Rhamnolipid oligomer

Abstract

The present invention relates to novel rhamnolipid esters, a method for preparing the same, and the use of rhamnolipid esters as a cosmetic additive, #imgabs0#

Description

Technical Field

[0001] The present invention relates to novel rhamnolipid esters, a method for preparing the same, and the use of the rhamnolipid esters as a cosmetic additive. Prior Art

[0002] EP3419985 discloses rhamnolipid esters of rhamnolipids and fatty alcohols having 7 - 32 carbon atoms.

[0003] WO2019038125 discloses a dispersion, in particular an emulsion, containing at least one rhamnolipid derivative, and the use of the rhamnolipid derivative as an emulsifier or a dispersion aid, wherein the rhamnolipid derivative is certain rhamnolipid esters or rhamnolipid amides.

[0004] Miao et al., Journal of Surfactants and Detergents, 17(6), 2014; 1069 - 1080 describes the synthesis of dirhamnolipid ethyl ester by esterification with ethanol and the suitability of the ester as a non - ionic surfactant.

[0005] WO2001010447 and EP1889623 disclose the pharmaceutical and cosmetic applications of rhamnolipids and short - chain rhamnolipid esters (C1 - C6; methyl to hexyl esters, straight - chain or branched), especially in wound healing.

[0006] WO2018195613 discloses a deodorant composition for controlling body odor in a local area of the body (such as under the armpit) or textiles, wherein the composition contains a specific amount of a specific component in combination with rhamnolipids to specifically act on Corynebacterium xerosis.

[0007] WO2008013899 discloses the application of a cleaning formulation containing 0.01% - 99.9% rhamnolipids, with the remainder being a carrier.

[0008] An object of the present invention is to provide a novel antiperspirant substance that is also suitable for suppressing body odor.

[0009] Description of the Invention

[0010] Surprisingly, it has been found that the following rhamnolipid esters can achieve the set objectives of the present invention.

[0011] Therefore, the present invention provides the rhamnolipid esters as described in claim 1.

[0012] The present invention also provides a method for preparing the rhamnolipid esters according to the present invention and its use.

[0013] One advantage of the present invention is that the rhamnolipid ester according to the present invention has excellent performance in reducing malodor and controlling sweating.

[0014] Another advantage of the present invention is that the rhamnolipid ester of the present invention can be added to numerous formulations without causing instability.

[0015] Another advantage of the present invention is that the rhamnolipid ester according to the present invention increases the mildness of the formulation.

[0016] Yet another advantage of the present invention is that the method for preparing the rhamnolipid ester according to the present invention can be carried out on standard assets on an industrial scale.

[0017] Another advantage of the present invention is that the composition according to the present invention potentially reduces the release of zinc and aluminum into the environment because the rhamnolipid ester of the present invention is an excellent alternative.

[0018] Yet another advantage is that, after applying the rhamnolipid ester of the present invention, the skin becomes less defatted and the skin hydration is improved.

[0019] Another advantage is that the product can be separated and processed in an excellent manner.

[0020] Yet another advantage is that the rhamnolipid ester according to the present invention does not cause unwanted skin irritation while leaving a good smooth, silky-soft skin feeling.

[0021] The terms "rhamnolipid" and "rhamnolipid ester" related to the present invention also always include their corresponding salts.

[0022] The term "rhamnolipid group" related to the present invention is understood to be a part of the general formula (I) shown below, i.e., the part within the parentheses with z as the subscript.

[0023] The term "dirhamnolipid" related to the present invention is understood to refer to the compound of the general formula (I) shown below or its salt, where A = H, z = 1, and n = 1.

[0024] The term "monorhamnolipid" related to the present invention is understood to refer to the compound of the general formula (I) shown below or its salt, where A = H, z = 1, and n = 0.

[0025] Different rhamnolipids are abbreviated according to the following nomenclature:

[0026] "diRL-CXCY" is understood to refer to the dirhamnolipid of the general formula (I) or its salt, where A = H, z = 1, and one of the groups R 1 and R 2 is (CH2)o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4.

[0027] "monoRL-CXCY" is understood to refer to a monorhamnolipid of general formula (I) or a salt thereof, where A = H, z = 1, and where one of the groups R 1 and R 2 is one of (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4.

[0028] Thus, the nomenclature used does not distinguish between "CXCY" and "CYCX".

[0029] For rhamnolipids with m = 0, monoRL-CX or diRL-CX is used accordingly.

[0030] If one of the above indices X and / or Y has ":N", this indicates that the corresponding group R 1 and / or R 2 = an unbranched, unsubstituted hydrocarbon group having X - 3 or Y - 3 carbon atoms with N double bonds.

[0031] A similar nomenclature is used for rhamnolipid esters of the form di / monoRL-CXCY:N esters.

[0032] "pH" as related to the present invention is defined as the value measured at 25 °C after stirring for 5 minutes using a pH electrode calibrated according to ISO 4319 (1977) for the corresponding substance.

[0033] Unless otherwise stated, all percentages (%) are by mass.

[0034] The present invention provides rhamnolipid esters of general formula (I)

[0035]

[0036] where

[0037] m = are the same or different and independently of one another 2, 1 or 0, in particular 1 or 0,

[0038] n = are the same or different and independently of one another 1 or 0, in particular 1,

[0039] z = 2 - 10, in particular 2 - 4, most preferably 2,

[0040] R 1 = independently of one another, are the same or different and are organic groups having 2 - 24, preferably 5 - 13 carbon atoms, in particular optionally branched, optionally substituted, in particular hydroxy - substituted, optionally unsaturated, in particular optionally mono - unsaturated, di - unsaturated or tri - unsaturated alkyl groups, preferably selected from pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and one of (CH2)o - CH3, where o = 1 - 23, preferably 4 - 12,

[0041] R 2 = independently of one another, are the same or different and are organic groups having 2 - 24, preferably 5 - 13 carbon atoms, in particular optionally branched, optionally substituted, in particular hydroxy - substituted, optionally unsaturated, in particular optionally mono - unsaturated, di - unsaturated or tri - unsaturated alkyl groups, preferably selected from pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and one of (CH2)o - CH3, where o = 1 - 23, preferably 4 - 12, and

[0042] A is a z - valent organic group.

[0043] Preferred rhamnolipid esters according to the invention are those in which the rhamnolipid groups are selected from the following groups: diRL - C10C10, diRL - C8C10, diRL - C10C12, diRL - C10C12:1 and monoRL - C10C10.

[0044] Particularly preferred rhamnolipid esters according to the invention are characterized in that z = 2 and A is selected from divalent hydrocarbon groups which may be substituted by one or more hydroxy groups,

[0045] preferably selected from

[0046]

[0047] where

[0048] R 3 and R 4 are selected from CH3 and H,

[0049] r = 0 - 3,

[0050] s = 0 - 24, and

[0051] t = 0 - 24,

[0052] where in the preferred structure

[0053] R 3 = R 4 = H, r = t = 0, s = 0 - 24, preferably 1 - 14,

[0054] R 3 =H, R 4 =CH3, r=0, s=0-2, t=0-23, preferably 1-15,

[0055] R 3 =CH3, R 4 =CH3, r=0-3, s=0-2, t=0-23, preferably 1-15,

[0056] The most preferred structure

[0057] R 3 =R 4 =H, r=t=0, s=0-8, 10, 12 or 14,

[0058] R 3 =H, R 4 =CH3, r=0, s=0 or 1, t=0,

[0059] R 3 =H, R 4 =CH3, r=0, s=0, t=3, 7, 9, 11 or 13,

[0060] R 3 =CH3, R 4 =CH3, r=s=2, t=0.

[0061] According to other particularly preferred rhamnolipid esters of the present invention, z=2 and A is selected from a divalent hydrocarbon group, which may be substituted with one or more hydroxyl groups, and A is selected from

[0062]

[0063] Alternatively, particularly preferred rhamnolipid esters according to the invention are characterized in that z=2 and A is selected from

[0064]

[0065] Alternatively, particularly preferred rhamnolipid esters according to the invention are characterized in that z=2 and A is selected from the group consisting of

[0066]

[0067] Particularly preferred rhamnolipid esters according to the invention are characterized in that

[0068] z=2,

[0069] The rhamnolipid group is selected from the group consisting of diRL-C10C10, diRL-C8C10, diRL-C10C12, diRL-C10C12:1 and monoRL-C10C10, and

[0070] A is selected from

[0071]

[0072] wherein

[0073] R 3 = R 4 = H, r = t = 0, s = 0 - 8, 10, 12 or 14,

[0074]

[0075] The particularly preferred rhamnolipid esters according to the invention constitute a mixture composition of different rhamnolipid esters of the general formula (I).

[0076] The rhamnolipid esters according to the invention are preferably a mixture composition of rhamnolipid esters, characterized in that they particularly contain mono - rhamnolipid esters and di - rhamnolipid esters and / or mixed mono / di - rhamnolipid esters, the latter being characterized by having at least one mono - rhamnolipid group and at least one di - rhamnolipid group in one molecule.

[0077] Depending on the application, it may be preferred that, in the mixture composition according to the invention, the weight percentage of the mono - rhamnolipid groups is greater than the weight percentage of the di - rhamnolipid groups, or the weight percentage of the di - rhamnolipid groups is greater than the weight percentage of the mono - rhamnolipid groups, wherein the weight percentages are based on all the mono - rhamnolipid groups and di - rhamnolipid groups in the rhamnolipid esters.

[0078] Thus, for example, the rhamnolipid esters as a mixture composition according to the invention may contain, for example, more than 60% by weight, particularly more than 80% by weight, or even more than 95% by weight of di - rhamnolipid groups, or also, for example, more than 60% by weight, particularly more than 80% by weight, or even more than 95% by weight of mono - rhamnolipid groups, wherein the weight percentages are based on all the mono - rhamnolipid esters and di - rhamnolipid groups in the rhamnolipid esters.

[0079] The present invention further provides a method for preparing rhamnolipid esters, which comprises the following method steps:

[0080] A) Providing at least one rhamnolipid,

[0081] B) Reacting the rhamnolipid with at least one coupling agent,

[0082] C) Reacting the rhamnolipid activated by method step B) with a polyol having 1 - 32 carbon atoms, and optionally

[0083] D) Purifying the rhamnolipid esters.

[0084] Method step A) is carried out according to known methods of the prior art, in particular using genetically modified microorganisms that preferably overexpress rhamnolipid synthesis genes, which genes are preferably selected from rhlA, rhlB, and rhlC. A person skilled in the art can find corresponding descriptions in, for example, US2014296168 and WO2012013554.

[0085] According to the invention, the coupling agent preferably used in method step B) is selected from or preferably consists of at least one of the group consisting of: dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-cyclohexyl-N'-(2'-morpholinoethyl)carbodiimide methyl-p-toluenesulfonate, N-benzyl-N'-3'-dimethylaminopropylcarbodiimide hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-ethylcarbodiimide hydrochloride, and carbonyldiimidazole, particularly preferably dicyclohexylcarbodiimide and diisopropylcarbodiimide.

[0086] Likewise, according to the invention, the catalyst preferably used in method step C) is selected from or preferably consists of at least one of the group consisting of: N-ethyldiisopropylamine, trialkylamine, pyridine, 4-dimethylaminopyridine, and hydroxybenzotriazole, particularly hydroxybenzotriazole.

[0087] The preferred method according to the invention preferably gives a rhamnolipid ester, which is described as the preferred rhamnolipid ester according to the invention above.

[0088] Thus, for example, preferably in method step A), rhamnolipids selected from diRLC10C10, diC8C10, diRLC10C12, diRLC10C12:1, and monoRLC10C10 or mixtures thereof are preferably used.

[0089] Thus, the alcohol used in method step C) is preferably selected from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,6-dimethyloctane-1,8-diol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 2,2,9,9-tetramethyl-1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, and 1,2-hexadecanediol.

[0090] Optionally, the alcohol preferably used in process step C) is selected from 1,4 - cyclohexanediol, 1,2 - cyclohexanediol, 1,3 - cyclohexanediol, 1,2 - cyclopentanediol, 1,3 - cyclopentanediol, 4,4 - dimethyl - 1,2 - cyclopentanediol, 4 - cyclopentene - 1,3 - diol, 3 - cyclopentene - 1,2 - diol, 2 - tert - butyl - 1,4 - cyclohexanediol, 2 - methyl - 1,4 - cyclohexanediol, 1,3 - cyclohexanedimethanol, 1,4 - cyclohexanedimethanol, 4,4′ - isopropylidenedicyclohexanol, and 4,4′ - dicyclohexanol.

[0091] Optionally, the alcohol preferably used in process step C) is selected from 1,4 - benzenediol, methylhydroquinone, 1,2 - benzenediol, 1,3 - benzenediol, 1,3 - dihydroxy - 4 - toluene, 4 - methyl - 1,2 - benzenediol, 3,5 - dihydroxytoluene, 2,6 - dihydroxytoluene, 4 - butyl - 1,3 - benzenediol, 4 - hexylresorcinol, 1,4 - benzenedimethanol, and 1,4 - bis(2 - hydroxyethyl)benzene.

[0092] Very preferably, the alcohol used in process step C) is selected from 1,2 - ethanediol, 1,3 - propanediol, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, 1,8 - octanediol, 1,10 - decanediol, 1,12 - dodecanediol, 1,4 - cyclohexanedimethanol, 1,4 - cyclohexanediol, 1,4 - benzenedimethanol, and 1,4 - bis(2 - hydroxyethyl)benzene.

[0093] The present invention also provides rhamnolipid esters obtainable by the process according to the invention.

[0094] The rhamnolipid esters according to the invention can advantageously be incorporated, in particular, into cosmetic formulations, preferably for antiperspirant applications.

[0095] Therefore, the present invention further provides

[0096] the use of the rhamnolipid esters according to the invention in the preparation of formulations, in particular cosmetic formulations, and

[0097] formulations themselves, in particular cosmetic formulations, preferably for antiperspirant applications, which comprise rhamnolipid esters according to the invention.

[0098] The formulations according to the invention are preferably aqueous formulations.

[0099] The term "aqueous formulation" in connection with the present invention is to be understood as a formulation comprising at least 5% by weight of water based on the total composition under consideration.

[0100] According to the invention, the formulation according to the invention preferably contains from 0.05% to 40% by weight, preferably from 0.1% to 20% by weight, particularly preferably from 0.2% to 5% by weight of the rhamnolipid ester according to the invention, where the percentages by weight are based on the total formulation.

[0101] In addition to the rhamnolipid ester according to the invention, the preferred formulation according to the invention further contains at least one additional component.

[0102] The formulation according to the invention may further contain at least one additional component selected from the following:

[0103] Emollient,

[0104] Emulsifier,

[0105] Thickener / viscosity regulator / stabilizer,

[0106] UV light protection filter,

[0107] Antioxidant,

[0108] Hydrotrope (or polyol),

[0109] Solid and filler,

[0110] Film-forming agent,

[0111] Pearlescent additive,

[0112] Deodorant and antiperspirant active ingredient,

[0113] Insect repellent,

[0114] Self-tanning agent,

[0115] Surfactant,

[0116] Fragrance,

[0117] Preservative,

[0118] Propellant,

[0119] Conditioner,

[0120] Dye,

[0121] Cosmetic active ingredient,

[0122] Care additive,

[0123] Lipid-rich agent,

[0124] Solvent,

[0125] Preferably, it contains a fragrance, an antiperspirant active ingredient, and a propellant.

[0126] Substances that can be used as exemplary representatives of the respective groups are known to those skilled in the art and can be found, for example, in German application DE 102008001788.4. This patent application is hereby incorporated by reference and thus forms part of this disclosure.

[0127] Regarding other optionally present components and the amounts of these components, explicit reference is made to relevant handbooks known to those skilled in the art, such as K. Schrader, "Grundlagen und Rezepturen der Kosmetika [Fundamentals and principles of cosmetics]", 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.

[0128] The amount of a specific additive depends on the intended use.

[0129] Typical guiding formulations for various applications are known in the prior art and are included, for example, in the handbooks of manufacturers of specific base materials and active ingredients. These existing formulations can generally be adopted without modification. However, if necessary, for adaptation and optimization purposes, the required modifications can be made through simple experiments without complexity.

[0130] The rhamnolipid esters according to the invention and the formulations according to the invention comprising the rhamnolipid esters according to the invention can advantageously be used for suppressing body odor.

[0131] The invention also provides the cosmetic use of the rhamnolipid esters according to the invention and / or the formulations according to the invention in antiperspirant applications.

[0132] The invention also provides the cosmetic use of the rhamnolipid esters according to the invention and / or the formulations according to the invention for suppressing sweating.

[0133] The following listed examples illustrate the invention by way of example, but the invention is not limited to the embodiments described in the examples, and its scope of application is obvious from the whole of the specification and the claims. Examples

[0134] Example 1: Preparation of dirhamnolipid

[0135] Fermentation was carried out using the recombinant strain Pseudomonas putida KT2440SpBBR1MCS2-Plac-rhlABC-T-Ptac-rhlC-T. The construction of this strain was described in US2014296168. As described in WO2012013554, precultivation was carried out in shake flasks. For the main culture, a mineral medium (M9) was also used. Fermentation was carried out in a glucose-limited fed-batch process in a 2-liter fermenter. The feeding of glucose was regulated by referring to the dissolved oxygen signal. The oxygen partial pressure of the fermentation broth was adjusted to 20% saturation by the stirrer speed. The pH was adjusted to 7 by a pH electrode and 2M sulfuric acid or 20 wt% ammonia solution was added. To prevent excessive foaming of the fermentation broth, antifoam DOW Corning 1500 was added as needed. Fermentation was carried out for 4 days until the dry biomass reached 15 g / l. The rhamnolipid concentration was determined to be 9.8 g / l by HPLC. After centrifuging the cells at 10,000 g, the fermentation broth was adjusted to pH 3.1 by adding concentrated H2SO4. Centrifugation was carried out again to obtain a paste-like solid concentrate with an RL fraction of 45 wt% and a viscosity > 10,000 mPas. With continuous stirring, an aqueous KOH solution with a concentration of 50 wt% was added to the paste-like suspension of the concentrated rhamnolipid precipitate, and pH 6 was established. At this time, the paste-like substance liquefied and the viscosity decreased sharply. The suspension produced a clear solution. The solution was adjusted to an active content of 35 wt% by adding water. Based on the dry mass, the rhamnolipid purity > 90 wt%. For synthesis, the rhamnolipid was lyophilized.

[0136] The rhamnolipid species verified by HPLC were:

[0137]

[0138] Example 2: Preparation of mono-rhamnolipid

[0139] The 35 wt% rhamnolipid solution prepared as described above was diluted to 1% by adding water. Two liters of this solution were heated to 50 °C. With gentle stirring, 200 units of thermostable rhamnosidase (ThermoActiveTM Rhamnosidase A, Prokazyme) were added, and the reaction was carried out overnight. After 20 hours, a solution sample was analyzed by HPLC. Dirhamnolipid had been completely converted to mono-rhamnolipid and rhamnose. Then, the enzyme was inactivated at 80 °C for one hour. The whole mixture was lyophilized.

[0140] Example 3: Synthesis of dirhamnolipid-di-ester 1

[0141] 25 g of the lyophilized dirhamnolipid from Example 1 was dissolved in THF with 6.6 ml of diisopropylcarbodiimide and stirred under nitrogen at 55 °C for 1 hour. Next, 1.6 g 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, the mixture was stirred and slowly cooled to 2 °C, and stirring was continued for 2 hours. The solid was filtered off through a glass filter. The filter cake was washed with a mixture of ethanol and water (6:1). Further purification can be achieved by reverse-phase liquid chromatography.

[0142] Example 4: Synthesis of dirhamnolipid - di - ester 2

[0143] A mixture of 25 g of the lyophilized dirhamnolipid from Example 1 and 4.4 g of N - hydroxysuccinimide (HSU) was dissolved in THF and stirred under nitrogen at room temperature for 1 hour. 6.6 ml of diisopropylcarbodiimide was added to the mixture over a period of about 10 minutes and rinsed with 2 ml of THF. The mixture was stirred at 55 °C for 1 hour. Next, 2 g of 1,4 - cyclohexanediol was added and stirring was continued at 55 °C for 7 hours and at 50 °C overnight. The next day, 2 ml of water was added to quench the reaction. Half of the mixture was distilled off and an additional 50 ml of methanol was added and the mixture was stirred at 50 °C. The turbid mixture was slowly cooled to 2 °C and stirred for 5 hours. The solid was filtered off through a glass filter. The filter cake was washed with a mixture of ethanol and water (6:1). Further purification can be achieved by reverse-phase liquid chromatography.

[0144] Example 5: Synthesis of monorhamnolipid - di - ester 1

[0145] 25 g of the lyophilized monorhamnolipid from Example 2 was dissolved in THF with 6.9 ml of diisopropylcarbodiimide and stirred under nitrogen at 55 °C for 1 hour. Next, 2.6 g 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 with stirring and continued for 2 hours. The solid was filtered off through a glass filter. The filter cake was washed with a mixture of ethanol and water (6:1). Further purification can be achieved by reverse-phase liquid chromatography.

[0146] Example 6: Synthesis of monorhamnolipid - di - ester 2

[0147] A mixture of 25 g of the freeze-dried mono-rhamnolipid from Example 2 and 5.7 g of N-hydroxy-succinimide (HSU) was dissolved in THF and stirred for 1 h at room temperature under nitrogen. 8.5 ml of diisopropylcarbodiimide was added to the mixture over a period of about 10 min and rinsed with 2 ml of THF. The mixture was stirred at 55 °C for 1 h. Next, 3.2 g of 1,4-cyclohexanedimethan was added and stirring was continued at 55 °C for 7 h and at 50 °C overnight. The next day, 2 ml of water was added to quench the reaction. Half of the mixture was distilled off, an additional 50 ml of methanol was added, and the mixture was stirred at 50 °C. The turbid mixture was slowly cooled to 2 °C and stirred for 5 h. The solid was filtered off through a glass filter. The filter cake was washed with a mixture of ethanol and water (6:1). Further purification can be carried out by reverse-phase liquid chromatography.

[0148] Example 7: Synthesis of mixed mono / di-rhamnolipid-di-esters

[0149] A mixture of 20 g of the freeze-dried di-rhamnolipid from Example 1, 15 g of the mono-rhamnolipid from Example 2 and 11 ml of diisopropylcarbodiimide was dissolved in THF and stirred for 1 h at 55 °C under nitrogen. Next, 2.5 g 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, the mixture was stirred and slowly cooled to 2 °C and stirred for 5 h. The solid was filtered off through a glass filter. The filter cake was washed with a mixture of ethanol and water (6:1) and dried overnight at 40 °C under vacuum.

[0150] Example 8: Application effect

[0151] To measure the effect of specific structures on the production of axillary sweating and odor. The following application tests were carried out with the formulations according to the invention.

[0152] The following formulations were prepared 24 h before use. Typically, 500 g of formulation was prepared in an 800 mL beaker. If the ingredients / phases needed to be heated, a water bath was used. If not otherwise stated, mixing was carried out by a four-blade stirrer driven by an IKA Eurostar 20 digital (IKA Werke, Staufen, Germany).

[0153] Example 8.1

[0154] Prepare 500 g of the formulation as follows: Mix the oil (Phase A) and the aqueous phase (Phase B, part of the water, butylene glycol, and, if specified, the structure of the present invention) separately and heat to 80 °C with stirring. The remaining water and PEG-6000 distearate are also mixed separately and heated to 80 °C.

[0155] While stirring at 250 rpm in an 800 mL beaker with a four-blade stirrer for 5 minutes, slowly add Phase B to Phase A. Then, add Phase C within 1 minute, still mixing the mixture and maintaining at 80 °C during this process. After adding Phase C, stir the mixture thoroughly (1000 rpm, 3 minutes), then stir gently (100 rpm) and cool to 40 °C. While stirring thoroughly (1000 rpm, 3 minutes), add Phase D at 40 °C, then add Phase E while stirring (1 minute, 250 rpm). Then the entire mixture needs to be cooled to room temperature while stirring thoroughly (1000 rpm).

[0156]

[0157] Formulations 8.1.3 to 8.1.7 are formulations according to the present invention.

[0158] Example 8.2

[0159] The following formulations were prepared:

[0160] Heat the water (Phase A) to 75 °C to dissolve xanthan gum (Phase B), while stirring (at least 15 minutes, 1000 rpm). Then cool the mixture to room temperature (100 rpm) to add ethanol (Phase C). Then, all other ingredients (Phase D) can be added while mixing slightly (100 rpm - 250 rpm).

[0161]

[0162]

[0163] Formulations 8.2.2 to 8.2.7 are formulations according to the present invention.

[0164] Example 8.3

[0165] Prepare this deodorant stick formulation 48 hours before application to allow the formulation to fully cure.

[0166] Heat ethylene glycol, glycerol, and water (Phase A) to 60 °C, and add sodium hydroxide (Phase B). Then heat the mixture to 90 °C with stirring (100 rpm), and add fatty acid (Phase C). Mix the mixture at 90 °C until it is homogenized (usually 60 minutes, 100 rpm). Check the pH of the formulation (dilute a small portion of the formulation with water), and the pH value should be between pH 8 and pH 9. Then fill the hot mixture into a deodorant stick tube and let it cure at room temperature for 24 hours to obtain a pale yellow paste stick.

[0167]

[0168] Formulations 8.3.3 to 8.3.7 are formulations according to the present invention.

[0169] Prepare dirhamnolipid hexyl ester as described in Example 3 of WO2017144317; replace lauryl alcohol with an equimolar amount of n-hexanol.

[0170] Example 8.4

[0171] After separately preparing Phases A and B at room temperature, add Phase A to Phase B with stirring (300 rpm, 1 minute). Then homogenize the mixture (5 minutes, 1800 rpm) to obtain a lotion. Then add the polymer (Phase C) with stirring, followed by a short homogenization step (0.5 minute, 300 rpm, 1 minute at 1800 rpm). Finally, add sodium hydroxide (Phase D) with stirring (10 minutes, 500 rpm) to obtain a lotion.

[0172] 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, Caprylyl Glycol 1 1 1 1 1 1 1 Example 3 3.5 Example 4 2.9 Example 5 0.35 Example 6 0.2 Example 7 0.7 Roll and apply Roll and apply Roll and apply Roll and apply Roll and apply Roll and apply Roll and apply

[0173] Formulations 8.4.3 to 8.4.7 are formulations according to the present invention.

[0174] Example 8.5

[0175] Mix the oil phase (Phase A) and the water phase (Phase B) separately, and homogenize them with a spatula while heating to 75 °C. Then, add Phase A to Phase B while stirring (2 minutes, 500 rpm), followed by a homogenization step (3 minutes, 1800 rpm). After obtaining an emulsified lotion, cool the mixture while stirring at 250 rpm.

[0176]

[0177]

[0178] Formulations 8.5.3 to 8.5.7 are formulations according to the present invention.

[0179] Prepare dirhamnolipid ethyl ester as described in Example 4 of WO2017144317.

[0180] Prepare dirhamnolipid octyl ester as described in Example 3 of WO2017144317; replace lauryl alcohol with an equimolar amount of 1-octanol.

[0181] Example 8.6

[0182] Preparing this water-in-oil emulsion requires (T 18 digital ultra-turrax, Ika, IkaWerke, Staufen, Germany).

[0183] Mix the liquid components of Phase A with a spatula. Then first add zinc stearate to the oil phase via ultra turrax (3 minutes, 10,000 rpm), and then add Aerosil in a similar manner (3 minutes, 10,000 rpm). The aqueous phase (Phase B) is also mixed with a spatula at room temperature and then slowly added to Phase A with minimal mixing input (2 minutes, 3000 rpm). After Phase B has been completely added, the white emulsion is homogenized briefly (1 minute, 10,000 rpm) and filled into applicators.

[0184]

[0185]

[0186] Formulations 8.6.3 to 8.6.7 are formulations according to the invention.

[0187] Prepare dirhamnolipid ethyl ester as described in Example 4 of WO2017144317.

[0188] Prepare dirhamnolipid octadecyl ester as described in Example 3 of WO2017144317; replace lauryl alcohol with an equimolar amount of 1-octadecanol.

[0189] Example 9: Panel test

[0190] Eight panelists were selected for the odor test (the panelists were numbered with letters A - H). Each panelist was provided with a lotion as described in Table 1.

[0191] Table 1: Fragrance-free lotion for cleaning the armpits of panelists

[0192]

[0193] This lotion is fragrance-free to avoid the influence of artificial scents on the panel results. The panelists were asked to clean their armpits as usual. However, the panelists used the provided fragrance-free lotion. After washing, the formulated product described in the above section was applied. The formulated product was packaged in a neutrally labeled container randomly. Thus, the formulated product of the present invention was also randomly applied under the left or right arm. The panelists were also advised not to use additional fragrances. The panelists applied the formulated product in the morning and evaluated the malodor intensity 8 - 10 hours after application. The panelists followed normal work procedures and did not use artificial sweat in a hot chamber because the formulated product was evaluated in a pairwise discrimination manner.

[0194] After 8 - 10 hours, six trained inspectors evaluated the malodor intensity scale of the panelists. Ratings were given from 0 to 10 according to the malodor intensity scale. (See IFSCC Monograph, Number 6, “Antiperspirants and Deodorants: Principles of Underarm Technology” Copyright International Federation of the Societies of Cosmetic Chemists 1998; ISBN 1 - 870228 - 19 - 7 and Table 2).

[0195] The inspectors scored the odor of the panelists' armpits, and each inspector calculated the difference in the evaluations to visualize the pairwise differences perceived by the inspectors. After all six inspectors gave their evaluations of a panelist, the differences in the pairwise evaluations were averaged. Untrained people may experience a difference with an average value of 1, while a difference of 2 or more is clearly distinguishable.

[0196] Table 2: Malodor Intensity Scale Used by Inspectors to Describe Odors

[0197] Score Odor Intensity Scale 0 None, no odor 1 Olfactory Threshold 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 Extremely strong odor

[0198] Example 9.1

[0199] In the first experiment, formulated products 8.1.1 and 8.1.2 were tested. Neither of the two formulated products contained the molecule according to the present invention. The difference in aluminum salt loading should be studied in this group.

[0200]

[0201]

[0202] Result: The formulation with 20% aluminum salt (8.1.1) is significantly superior to the formulation with 10% salt (8.1.2).

[0203] Example 9.2

[0204] The next set of experiments was conducted to observe whether the structure of the present invention could compensate for lower levels of aluminum salt. Therefore, a comparative test was carried out between formulation 8.1.1 (20% aluminum salt) and formulation 8.1.4 (10% aluminum salt + structure 4 of the present invention).

[0205]

[0206]

[0207] Result: The inspector could not distinguish between the two formulations, and structure 4 of the present invention was able to compensate for the reduction in the amount of aluminum salt.

[0208] Example 9.3

[0209] 8.2.2 vs. 8.2.7

[0210]

[0211]

[0212] Result: The results clearly showed that structure 7 of the present invention was able to reduce malodor.

[0213] Example 9.4

[0214]

[0215] Result: Compared with pure dirhamnolipid, structure 3 of the present invention was excellent in reducing malodor.

[0216] Example 9.5

[0217] 8.3.2 vs 8.3.5

[0218]

[0219] Result: Compared with pure rhamnolipid hexyl ester, structure 5 of the present invention was excellent in reducing malodor. In addition, team members A, C, D, G, and H complained of itching of the axillary skin treated with formulation 8.3.2.

[0220] Example 9.6

[0221]

[0222] Result: This set of data clearly showed that the low polyesters of the monorhamnolipids of the present invention were more suitable for reducing malodor compared with the monoesters.

[0223] List of ingredients used

[0224]

[0225]

Claims

1. Rhamnolipid esters of general formula (I) wherein m = independently of one another are the same or different and are 2, 1 or 0, n = independently of one another are the same or different and are 1 or 0, z＝2， R 1 = independently of one another, identical or different, is an optionally branched, optionally hydroxy-substituted alkyl group having 2 to 24 carbon atoms R 2 = independently of one another, identical or different, is an optionally branched, optionally hydroxy-substituted alkyl group having 2 to 24 carbon atoms, and A is selected from wherein R 3 and R 4 selected from CH3 and H, r＝0-3， s = 0 - 24, and t = 0 - 24, and or A is selected from 2. The rhamnolipid ester according to claim 1, wherein m = 1 or 0.

3. The rhamnolipid ester according to claim 1, characterized in that, n＝1。 4. The rhamnolipid ester according to claim 1, wherein R 1 and R 2 are each independently the same or different and are an alkyl group having 5 to 13 carbon atoms.

5. The rhamnolipid ester according to claim 1, characterized in that, R 1 and R 2 each independently is the same as or different from (CH2) o -CH3, where o = 1 - 23.

6. The rhamnolipid ester according to claim 1, characterized in that, R 1 and R 2 each independently is the same or different and is (CH2) o -CH3, where o = 4 - 12 7. The rhamnolipid ester according to any one of claims 1-6, characterized in that, The rhamnolipid groups in general formula (I) are selected from the groups diRL-C10C10, diRL-C8C10, diRL-C10C12 and monoRL-C10C10, "diRL-CXCY" refers to a dirhamnolipid of general formula (I) or a salt thereof, wherein A = H, z = 1, and wherein one of the groups R 1 and R 2 is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4, "monoRL-CXCY" refers to a monorhamnolipid of general formula (I) or a salt thereof, where A = H, z = 1, and where one of the groups R 1 and R 2 is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4.

8. The rhamnolipid ester according to any one of claims 1 - 6, characterized in that the rhamnolipid groups in general formula (I) are selected from the groups diRL-C10C10, diRL-C8C10, diRL-C10C12 and monoRL-C10C10, and z＝2， and A is selected from wherein R 3 = R 4 = H, r = t = 0, s = 0 - 8, 10, 12 or 14 "diRL-CXCY" refers to a dirhamnolipid of general formula (I) or a salt thereof, where A = H, z = 1, and where the group R 1 and R 2 one of which is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4, "monoRL-CXCY" refers to a monorhamnolipid of general formula (I) or a salt thereof, where A = H, z = 1, and where one of the groups R 1 and R 2 is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4.

9. A method for preparing the rhamnolipid ester according to any one of claims 1 - 8, which comprises the following method steps A) providing at least one rhamnolipid, B) reacting the rhamnolipid with at least one coupling agent, C) reacting the rhamnolipid activated by method step B) with a polyol having 1 - 32 carbon atoms, and optionally D) purifying the rhamnolipid ester.

10. The method according to claim 9, wherein The coupling agent used in method step B) is selected from at least one of the following: dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-cyclohexyl-N'-(2'-morpholinoethyl)carbodiimide methyl-p-toluenesulfonate, N-benzyl-N'-3'-dimethylaminopropylcarbodiimide hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-ethylcarbodiimide hydrochloride and carbonyldiimidazole.

11. The method according to claim 10, wherein The coupling agent used in method step B) is selected from at least one of dicyclohexylcarbodiimide and diisopropylcarbodiimide.

12. The method according to claim 9 or 10, characterized in that, In method step C), at least one catalyst selected from the following is used: N-ethyldiisopropylamine, trialkylamine, pyridine, 4-dimethylaminopyridine and hydroxybenzotriazole.

13. The method according to claim 12, characterized in that, The catalyst is hydroxybenzotriazole.

14. The method according to claim 9 or 10, characterized in that In method step A), a rhamnolipid selected from diRL-C10C10, diRL-C8C10, diRL-C10C12 and monoRL-C10C10 or a mixture thereof is used, "diRL-CXCY" refers to a dirhamnolipid of general formula (I) or a salt thereof, wherein A = H, z = 1, and wherein one of the groups R 1 and R 2 is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4 "monoRL-CXCY" refers to a monorhamnolipid of general formula (I) or a salt thereof, where A = H, z = 1, and where one of the groups R 1 and R 2 is (CH2) o -CH3, where o = X - 4, and the remaining group R 1 or R 2 is (CH2) o -CH3, where o = Y - 4.

15. The method according to claim 9 or 10, characterized in that, In method step C), the alcohol is selected from 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol and 1,16-hexadecanediol.

16. A formulation comprising at least one rhamnolipid ester according to at least one of claims 1 - 8.

17. The formulation according to claim 16, characterized in that, It is a cosmetic formulation.

18. The cosmetic use of the rhamnolipid ester according to at least one of claims 1 - 8 or the formulation according to claim 16 or 17 in antiperspirant applications.

19. Cosmetic use of the rhamnolipid ester according to at least one of claims 1 - 8 or of the formulation according to claim 16 or 17 in a formulation for inhibiting body odor and / or sweat.

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