NEW RHAMNOLIPID OLIGO-ESTERS

Abstract

A rhamnolipid ester is useful as a cosmetic additive. A method of its production involves providing at least one rhamnolipid, reacting the at least one rhamnolipid with at least one coupling reagent, reacting the at least one rhamnolipid with a polyhydric alcohol having 1 to 32 carbon atoms, and optionally purifying the at least one rhamnolipid ester.

Claims

1: A rhamnolipid (RL) ester of the general formula (I) ##STR00008## general formula (I), wherein m=independently of one another, identical or different, 2, 1, or 0, n=independently of one another, identical or different, 1 or 0, z=2 to 10, R.sup.1=independently of one another, identical or different, an organic radical having 2 to 24 carbon atoms, R.sup.2=independently of one another, identical or different, an organic radical having 2 to 24 carbon atoms, and A is a z-valent organic radical.

2: The rhamnolipid ester according to claim 1, wherein a rhamnolipid radical of the general formula (I) is selected from the group consisting of diRL-C10C10, diRL-C8C10, diRL-C10C12, diRL-C10C12:1, and monoRL-C10C10.

3: The rhamnolipid ester according to claim 1, wherein z=2, and A is a two valent hydrocarbyl radical, which can be substituted by one or more hydroxyl groups

4: The rhamnolipid ester according to claim 1, wherein z=2, and A is selected from the group consisting of ##STR00009## ##STR00010##

5: The rhamnolipid ester according to claim 1, wherein z=2, and A is selected from the group consisting of ##STR00011##

6: The rhamnolipid ester according to claim 1, wherein a rhamnolipid radical of the general formula (I) is selected from the group consisting of diRL-C10C10, diRL-C8C10, diRL-C10C12, diRL-C10C12:1, and monoRL-C10C10, z=2, and A is selected from the group consisting of ##STR00012##  wherein R.sup.3=R.sup.4=H, r=t=0, s=0 to 8, 10, 12, or 14, ##STR00013##

7: A process for the preparation of at least one rhamnolipid ester, comprising: A) providing at least one rhamnolipid, B) reacting the at least one rhamnolipid with at least one coupling reagent, C) reacting the at least one rhamnolipid activated by process step B) with a polyhydric alcohol having 1 to 32 carbon atoms, to obtain the at least one rhamnolipid ester, and optionally D) purifying the at least one rhamnolipid ester.

8: The process according to claim 7, wherein in B), the at least one coupling reagent s at least one selected from the group consisting of dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-cyclohexyl-N′-(2′-morpholinoethyl)carbodiimide metho-p-toluenesulphonate, N-benzyl-N′-3′dimethylaminopropylcarbodiimide hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-ethylcarbodiimide hydrochloride, and carbonyldiimidazole.

9: The process according to claim 7, wherein the reacting in C) is with at least one catalyst selected from the group consisting of N-ethyldiisopropylamine, trialkylamine, pyridine, 4-dimethylaminopyridine and hydroxybenzotriazole.

10: The process according to claim 7, wherein in A), the at least one rhamnolipid is selected from the group consisting of diRLC10C10, diC8C10, diRLC10C12, diRLC10C12:1, monoRLC10C10 and a mixture thereof.

11: The process according to claim 7, wherein in C), the polyhydric alcohol is at least one selected from the group of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octandiol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,2-tetradecandiol, 1,14-tetradecanediol, and 1,16-hexadecanediol.

12: A rhamnolipid ester obtainable by the process according to claim 7.

13: A formulation, comprising at least one rhamnolipid ester according to claim 1.

14: A cosmetic formulation for anti-perspirant applications, comprising: the rhamnolipid ester according to claim 1.

15: A method, comprising: adding the rhamnolipid ester according to claim 1 to a formulation for inhibiting body odor and/or sweat.

16: The rhamnolipid ester according to claim 1, wherein in general formula (I), R.sup.1=independently of one another, an optionally branched, optionally substituted, and optionally unsaturated alkyl radical; and/or R.sup.2=independently of one another, an optionally branched, optionally substituted, and optionally unsaturated alkyl radical.

17: The rhamnolipid ester according to claim 1, wherein in general formula (I), R.sup.1=independently of one another, selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl, tridecenyl, and (CH.sub.2).sub.o—CH.sub.3 wherein o=1 to 23.

18: The rhamnolipid ester according to claim 1, wherein in general formula (I), R.sup.2=independently of one another, selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl, tridecenyl, and (CH.sub.2).sub.o—CH.sub.3 wherein o=1 to 23.

19: The rhamnolipid ester according to claim 3, wherein A is ##STR00014## wherein R.sup.3 and R.sup.4 are CH.sub.3 or H, r=0 to 3, s=0 to 24, and t=0 to 24.

20: The rhamnolipid ester according to claim 3, wherein A is ##STR00015##

Description

EXAMPLES

Example 1: Preparation of Di-Rhamnolipids

[0126] A fermentation with a recombinant strain Pseudomonas putida KT2440S pBBR.sup.1MCS2-Plac-rhIABC-T-Ptac-rhIC-T was carried out. The construction of the strain was described in US2014296168. The preculture in the shake flask was carried out as described in WO2012013554. For the main culture, a mineral medium (M9) was likewise used. The fermentation takes place in a glucose-limited fed-batch process in a 2 litre fermenter. The feeding in of glucose was regulated by reference to the dissolved-oxygen signal. The oxygen partial pressure of the fermentation broth was regulated at 20% saturation via the stirrer speed. The pH was regulated to 7 via a pH electrode and addition of 2M sulphuric acid or of a 20% by weight ammonia solution. In order to prevent excessive foaming of the fermentation broth, the antifoam DOW Corning 1500 was metered in as required. The fermentation was conducted over 4 days to a dry biomass of 15 WI. The rhamnolipid concentration was determined by HPLC and was 9.8 g/l. After separating off the cells by means of centrifugation at 10 000 g, the fermentation broth was adjusted to a pH of 3.1 by adding concentrated H.sub.2SO.sub.4. Renewed centrifugation gave a pasty solid concentrate with an RL fraction of 45% by weight and with a viscosity of >10 000 mPas. With continuous stirring, a 50% strength by weight aqueous KOH solution was added to the pasty suspension of the concentrated rhamnolipid precipitate and a pH of 6 was established. The pasty mass liquefied at this point with an accompanying sharp drop in viscosity. The suspension gave rise to a clear solution. By adding water, the solution was adjusted to an active content of 35% by weight. The rhamnolipid purity was >90% by weight, based on the dry mass. For the synthesis the rhamnolipid was freeze-dried.

[0127] Rhamnolipid species verified by HPLC were:

TABLE-US-00001 RL total [%] (HPLC) 91 diRL-C8C10 13.9 monoRL-C8C10 0.51 diRL-C10C10 61.4 monoRL -C10C10 1.4 diRL-C10C12:1 5.9 diRL-C10C12 5.5 other RL 2.2

Example 2: Preparation of Mono-Rhamnolipids

[0128] The 35% by weight rhamnolipid solution prepared as described above was diluted to 1% by adding water. Two litres of this solution were heated to 50° C. With gentle stirring, 200 units of a thermostable rhamnosidase (ThermoActive™ Rhamnosidase A, Prokazyme) were added and the reaction was carried out overnight. After 20 h, a sample of the solution was analysed by means of HPLC. The di-rhamnolipid had been completely converted to mono-rhamnolipid and rhamnose. Then, the enzyme was deactivated for one hour at 80° C. The entire mixture was freeze-dried.

Example 3: Synthesis of Di-Rhamnolipid-Di-Ester 1

[0129] 25 g of freeze-dried di-rhamnolipid from example 1 with 6.6 ml of diisopropylcarbodiimide were dissolved in THF and stirred under nitrogen at 55° C. for 1 hour. Next 1.6 grams of 1,4-butanediol and 1% (w/w) of 4-dimethylaminopyridine were added and stirring was continued at 55° C. for 20 h. The reaction was quenched by adding 2 ml of water and the mixture was stirred and slowly cooled to 2° C. and stirring continued for 2 hours. The solids were filtered off over a glass filter. The cake was washed with a mixture of ethanol and water (6:1). Further purification could be achieved by reverse liquid chromatography.

Example 4: Synthesis of Di-Rhamnolipid-Di-Ester 2

[0130] A mixture 25 g of freeze-dried di-rhamnolipid from example 1 with 4.4 grams of N-Hydroxy-succinimide (HSU) were dissolved in THF and stirred under nitrogen at RT for 1 hour. 6.6 ml of diisopropylcarbodiimide was added into the mixture over a period of ca 10 minutes, rinsed with 2 ml of THF. The mixture was stirred at 55° C. for 1 hour. Next 2 grams of 1,4-cyclohexanediol were added and stirring was continued at 55° C. for 7 hours and at 50° C. overnight. The next day 2 ml of water were added to quench the reaction. The mixture was distilled half off and additional 50 ml methanol were added and the mixture was stirred at 50° C. The turbid mixture was slowly cooled to 2° C. and stirred for 5 hours. The solids were filtered off over a glass filter. The cake was washed with a mixture of ethanol and water (6:1). Further purification could be achieved by reverse liquid chromatography.

Example 5: Synthesis of Mono-Rhamnolipid-Di-Ester 1

[0131] 25 g of freeze-dried mono-rhamnolipid from example 2 with 6.9 ml of diisopropylcarbodiimide were dissolved in THF and stirred under nitrogen at 55° C. for 1 hour. Next 2.6 grams of 1,6-hexanediol and 1% (w/w) of 4-dimethylaminopyridine were added and stirring was continued at 55° C. for 20 h. The reaction was quenched by adding 2 ml of water and the mixture was slowly cooled to 2° C. under stirring and continued for 2 hours. The solids were filtered off over a glass filter. The cake was washed with a mixture of ethanol and water (6:1). Further purification could be achieved by reverse liquid chromatography.

Example 6: Synthesis of Mono-Rhamnolipid-Di-Ester 2

[0132] A mixture 25 g of freeze-dried mono-rhamnolipid from example 2 with 5.7 grams of N-Hydroxy-succinimide (HSU) were dissolved in THF and stirred under nitrogen at RT for 1 hour. 8.5 ml of diisopropylcarbodiimide were added to the mixture over a period of ca 10 minutes, rinsed with 2 ml of THF. The mixture was stirred at 55° C. for 1 hour. Next 3.2 grams of 1,4-cyclohexanedimethan were added and stirring was continued at 55° C. for 7 hours and at 50° C. overnight. The next day 2 ml of water were added to quench the reaction. The mixture was distilled half off and additional 50 ml methanol were added and the mixture was stirred at 50° C. The turbid mixture was slowly cooled to 2° C. and stirred for 5 hours. The solids were filtered off over a glass filter. The cake was washed with a mixture of ethanol and water (6:1). Further purification could be achieved by reverse liquid chromatography.

Example 7: Synthesis of Mixed Mono/Di-Rhamnolipid-Di-Ester

[0133] A mixture 20 g of freeze-dried di-rhamnolipid from example 1, 15 g of mono-rhamnolipid from example 2 and 11 ml of diisopropylcarbodiimide were dissolved in THF and stirred under nitrogen at 55° C. for 1 hour. Next 2.5 grams of 1,4-Butanediol and 1% (w/w) of 4-dimethylaminopyridine were added and stirring was continued at 55° C. for 20 h. The reaction was quenched by adding 4 ml of water and the mixture was stirred and slowly cooled to 2° C. and stirred for 5 hours. The solids were filtered off over a glass filter. The cake was washed with a mixture of ethanol and water (6:1), dried at 40° C. over night under vacuum.

Example 8: Application Effects

[0134] In order to measure the influence of the specified structures on producing underarm sweating and odor. The following application tests with the formulations according to the invention were carried out.

[0135] The following formulations were prepared 24 hours before use. Typically, 500 g of formulation were prepared in a 800 mL beaker. If ingredients/phases need to be heated, a water bath was used. Mixing was done by a four-blade-stirrer, driven by a Eurostar 20 digital by IKA (IKAWerke, Staufen, Germany) if not otherwise stated.

Example 8.1

[0136] 500 g of the formulation were prepared as follows: Oils (Phase A) and aqueous phase (Phase B, part of the water, butylene glycol and, if indicated the inventive structures) were mixed separately and heated up under stirring to 80° C. The rest of the water and PEG-6000 Distearate were also mixed separately and heated to 80° C.

[0137] Phase B was slowly added to phase A while stirred with a four-blade-stirrer at 250 rpm in a 800 mL beaker within 5 minutes. Then, phase C was added within 1 minute, the mixture is still mixed and kept at 80° C. during the process. After addition of phase C, the mixture was stirred well (1000 rpm, 3 minutes), and then allowed to cool down to 40° C. with gentle stirring (100 rpm). Phase D was added at 40° C. under well stirring (1000 rpm, 3 minutes), phase E was then added under stirring (1 minute, 250 rpm). The whole mixture then needs to cool down to room temperature under well stirring (1000 rpm).

TABLE-US-00002 Phase 8.1.1 8.1.2 8.1.3 8.1.4 8.1.5 8.1.6 8.1.7 A Isoceteth-20 5 5 5 5 5 5 5 Diethylhexyl Carbonate 3 3 3 3 3 3 3 Triisostearin 2 2 2 2 2 2 2 Glyceryl Isostearate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 B Water 52.5 52.5 52.5 52.5 52.5 52.5 52.5 Butylene Gylcol 3 3 3 3 3 3 3 C Water 9 19 18.5 18.5 18.5 18.5 18.5 PEG-6000 Distearate 1 1 1 1 1 1 1 D PEG-18 Glyceryl Oleate/Cocoate 2 2 2 2 2 2 2 E Chlorohydrol (Alumminium 20 10 10 10 10 10 10 Cholrohydrate) B Example 3 0.5 Example 4 0.5 Example 5 0.5 Example 6 0.5 Example 7 0.5 Roll-on Roll-on Roll-on Roll-on Roll-on Roll-on Roll-on Formulations 8.1.3 to 8.1.7 are formulations according to the instant invention

Example 8.2

[0138] The following formulations were prepared:

[0139] Water (phase A) was heated to 75° C. to dissolve the Xanthan Gum (phase B) while stirring (at least 15 minutes, 1000 rpm). The mixture was then cooled to room temperature (100 rpm) to add the ethanol (Phase C). Then, all other ingredients (Phase D) can be added under slight mixing (100 rpm-250 rpm).

TABLE-US-00003 Phase 8.2.1 8.2.2 8.2.3 8.2.4 8.2.5 8.2.6 8.2.7 A Water 77.8 77.3 77.3 77.3 77.3 77.3 77.3 B Xanthan Gum 0.4 0.4 0.4 0.4 0.4 0.4 0.4 C Ethylalcohol 20.0 20.0 20.0 20.0 20.0 20.0 20.0 D Propylen Glycol 1 1 1 1 1 1 1 Ethylhexylglycerin 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Citric acid to pH 5.5 q.s. q.s. q.s. q.s. q.s. q.s. q.s. Panthenol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 A Example 2 0.5 Example 3 0.5 Example 4 0.5 Example 5 0.5 Example 6 0.5 Example 7 0.5 spray spray spray Spray spray Spray spray Formulations 8.2.2 to 8.2.7 are formulations according to the instant invention

Example 8.3

[0140] This deo-stick formulation was prepared 48 hours before application to allow the formulation to solidify completely.

[0141] Glycol, glycerine and water (Phase A) were heated to 60° C. and the sodium hydroxide was added (phase B). This mixture was then heated under stirring (100 rpm) to 90° C. and the fatty acids are added (phase C). The mixture was mixed at 90° C. until it appears homogeneously (typically 60 minutes, 100 rpm). The pH of the formulation was checked (dilution of a small part of the formulation with water), pH-value should be between pH 8 and pH 9. The hot mixture was then filled into deo stick tubes and allowed to solidify at room temperature within 24 hours to give light yellowish pasty sticks.

TABLE-US-00004 Phase 8.3.1 8.3.2 8.3.3 8.3.4 8.3.5 8.3.6 8.3.7 A Propandiol 57 58 57.5 57.6 57.7 57.1 57.0 Glycerin 22.5 22.5 22.5 22.5 22.5 22.5 22.5 Water 2.55 2.55 2.55 2.55 2.55 2.55 2.55 B Sodium Hydroxide 10% 9.9 9.9 9.9 9.9 9.9 9.9 9.9 C Stearic Acid 3.15 3.15 3.15 3.15 3.15 3.15 3.15 Palmitic Acid 3.15 3.15 3.15 3.15 3.15 3.15 3.15 Ethylhexylglycerin 0.75 0.75 0.75 0.75 0.75 0.75 0.75 A Example 1 0.4 di-rhamnolipid 0.4 hexylester (monoester) Example 3 0.2 Example 4 0.3 Example 5 0.4 Example 6 0.8 Example 7 0.9 Deo- Deo- Deo- Deo- Deo- Deo- Deo- stick stick stick stick stick stick stick Formulations 8.3.3 to 8.3.7 are formulations according to the instant invention di-Rhamnolipid hexylester was prepared as described in example 3 of WO2017144317; instead of lauryl-alcohol, n-hexyl alcohol was used at equal molar amount.

Example 8.4

[0142] After phases A and B were prepared separately at room temperature, phase A was added to phase B under stirring (300 rpm, 1 minute). The mixture was then homogenized (5 minutes, 1800 rpm) to obtain a lotion. Then the polymers were added (Phase C) under stirring, followed by a short homogenization step (0.5 minutes, 300 rpm, 1 minute 1800 rpm). Finally, the sodium hydroxide was added (phase D) under stirring (10 minutes, 500 rpm) to obtain a lotion.

TABLE-US-00005 Phase 8.4.1 8.4.2 8.4.3 8.4.4 8.4.5 8.4.6 8.4.7 A Abil Care 85 2 2 2 2 2 2 2 Cyclopentasiloxane 8 8 8 8 8 8 8 B Polysorbate 80 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Water 83.67 79.67 80.82 81.57 84.32 84.47 83.97 Allantoin 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Propylene Glycol 2 2 2 2 2 2 2 C Carbomer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Xanthan Gum 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Mineral Oil (30 mPas) 1.06 1.06 1.06 1.06 1.06 1.06 1.06 D Sodium Hydroxide (10%) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 B Example 1 1 5 Phenoxyethanol, 1 1 1 1 1 1 1 Caprylyl Glycol Example 3 3.5 Example 4 2.9 Example 5 0.35 Example 6 0.2 Example 7 0.7 Roll-on Roll-on Roll-on Roll-on Roll-on Roll-on Roll-on Formulations 8.4.3 to 8.4.7 are formulations according to the instant invention

Example 8.5

[0143] The oil phase (phase A) and the aqueous phase (phase B) were mixed separately and homogenized by a spatula while being heated up to 75° C. Then, phase A was added to phase B while stirring (2 minutes, 500 rpm) followed by a homogenization step (3 minutes, 1800 rpm). After obtaining a milky lotion, the mixture was cooled down while being stirred at 250 rpm.

TABLE-US-00006 Phase 8.5.1 8.5.2 8.5.3 8.5.4 8.5.5 8.5.6 8.5.7 A Tego Care APD 18 MB 5 5 5 5 5 5 5 Isopropyl Palmitate 5 5 5 5 5 5 5 B Water 85 85 85 85 85 85 85 Glycerin 3 3 3 3 3 3 3 Phenoxyethanol, 1 1 1 1 1 1 1 Caprylyl Glycol di-RL-C2-Ester 1 m-RL-C8-Ester 1 Example 3 1 Example 4 1 Example 5 1 Example 6 1 Example 7 1 Roll-on not Roll-on Roll-on Roll-on Roll-on Roll-on Roll-on possible, viscosity too high Formulations 8.5.3 to 8.5.7 are formulations according to the instant invention di-rhamnolipid ethylester was prepared as described in example 4 of WO2017144317. di-rhamnolipid octylester was prepared as described in example 3 of WO2017144317; instead of lauryl-alcohol, n-octyl alcohol was used at equal molar amount.

Example 8.6

[0144] Formulating this water-in-oil emulsion requires the help of a ultra-turrax® (T 18 digital ultra-turrax, Ika, Ika Werke, Staufen, Germany).

[0145] The liquid components of phase A were mixed with a spatula. Then first the zinc stearate was incorporated into the oil phase by the ultra turrax (3 minutes, 10.000 rpm) before the Aerosil was added in similar way (3 minutes, 10.000 rpm). The aqueous phase (phase B) was also mixed with a spatula at room temperature and then slowly added in phase A with minimum input of mixing (2 minutes, 3000 rpm). After complete addition of phase B, the white emulsion was homogenized for short time (1 minute, 10.000 rpm) and filled into applicators.

TABLE-US-00007 Phase 8.6.1 8.6.2 8.6.3 8.6.4 8.6.5 8.6.6 8.6.7 A Abil EM 97 S 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Abil EM 90 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Diethylhexyl Carbonate 10.9 10.9 10.9 10.9 10.9 10.9 10.9 Dimethicone 5 mPas 10.9 10.9 10.9 10.9 10.9 10.9 10.9 Silica (Aerosil R 812) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Zinc stearate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 B Water 65 65 65 65 65 65 65 Glycerin 3 3 3 3 3 3 3 Sodium Chloride 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Phenoxyethanol, 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Caprylyl Glycol di-RL C2 Ester 5 di-RL C18 Ester 5 Example 3 5 Example 4 5 Example 5 5 Example 6 5 Example 7 5 Roll-on Roll-on Roll-on Roll-on Roll-on not Roll-on Roll-on possible, viscosity too high Formulations 8.6.3 to 8.6.7 are formulations according to the instant invention di-Rhamnolipid ethylester was prepared as described in example 4 of WO2017144317. di-Rhamnolipid octadecylylester was prepared as described in example 3 of WO2017144317; instead of lauryl-alcohol, n-octadecyl alcohol was used at equal molar amount.

Example 9: Panel Testing

[0146] Eight panelists were selected for odor tests (panelists are coded with letters A-H). Every panelist was equipped with a wash lotion as described in table 1.

TABLE-US-00008 TABLE 1 perfume free wash lotion for cleaning of underarms of panelists Active matter/ Concentration/ INCI Tradename/Supplier % % water 13.7 PEG-7 Glyceryl Cocoate TEGOSOFT ® GC/Evonik 100 5.4 Sodium Laureth Sulfate Texapon NSO/BASF 28 65.80 Cocamidopropyl Betaine; Glyceryl TEGO ® Betain HS/Evonik 10.00 Laurate PEG-18 Glyceryl Oleate/Cocoate ANTIL ® 171/Evonik 100 4.10 Verstatil PC Phenoxyethanol, Caprylyl Glycol/ 100 1 Evonik

[0147] This wash lotion was free of perfumes to avoid an influence of artificial odors on the panel results.

[0148] The panelists were asked to clean their armpits as usual in their daily routine, however, the panelists used the perfume free wash lotion provided. After cleaning, the formulations described in the section above were applied. The formulations were packed in neutral containers which were randomly labeled. Thus, the inventive formulations were applied also randomly under the left or the right arm. The panelists were also advised to use no additional perfume. The panelists applied the formulations in the morning and the degree of malodor was accessed after 8-10 hours after application. The panelists followed the normal working routine, the artificial sweat generation in hot rooms was not used since the formulations were evaluated in pairwise discrimination.

[0149] Six trained examiners evaluated the malodor intensity scale of the panelists after 8-10 hours. The ratings were given according to the malodor intensity scale ranging from 0 to 10. (see IFSCC Monograph, Number 6, “Antiperspirants and Deodorants: Priciples of Underarm Technology” Copyright© International Federation of the Societies of Cosmetic Chemists 1998; ISBN 1-870228-19-7 and Table 2).

[0150] The examiners scored the odor of the armpits of the panelists, the difference of the evaluation were calculated per examiner to visualize the pairwise difference perceived by the examiner. After all six examiners gave their evaluation on one panelists, the difference of the pairwise evaluation is averaged. A difference of the average of 1 is likely to be experienced by an untrained person, whereas a difference of 2 or more is clearly recognized.

TABLE-US-00009 TABLE 2 malodor intensity scale used for description of odor by the examiners Score malodor intensity scale 0 None, no odor 1 Threshold odor 2 Very slight odor 3 Slight odor 4 Slight to moderate odor 5 Moderate odor 6 Slightly strong odor 7 Moderately strong odor 8 Strong odor 9 Very strong odor 10 Extremly strong odor

Example 9.1

[0151] In a first experiment, formulations 8.1.1 and 8.1.2 were tested. Both formulations contain no molecules according to the instant invention. The difference in loading of aluminium salts should be investigated in that set.

TABLE-US-00010 difference Examiner 1 2 3 4 5 6 8.1.2 to 8.1.1 Panelist A left 8.1.2 4 5 6 5 6 5 right 8.1.1 1 1 1 2 0 0 −3 −4 −5 −3 −6 −5 −4.33 4.33 Panelist B left 8.1.1 2 1 1 2 1 1 right 8.1.2 6 5 6 6 6 5 4 4 5 4 5 4 4.33 4.33 Panelist C left 8.1.2 4 4 5 5 4 5 right 8.1.1 2 2 2 1 1 2 −2 −2 −3 −4 −3 −3 −2.83 2.83 Panelist D left 8.1.1 6 4 4 4 5 5 right 8.1.2 10 7 8 8 9 8 4 3 4 4 4 3 3.67 3.67 Panelist E left 8.1.2 8 6 7 6 7 7 right 8.1.1 3 2 4 2 3 3 −5 −4 −3 −4 −4 −4 −4.00 4.00 Panelist F left 8.1.1 2 2 2 3 2 1 right 8.1.2 5 5 6 7 6 6 3 3 4 4 4 5 3.83 3.83 Panelist G left 8.1.2 5 6 4 5 6 6 right 8.1.1 1 1 2 1 1 2 −4 −5 −2 −4 −5 −4 −4.00 4.00 Panelist H left 8.1.2 6 6 6 5 5 6 right 8.1.1 3 2 2 3 2 2 −3 −4 −4 −2 −3 −4 −3.33 3.33 Average of differences 3.79 over all panellists Results: It is obvious that the formulation with 20% aluminium salt (8.1.1) outperformed the formulation with 10% salt (8.1.2).

Example 9.2

[0152] The next set of experiments was made in order to see if the inventive structures can compensate the lower level of aluminium salt. Thus formulation 8.1.1 (20% aluminium salt) was tested against formulation 8.1.4 (10% aluminium salt+inventive structure 4)

TABLE-US-00011 difference Examiner 1 2 3 4 5 6 8.1.1 to 8.1.4 Panelist A left 8.1.1 2 3 1 2 3 2 right 8.1.4 2 1 2 1 2 3 0 −2 1 −1 −1 1 −0.33 0.33 Panelist B left 8.1.4 1 1 2 2 1 3 right 8.1.1 0 2 3 1 2 2 −1 1 1 −1 1 −1 0.00 0.00 Panelist C left 8.1.4 1 2 3 2 3 2 right 8.1.1 3 1 1 3 1 3 2 −1 −2 1 −2 1 −0.17 −0.17 Panelist D left 8.1.4 5 5 6 7 7 8 right 8.1.1 6 6 6 5 7 7 1 1 0 −2 0 −1 −0.17 −0.17 Panelist E left 8.1.4 6 6 5 8 5 7 right 8.1.1 7 5 4 6 7 6 1 −1 −1 −2 2 −1 −0.33 −0.33 Panelist F left 8.1.1 2 2 2 3 2 2 right 8.1.4 1 3 2 2 1 2 −1 1 0 −1 −1 0 −0.33 0.33 Panelist G left 8.1.1 1 2 2 1 0 2 right 8.1.4 0 3 1 0 2 1 −1 1 −1 −1 2 −1 −0.17 0.17 Panelist H left 8.1.4 0 1 2 2 2 1 right 8.1.1 1 2 1 1 2 0 1 1 −1 −1 0 −1 −0.17 −0.17 Average of differences 0.00 over all panellists Results: The two formulations could not be differentiated by the examiners, inventive structure 4 is able to compensate the reduced amount of aluminium salt.

Example 9.3

[0153] 8.2.2 vs. 8.2.7

TABLE-US-00012 difference Examiner 1 2 3 4 5 6 8.2.7 to 8.2.2 Panelist A left 8.2.7 2 2 1 2 2 2 right 8.2.2 3 4 3 5 3 2 1 2 2 3 1 0 1.50 1.50 Panelist B left 8.2.7 5 4 2 3 3 4 right 8.2.2 7 7 6 5 4 7 2 3 4 2 1 3 2.50 2.50 Panelist C left 8.2.2 5 3 2 4 5 6 right 8.2.7 3 2 2 2 3 3 −2 −1 0 −2 −2 −3 −1.67 1.67 Panelist D left 8.2.7 6 5 4 5 5 6 right 8.2.2 8 7 8 8 9 9 2 2 4 3 4 3 3.00 3.00 Panelist E left 8.2.7 5 5 5 4 7 6 right 8.2.2 8 9 7 8 10 9 3 4 2 4 3 3 3.17 3.17 Panelist F left 8.2.2 5 4 4 4 3 4 right 8.2.7 2 2 1 2 2 3 −3 −2 −3 −2 −1 −1 −2.00 2.00 Panelist G left 8.2.2 4 4 5 3 3 3 right 8.2.7 2 2 2 2 1 2 −2 −2 −3 −1 −2 −1 −1.83 1.83 Panelist H left 8.2.2 3 4 4 3 3 2 right 8.2.7 2 3 3 2 1 2 −1 −1 −1 −1 −2 0 −1.00 1.00 Average of differences 2.08 over all panellists Results: The results clearly show that the inventive structure 7 is able to reduce malodor.

Example 9.4

[0154]

TABLE-US-00013 difference Examiner 1 2 3 4 5 6 8.3.1 to 8.3.3 Panelist A left 8.3.1 3 4 5 3 3 4 right 8.3.3 1 2 1 0 1 2 2 2 4 3 2 2 2.50 2.50 Panelist B left 8.3.1 5 3 3 4 2 3 right 8.3.3 1 0 2 1 1 1 −4 −3 −1 −3 −1 −2 −2.33 2.33 Panelist C left 8.3.3 2 2 4 3 4 1 right 8.3.1 4 6 6 6 7 5 2 4 2 3 3 4 3.00 3.00 Panelist D left 8.3.1 8 7 10 9 9 8 right 8.3.3 4 5 7 4 5 6 4 2 3 5 4 2 3.33 3.33 Panelist E left 8.3.3 2 3 5 4 3 2 right 8.3.1 7 8 8 9 9 9 5 5 3 5 6 7 5.17 5.17 Panelist F left 8.3.3 2 3 4 3 2 1 right 8.3.1 6 7 5 5 4 4 −4 −4 −1 −2 −2 −3 −2.67 2.67 Panelist G left 8.3.1 6 5 5 5 7 4 right 8.3.3 3 2 3 3 4 1 −3 −3 −2 −2 −3 −3 −2.67 2.67 Panelist H left 8.3.3 1 1 3 1 2 2 right 8.3.1 5 6 4 3 3 4 4 5 1 2 1 2 2.50 2.50 Average of differences 3.02 over all panellists Results: The inventive structure 3 is superior in reduction of malodors as compared to the pure di-Rhamnolipid.

Example 9.5

[0155] 8.3.2 vs 8.3.5

TABLE-US-00014 difference Examiner 1 2 3 4 5 6 8.3.5 to 8.3.2 Panelist A left 8.3.5 1 1 0 1 2 1 right 8.3.2 2 3 3 4 4 4 1 2 3 3 2 3 2.33 2.33 Panelist B left 8.3.2 3 3 4 4 3 3 right 8.3.5 1 1 1 2 2 1 −2 −2 −3 −2 −1 −2 −2.00 2.00 Panelist C left 8.3.5 3 3 2 3 4 2 right 8.3.2 5 6 5 6 6 4 2 3 3 3 2 2 2.50 2.50 Panelist D left 8.3.5 5 5 6 5 6 7 right 8.3.2 8 8 10 9 9 9 3 3 4 4 3 2 3.17 3.17 Panelist E left 8.3.5 4 5 5 5 5 4 right 8.3.2 8 8 9 10 9 10 4 3 4 5 4 6 4.33 4.33 Panelist F left 8.3.2 5 6 6 5 4 5 right 8.3.5 3 2 2 3 2 2 −2 −4 −4 −2 −2 −3 −2.83 2.83 Panelist G left 8.3.2 5 5 6 5 6 4 right 8.3.5 2 2 3 3 2 1 −3 −3 −3 −2 −4 −3 −3.00 3.00 Panelist H left 8.3.5 2 2 2 1 2 3 right 8.3.2 4 5 4 3 4 6 2 3 2 2 2 3 2.33 2.33 Average of differences 2.81 over all panellists Results: The incentive structure 5 is superior in reduction of malodors as compared to the pure di-Rhamnolipid Hexylester. Furthermore, Panelists A, C, D, G and H complained on itching skin in the armpits treated with formulation 8.3.2.

Example 9.6

[0156]

TABLE-US-00015 difference Examiner 1 2 3 4 5 6 8.5.2 to 8.5.6 Panelist A left 8.5.2 8 7 6 7 8 8 right 8.5.6 3 4 2 4 5 5 −5 −3 −4 −3 −3 −3 −3.50 3.50 Panelist B left 8.5.6 7 7 6 8 7 6 right 8.5.2 4 4 3 5 4 4 −3 −3 −3 −3 −3 −2 −2.83 2.83 Panelist C left 8.5.6 3 3 4 4 4 3 right 8.5.2 8 8 7 6 7 7 5 5 3 2 3 4 3.67 3.67 Panelist D left 8.5.2 10 10 8 9 9 9 right 8.5.6 5 5 5 5 4 6 −5 −5 −3 −4 −5 −3 −4.17 4.17 Panelist E left 8.5.6 5 5 4 7 5 6 right 8.5.2 9 8 10 10 8 8 4 3 6 3 3 2 3.50 3.50 Panelist F left 8.5.6 5 7 8 7 7 8 right 8.5.2 5 4 6 5 5 5 0 −3 −2 −2 −2 −3 −2.00 2.00 Panelist G left 8.5.2 6 6 7 8 6 6 right 8.5.6 3 2 5 5 4 2 −3 −4 −2 −3 −2 −4 −3.00 3.00 Panelist H left 8.5.2 8 7 6 8 7 8 right 8.5.6 3 4 5 5 5 4 −5 −3 −1 −3 −2 −4 −3.00 3.00 Average of differences 3.21 over all panellists Results: The set of data clearly shows that the inventive oligo ester of mono-rhamnolipid is better suited in reduction of malodor as compared to the mono-ester.

List of Ingredients Used

[0157]

TABLE-US-00016 INCI Tradename Supplier Isoceteth-20 Tego Alkaonol IC 20 Evonik Diethylhexyl Carbonate Tegosoft DEC Evonik Triisostearin Tegosoft TIS Evonik Glyceryl Isostearate Sympatens-GMIS KLK Oleo Europe Butylene Gylcol Butylene Gylcol Dow PEG-6000 Distearate Rewopal PEG 6000 Evonik DS PEG-18 Glyceryl Oleate/Cocoate Antil 171 Evonik Alumminium Cholrohydrate Chlorohydrol Elementis Xanthan Gum Satiaxane Cargill Ethylalcohol Ethanol Cremer Oleo Propylen Glycol Propylen Glycol Dow Ethylhexylglycerin Ethylhexylglycerin Hubei Artec Biotechnology Co., Ltd. Citric acid Citric acid Sigma Aldrich Panthenol Panthenol Parchem Glycerin Glycerin Cremer Oleo Sodium Hydroxide 10% Sodium Hydroxide Sigma Aldrich Stearic Acid CremerAC SA 18/92 Cremer Oleo Palmitic Acid CremerAC C16/98 Cremer Oleo Bis-PEG/PPG-16/16 PEG/PPG-16/16 Dimethicone Abil Care 85 Evonik (and) Caprylic/Capric Triglyceride Tego SMO 80 V Polysorbate 80 Evonik Carbomer Carbomer 940 Ashland Mineral Oil Agrol 13 Sonneborn Polyglyceryl-6 Stearate (and) Polyglyceryl-6 Tego Care APD 18 Evonik Behenate (and) C18-22 Hydroxyalkyl Hydroxypropyl Guar Isopropyl Palmitate Tegosoft P Evonik Bis-PEG/PPG-14/14 Dimethicone; Dimethicone Abil EM 97 S Evonik Cetyl PEG/PPG-10/1 Dimethicone Abil EM 90 Evonik Dimethicone 5 mPas Belsil DM 5 Wacker Silica Aerosil R 812 Evonik Zinc stearate Zinc stearate Sigma Aldrich Sodium Chloride Sodium Chloride Sigma Aldrich Phenoxyethanol, Caprylyl Glycol Verstatil PC Evonik Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 Schülke & Mayr