTIL ® HS 60, Evonik Goldschmidt GmbH, (INCI: 3.00 Cocamidopropyl Betaine; Glyceryl Laurate) Preservative 0.60 N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.00

(46) TABLE-US-00011 TABLE 10 Formulation Example 9, body cleanser A TEXAPON ® NSO Cognis 28% strength, 30.00 (INCI: Sodium Laureth Sulfate) ABIL ® B 8832, Evonik Goldschmidt GmbH, 0.30 (INCI: Bis-PEG/PPG-20/20 Dimethicone) Perfume 0.30 B Water 52.50 TEGOCEL ® fluid HPM 4000, Evonik Goldschmidt GmbH, 1.20 (INCI: Hydroxypropyl Methylcellulose) Citric Acid Monohydrate 0.50 REWOTERIC ® AM C, Evonik Goldschmidt GmbH, 32% 10.00 strength, (INCI: Sodium Cocoamphoacetate) TECO ® Pearl N 300, Evonik Goldschmidt GmbH, 2.00 (INCI: Glycol Distearate; Laureth-4; Cocamidopropyl Betaine) REWODERM ® LI S 80, Evonik Goldschmidt GmbH, 1.60 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.60 Citric Acid, 30% strength q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(47) TABLE-US-00012 TABLE 11 Formulation Example 10, sprayable hair milk, PEG-free A Water 95.30 Lactic Acid, 80% strength 0.40 B TEGO ® AMID S 18, Evonik Goldschmidt GmbH, 1.20 (INCI: Stearamidopropyl Dimethylamine) TEGIN ® G 1100 Pellets, Evonik Goldschmidt GmbH, 0.60 (INCI: Glycol Distearate) TECO ® Care PS, Evonik Goldschmidt GmbH, 1.20 (INCI: Methyl Glucose Sesquistearate) TEGOSOFT ® DEC, Evonik Goldschmidt GmbH, 0.30 (INCI: Diethylhexyl Carbonate) Perfume, preservative q.s. N-(2-aminoethyl)-12-hydroxystearamide 1.00

(48) TABLE-US-00013 TABLE 12 Formulation Example 11, body cleansing foam TEXAPON ® NSO, Cognis, 28% strength 14 (INCI: Sodium Laureth Sulfate) Perfume 0.3 REWOTERIC ® AM C, Evonik Goldschmidt GmbH, 32% strength 8 (INCI: Sodium Cocoamphoacetate) Water 75.0 TEGOCEL ® HPM 50, Evonik Goldschmidt GmbH 0.5 (INCI: Hydroxypropyl Methylcellulose) LACTIL ® Evonik Goldschmidt GmbH (INCI: Sodium Lactate; 1 Sodium PCA; Glycine; Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid) Citric Acid Monohydrate 0.5 N-(2-hydroxypropyl)-12-hydroxystearamide 0.7

(49) TABLE-US-00014 TABLE 13 Formulation Example 12, conditioning shampoo TEXAPON ® NSO, Cognis, 28% strength 32.00 (INCI: Sodium Laureth Sulfate) VARISOFT ® PATC, Evonik Goldschmidt GmbH 1.50 (INCI: Palmitamidopropyltrimonium Chloride) REWODERM ® LI S 80, Evonik Goldschmidt GmbH 2.00 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Perfume 0.25 Water 53.75 TEGO ® Cosmo C 100, Evonik Goldschmidt GmbH, 1.00 (INCI: Creatine) Jaguar C-162, Rhodia (INCI: Hydroxypropyl Guar Hydroxy- 0.20 propyltrimonium Chloride) TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength 8.00 (INCI: Cocamidopropyl Betaine) NaCl 0.50 Preservative q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 0.80

(50) TABLE-US-00015 TABLE 14 Formulation Example 13, pearlized shampoo TEXAPON ® NSO, Cognis, 28% strength 32.00 (INCI: Sodium Laureth Sulfate) Perfume 0.25 Water 54.75 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength 8.00 (INCI: Cocamidopropyl Betaine) TEGO ® Pearl N 300 Evonik Goldschmidt GmbH (INCI: Glycol 2.00 Distearate; Laureth-4; Cocamidopropyl Betaine) ANTIL ® 171 Evonik Goldschmidt GmbH (INCI: PEG-18 1.50 Glyceryl Oleate/Cocoate) NaCl 0.50 Preservative q.s. N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.00

(51) TABLE-US-00016 TABLE 15 Formulation Example 14, rinse-off conditioner Water 90.00 VARISOFT ® EQ 65, Evonik Goldschmidt GmbH 2.00 (INCI: Distearyl Dimonium Chloride, Cetearyl Alcohol) VARISOFT ® BT 85, Evonik Goldschmidt GmbH 2.00 (INCI: Behentrimonium Chloride) TEGO ® Alkanol 1618, Evonik Goldschmidt GmbH 5.00 (INCI: Cetearyl Alcohol) Preservative, perfume q.s. N-(N,N-dimethyl-3-aminopropyl)-12- 1.00 hydroxystearamide

(52) TABLE-US-00017 TABLE 16 Formulation Example 15, conditioning shampoo TEXAPON ® NSO, Cognis, 28% strength 32.00 (INCI: Sodium Laureth Sulfate) ANTIL ® 200, Evonik Goldschmidt GmbH 2.00 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Perfume 0.25 Water 56.25 Polymer JR 400, Amerchol (INCI: Polyquaternium-10) 0.20 TEGO ® Betain F 50, 8.00 Evonik Goldschmidt GmbH, 38% strength (INCI: Cocamidopropyl Betaine) NaCl 0.30 Preservative q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(53) TABLE-US-00018 TABLE 17 Formulation Example 16, moisturizing skin cleanser A TEXAPON ® NSO, Cognis, 28% strength, 30.00 (INCI: Sodium Laureth Sulfate) Cap01 0.70 Perfume 0.30 B Water 55.10 TEGOCEL ® fluid HPM 4000, 1.20 Evonik Goldschmidt GmbH, (INCI: Hydroxypropyl Methylcellulose) TEGO ® Betain C 60, 8.10 Evonik Goldschmidt GmbH, 46% strength, (INCI: Cocamidopropyl Betaine) TEGOSOFT ® APM, Evonik Goldschmidt GmbH, 1.00 (INCI: PPG-3 Myristyl Ether) Cutina TS, Cognis (INCI: PEG- 3 Distearate) 1.00 REWODERM ® LI S 80, Evonik Goldschmidt GmbH, 1.00 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.60 Citric Acid, 30% strength q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(54) TABLE-US-00019 TABLE 18 Formulation Example 17, shower gel TEXAPON ® NSO, Cognis, 28% strength 15.00 (INCI: Sodium Laureth Sulfate) Perfume 0.30 PGFAC-S, Cognis (INCI: Sodium cocoyl 1.50 hydrolyzed wheat protein glutamate) REWOPOL SB CS 50 B, Evonik 7.50 Goldschmidt GmbH, 40% strength, (INCI: Disodium PEG-5 Lauryl Citrate Sulfosuccinate; Sodium Laureth Sulfate) Water 59.35 TEGO ® Betain F 50, Evonik 9.00 Goldschmidt GmbH, 38% strength, (INCI: Cocamidopropyl Betaine) TEGO ® Betain 810, Evonik 4.00 Goldschmidt GmbH, 38% strength, (INCI: Capryl/Capramidopropyl Betaine) Polyquaternium- 7, Nalco, (INCI: Merquat 550) 0.50 ANTIL ® 200, Evonik Goldschmidt GmbH, 1.80 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.30 N-(2-hydroxypropyl)-12-hydroxystearamide 0.75

(55) TABLE-US-00020 TABLE 19 Formulation Example 18, body cleanser A TEXAPON ® NSO Cognis 28% strength, 30.00 (INCI: Sodium Laureth Sulfate) ABIL ® B 8832, Evonik Goldschmidt GmbH, 0.30 (INCI: Bis-PEG/PPG-20/20 Dimethicone) Perfume 0.30 B Water 52.50 TEGOCEL ® fluid HPM 4000, 1.20 Evonik Goldschmidt GmbH, (INCI: Hydroxypropyl Methylcellulose) Citric Acid Monohydrate 0.50 REWOTERIC ® AM C, 10.00 Evonik Goldschmidt GmbH, 32% strength, (INCI: Sodium Cocoamphoacetate) Cutina TS, Cognis (INCI: PEG- 3 Distearate) 2.00 REWODERM ® LI S 80, 1.60 Evonik Goldschmidt GmbH, (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Preservative 0.60 Citric Acid, 30% strength q.s. N-(2-aminoethyl)-12-hydroxystearamide 1.00

(56) TABLE-US-00021 TABLE 20 Formulation Example 19, body cleansing foam TEXAPON ® NSO, Cognis, 28% strength 14 (INCI: Sodium Laureth Sulfate) Perfume 0.3 REWOTERIC ® AM C, 8 Evonik Goldschmidt GmbH, 32% strength (INCI: Sodium Cocoamphoacetate) Water 74.7 TEGOCEL ® HPM 50, 0.5 Evonik Goldschmidt GmbH (INCI: Hydroxypropyl Methylcellulose) LACTIL ® Evonik Goldschmidt GmbH 1 (INCI: Sodium Lactate; Sodium PCA; Glycine; Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid) Panthenol, BASF, (INCI: D- Panthenol USP) 0.2 Citric Acid Monohydrate 0.5 N-(2-hydroxypropyl)-12-hydroxystearamide 0.8

(57) TABLE-US-00022 TABLE 21 Formulation Example 20, rinse-off conditioner Water 89.40 VARISOFT ® EQ 65, Evonik Goldschmidt GmbH 2.00 (INCI: Distearyl Dimonium Chloride, Cetearyl Alcohol) VARISOFT ® BT 85, Evonik Goldschmidt GmbH 2.00 (INCI: Behentrimonium Chloride) TEGO ® Alkanol 16, Evonik Goldschmidt GmbH 5.00 (INCI: Cetyl Alcohol) Preservative, perfume q.s. N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.6

(58) TABLE-US-00023 TABLE 22 Formulation Example 21, rinse-off conditioner Water 89.40 VARISOFT ® EQ 65, Evonik Goldschmidt GmbH 2.00 (INCI: Distearyl Dimonium Chloride, Cetearyl Alcohol) VARISOFT ® BT 85, Evonik Goldschmidt GmbH 2.00 (INCI: Behentrimonium Chloride) TEGO ® Alkanol 18, Evonik Goldschmidt GmbH, 5.00 (INCI: Stearyl Alcohol) Preservative, perfume q.s. N-(N,N-Dimethyl-3-aminopropyl)-12-hydroxystearamide 1.6

(59) TABLE-US-00024 TABLE 23 Formulation Example 22, rinse-off conditioner Water 88.40 VARISOFT ® EQ 65, Evonik Goldschmidt GmbH 2.00 (INCI: Distearyl Dimonium Chloride, Cetearyl Alcohol) VARISOFT ® BT 85, Evonik Goldschmidt GmbH 2.00 (INCI: Behentrimonium Chloride) TEGO ® Alkanol 1618, Evonik Goldschmidt GmbH 5.00 (INCI: Cetearyl Alcohol) DC 949, Dow Corning, (INCI: Amodimethicone) 1.00 Preservative, perfume q.s. N-(N,N-Dimethyl-3-aminopropyl)-12- 1.6 hydroxystearamide

(60) TABLE-US-00025 TABLE 24 Formulation Example 23, rinse-off conditioner Water 88.40 VARISOFT ® EQ 65, Evonik Goldschmidt GmbH 2.00 (INCI: Distearyl Dimonium Chloride, Cetearyl Alcohol) VARISOFT ® BT 85, Evonik Goldschmidt GmbH 2.00 (INCI: Behentrimonium Chloride) TEGO ® Alkanol 1618, Evonik Goldschmidt GmbH 5.00 (INCI: Cetearyl Alcohol) DC 1503 Fluid, Dow Corning, 1.00 (INCI: Dimethicone, Dimethiconol) Preservative, perfume q.s. N-(N,N-dimethyl-3-aminopropyl)-12-hydroxystearamide 1.6

(61) TABLE-US-00026 TABLE 25 Formulation Example 24, turbid conditioning shampoo TEXAPON ® NSO, Cognis, 28% strength 32.00 (INCI: Sodium Laureth Sulfate) ANTIL ® 200, Evonik Goldschmidt GmbH 2.00 (INCI: PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 Glyceryl Cocoate) Perfume 0.25 Water 53.25 Polymer JR 400, Amerchol (INCI: Polyquaternium-10) 0.20 TEGO ® Betain F 50, Evonik Goldschmidt GmbH, 38% strength 8.00 (INCI: Cocamidopropyl Betaine) DC1503 Fluid, Dow Corning, 1.00 (INCI: Dimethicone, Dimethiconol) TEGO ® Pearl N 300 Evonik Goldschmidt GmbH 2.00 (INCI: Glycol Distearate; Laureth-4; Cocamidopropyl Betaine) NaCl 0.30 Preservative q.s. N-(2-hydroxypropyl)-12-hydroxystearamide 1.00

(62) TABLE-US-00027 TABLE 26 Formulation Example 25, conditioning antidandruff sham A TEGIN ® G 1100 Pellets, Evonik Goldschmidt GmbH, 3.00 (INCI: Glycol Distearate) TEXAPON ® NSO, Cognis, 28% strength 40.0 (INCI: Sodium Laureth Sulfate) B Perfume 0.30 Zinc- Pyrion NF, WeylChem, 48% strength 2.00 (INCI: Zinc Pyrithione) ABIL ® Quat 3272, Evonik Goldschmidt GmbH, 1.00 (INCI: Quaternium- 80) C Water 37.4 TEGO ® Carbomer 341 ER, Evonik Goldschmidt GmbH, 0.20 (INCI: Acrylates/C10-30 Alkyl Acrylate Crosspolymer) Polymer JR 400, Amerchol, (INCI: Polyquaternium-10) 0.30 NaOH, 25% strength 0.30 D Rewoteric AM B U 185 ® Evonik Goldschmidt GmbH, 12.5 (INCI: Undecylenamidopropyl Betaine) Preservative q.s N-(2-hydroxypropyl)-12-hydroxystearamide 3.00

(63) TABLE-US-00028 TABLE 27 Formulation Example 26, conditioning antidandruff sham A TEGIN ® G 1100 Pellets, Evonik Goldschmidt GmbH, 3.00 (INCI: GlycoDistearate) TEXAPON ® NSO, Cognis, 28% strength 40.0 (INCI: Sodium Laureth Sulfate) B Perfume 0.30 Crinipan AD, Haarmann & Reimer Fragrance 0.30 GmbH (INCI: Climbazole) ABIL ® Quat 3272, Evonik Goldschmidt 1.00 GmbH, (INCI: Quaternium- 80) C Water 39.1 TEGO ® Carbomer 341 ER, Evonik Goldschmidt GmbH, 0.20 (INCI: Acrylates/C10-30 Alkyl Acrylate Crosspolymer) Polymer JR 400, Amerchol, (INCI: Polyquaternium-10) 0.30 NaOH, 25% strength 0.30 D Rewoteric AM B U 185 ® Evonik Goldschmidt GmbH, 12.5 (INCI: Undecylenamidopropyl Betaine) Preservative q.s N-(2-hydroxypropyl)-12-hydroxystearamide 3.00

(64) TABLE-US-00029 TABLE 28 Formulation Example 27, conditioning antidandruff sham A TEGIN ® G 1100 Pellets, Evonik Goldschmidt GmbH, 3.00 (INCI: Glycol Distearate) TEXAPON ® NSO, Cognis, 28% strength 40.0 (INCI: Sodium Laureth Sulfate) B Perfume 0.30 Zinc-Pyrion NF, WeylChem, 48% strength 2.00 (INCI: Zinc Pyrithione) ABIL ® Quat 3272, Evonik Goldschmidt GmbH, 1.00 (INCI: Quaternium- 80) C Water 37.1 TEGO ® Carbomer 140, Evonik Goldschmidt 0.50 GmbH, (INCI: Carbomer) Polymer JR 400, Amerchol, (INCI: Polyquaternium-10) 0.30 NaOH, 25% strength 0.30 D Rewoteric AM B U 185 ® Evonik Goldschmidt GmbH, 12.5 (INCI: Undecylenamidopropyl Betaine) Preservative q.s N-(2-hydroxypropyl)-12-hydroxystearamide 3.00

(65) TABLE-US-00030 TABLE 29 Formulation Example 28, conditioning antidandruff sham A TEGIN ® G 1100 Pellets, Evonik Goldschmidt GmbH, 3.00 (INCI: Glycol Distearate) TEXAPON ® NSO, Cognis, 28% strength 40.0 (INCI: Sodium Laureth Sulfate) B Perfume 0.30 Piroctone Olamine, Clariant (INCI: Octoprirox) 0.30 ABIL ® Quat 3272, Evonik Goldschmidt GmbH, 1.00 (INCI: Quaternium- 80) C Water 39.1 TEGO ® Carbomer 341 ER, Evonik Goldschmidt GmbH, 0.20 (INCI: Acrylates/C10-30 Alkyl Acrylate Crosspolymer) Polymer JR 400, Amerchol, (INCI: Polyquaternium-10) 0.30 NaOH, 25% strength 0.30 D Rewoteric AM B U 185 ® Evonik Goldschmidt GmbH, 12.5 (INCI: Undecylenamidopropyl Betaine) Preservative q.s N-(2-hydroxypropyl)-12-hydroxystearamide 3.00