Composition comprising glycerol and glycerol fatty acid monoesters

Abstract

The invention relates to compositions comprising glycerol and glycerol fatty acid monoesters, a method for their production and their use.

Description

[0001] 202300252 Foreign Filing 1

[0002] Composition comprising glycerol and glycerol fatty acid monoesters

[0003] Field of the invention

[0004] The invention relates to compositions comprising glycerol and glycerol fatty acid monoesters, a method for their production and their use.

[0005] Prior art

[0006] Glycerol fatty acid esters have been used in cosmetic formulations for many decades, for example as thickeners, antimicrobials and skin care agents or as emulsifiers.

[0007] The thickeners are mostly glycerol monocarboxylic acid esters of short- and medium-chain as well as unsaturated fatty acids with a purity of about 90 % in relation to the monocarboxylic acid ester content. These can usually be clearly incorporated into aqueous surfactant systems due to the low content of hydrophobic dicarboxylic acid esters.

[0008] Glyceryl monooleate, in addition to thickening, also contributes in particular to the moisturizing and refatting effect of aqueous skin cleansing formulations.

[0009] In creams and lotions, glycerol mono-, glyceryl di- and glyceryl tricarboxylic acid esters of long- chain fatty acids, such as stearic acid, as well as mixtures thereof are used as (co-)emulsifiers. A disadvantage of most glycerol fatty acid esters, especially those with a high purity in terms of monocarboxylic acid ester content, is that they exist as pastes or usually even as solids at a typical ambient temperature of 15°C to 30 °C in chemical production facilities. It is true that some glycerol carboxylic acid esters of branched fatty acids, such as those of isostearic acid, are liquid at such temperatures. However, due to their hydrophobicity, they are not compatible with aqueous surfactant formulations, even as monocarboxylic acid esters. Glycerol carboxylic acid esters of short-chain or unsaturated fatty acids, such as caprylic acid, capric acid or oleic acid, can also be present in liquid form at temperatures of about 30 °C, especially if they are mixtures of glycerol mono- and glycerol dicarboxylic acid esters. One example of this is TEGIN® O V MB produced by Evonik with the INCI name Glyceryl Oleate, which, however, is also not compatible with aqueous surfactant formulations due to the hydrophobicity of the glyceryl dioleates comprised therein. Glyceryl monooleate, on the other hand, can generally be homogeneously incorporated into aqueous surfactant formulations. This skin-identical lipid is a popular ingredient that has moisturizing, refatting, skin-nourishing and smoothing properties, which counteracts the irritation and dehydration of the skin by the surfactants. One disadvantage, however, is that glyceryl monooleate is a paste-like solid at 15 to 30 °C and therefore cannot be processed without heating. As a result, additional energy and time is required for the incorporation into a surfactant formulation, and processing usually takes several hours, even at around 80 °C. Therefore, there are alternative products on the market that allow for an easier and faster processing, in which the glyceryl monooleate is mixed with non-ionic surfactants and water. An example of this is 202300252 Foreign Filing 2

[0010] LAMESOFT PO 65 (INCI: Coco Glucoside; Glyceryl Oleate) from BASF, which, however, cannot be processed at temperatures below 30 °C without heating due to its paste-like consistency. Other disadvantages of such mixtures are the low glycerol fatty acid ester content of less than 50 percent by weight and the lack of flexibility, as the ingredients of the mixture inevitably become part of the final formulation.

[0011] It is an object of the invention to provide compositions containing glycerol fatty acid esters which can overcome the described disadvantages, i.e. have very good sensory properties and are present between 15 °C and 30 °C as pumpable liquids, so that cold processing is possible.

[0012] Description of the invention

[0013] It was found, surprisingly, that a composition comprising glycerol and at least two different glycerol fatty acid monoesters can solve the problem from above.

[0014] The present invention therefore provides a composition comprising

[0015] A) glycerol,

[0016] B) at least one first glycerol fatty acid monoester comprising at least one C-C double bond, and

[0017] C) at least one second glycerol fatty acid monoester comprising no C-C double bond.

[0018] The invention further provides a process for the preparation of a composition comprising glycerol and glycerol fatty acid monoesters as described in claim 9.

[0019] The invention further provides the use of a composition according to the invention for preparation of a formulation.

[0020] An advantage of the present invention is that the compositions according to the invention are liquid at 15 to 30 °C and thus pumpable.

[0021] A further advantage is that the compositions according to the invention can be cold-processed, i.e. quickly incorporated into aqueous surfactant formulations at typical ambient temperatures in chemical production plants without increasing the temperature.

[0022] A further advantage is that the compositions of the invention are homogeneous and clearly processable into clear aqueous surfactant formulations.

[0023] A further advantage is that the compositions of the invention have a high glyceryl ester content and do not need to be diluted with other excipients, e.g. non-ionic surfactants, resulting in greater flexibility for the formulation composition.

[0024] A further advantage is that the compositions according to the invention have moisturizing, refatting, softening and smoothing properties. 202300252 Foreign Filing 3

[0025] Another advantage is that the compositions of the invention have thickening properties in aqueous surfactant formulations.

[0026] Another advantage is that the compositions according to the invention create a higher foam density in aqueous surfactant systems, resulting in a preferred skin feel during washing.

[0027] Another advantage is that the compositions of the invention can replace non-sustainable, PEG- based ingredients, which are often still used as sensory additives today.

[0028] Another advantage is that the compositions of the invention can cause a better deposition of glycerol esters on the skin.

[0029] The composition according to the instant invention thus comprises

[0030] A) glycerol,

[0031] B) at least one first glycerol fatty acid monoester comprising at least one C-C double bond, and

[0032] C) at least one second glycerol fatty acid monoester comprising no C-C double bond, and is preferably characterised in that the sum of glycerol and all glycerol fatty acid esters comprised in the composition make up for at least 60 wt.-%, preferably 75 wt.-% to 99 wt.-%, wherein the weight percentages refer to the total composition.

[0033] Fatty acids and fatty acid acyl groups refer to all carboxylic acids and carboxylic acid acyl groups with 6 to 24 carbon atoms.

[0034] In the context of the instant invention the fatty acids in the glycerol fatty acid esters are preferably natural fatty acids that can be produced based on naturally occurring vegetable or animal oils and have preferably 7 to 22 carbon atoms. Natural fatty acids are generally unbranched and usually consist of an even number of carbon atoms. Any double bonds have cis configuration. Even more preferred natural fatty acids in the context of the instant invention are selected from caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable for example from the ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0035] The glyceryl monocarboxylic acid esters and glyceryl dicarboxylic acid esters mentioned herein comprise all possible regioisomers.

[0036] The term “glycerol fatty acid ester” refers to glycerol fatty acid mono-, di- and triesters.

[0037] In the context of the present invention, the term “surfactant” is understood to mean organic substances having interface-active properties that have the ability to reduce the surface tension of an aqueous solution at a concentration of 0.5% by weight at 20°C to below 45 mN / m. The surface tension is determined by the Du Nouy ring method at 20°C. 202300252 Foreign Filing 4

[0038] In the context of the present invention, the terms “liquid” is understood to be liquid at a temperature of 25°C and a pressure of 1013 mbar.

[0039] In the context of the present invention, a pumpable liquid is understood to be a composition which has a viscosity of less than 10000 mPa at 25 °C (Brookfield).

[0040] Unless stated otherwise, percentages are data in per cent by weight. The same is true for parts per million (ppm).

[0041] Where average values are stated hereinbelow, then, unless stated otherwise, these are number- averaged average values.

[0042] Wherever measurement values are stated hereinbelow, then, unless stated otherwise, these have been determined at a temperature of 25°C and a pressure of 1013 mbar.

[0043] The quantification of the individual components of the inventive and non-inventive compositions is carried out by a GC / FID analysis according to the following description. The content of glycerol is determined quantitatively as weight percent (wt.-%), while the content of all other components is determined without using reference substances.

[0044] For the analysis, 25 mg 1 ,3-propanediol (as internal standard for the glycerol quantification) and 100 mg of the respective composition are dissolved in 5 ml of a mixture of pyridine / chloroform (4:1). Then, 0.25 ml of the clear solution are transferred into an autosampler vial. Subsequently, 0.5 ml of N-Methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) are added. The derivatization of the hydroxyl groups is completed by heating to 80°C for 30 min.

[0045] An aliquot of the final sample is analyzed by GC / FID using the following conditions.

[0046] Instrument: Gas chromatograph Agilent 7890

[0047] Column: Agilent DB5-HT, 30 m * 0.32 mm, df 0.1 pm

[0048] Flow: 1 ml / min constant flow, hydrogen

[0049] Oven Temp. Prog.: 65 °C; 10°C / min; 365°C, 15 min

[0050] Injector: 1 pl Split 1 :20

[0051] Detector: FID, 375°C

[0052] Glycerol is quantified using 1 ,3-propanediol as internal standard, based on an internal standard calibration established from calibration reference mixtures. All other components are being quantified as wt.-% by applying the respective peak area-% without any comparison to references. Based on the difference of the quantified glycerol content in wt.-% and the area-% of the respective glycerol peak, the area-% of all other peaks, representing all the other components of the composition, are being multiplied with a correction factor cf that is given by the following equation: cf = (100 - wt.-% of quantified glycerol content) : (100 - area-% of glycerol peak)

[0053] Alternative GC / FID measurement conditions for the quantification of glycerol as weight percent (wt.-%) in accordance with the method described above are as follows: 202300252 Foreign Filing 5

[0054] Instrument: Gas chromatograph Agilent 7890

[0055] Column: Agilent HP-1 , 30 m * 0.32 mm, df 0.25 pm

[0056] Flow: 2 ml / min constant flow, hydrogen

[0057] Oven Temp. Prog.: 80°C; 8°C / min; 300°C, 15 min

[0058] Injector: 1 pl Split 1 :20

[0059] Detector: FID, 310°C

[0060] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component A) in an amount of 2.0 wt.-% to 50 wt.-%, preferably 3.0 wt.-% to 30 wt.-%, more preferably 4.0 wt.-% to 15 wt.-%, most preferably 6.0 wt.-% to 12 wt.-%, wherein the weight percentages refer to the total composition.

[0061] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component B) in an amount of 10 wt.-% to 60 wt.-%, preferably 15 wt.-% to 45 wt.-%, more preferably 17 wt.-% to 37 wt.-%, wherein the weight percentages refer to the total composition.

[0062] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component C) in an amount of 3.0 wt.-% to 45 wt.-%, preferably 5.0 wt.-% to 35 wt.-%, more preferably 7.0 wt.-% to 25 wt.-%, wherein the weight percentages refer to the total composition.

[0063] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component A) in an amount of 2.0 wt.-% to 50 wt.-%, preferably 3.0 wt.-% to 30 wt.-%, more preferably 4.0 wt.-% to 15 wt.-%, most preferably 6.0 wt.-% to 12 wt.-%, component B) in an amount of 10 wt.-% to 60 wt.-%, preferably 15 wt.-% to 45 wt.-%, more preferably 17 wt.-% to 37 wt.-%, and component C) in an amount of 3.0 wt.-% to 45 wt.-%, preferably 5.0 wt.-% to 35 wt.-%, more preferably 7.0 wt.-% to 25 wt.-%, most preferred component A) in an amount of 6.0 wt.-% to 12 wt.-%, component B) in an amount of 17 wt.-% to 37 wt.-%, and component C) in an amount of 7.0 wt.-% to 25 wt.-%, wherein the weight percentages refer to the total composition. 202300252 Foreign Filing 6

[0064] A preferred composition according to the instant invention is characterised in that it comprises

[0065] D) at least one glycerol fatty acid diester, in which the fatty acid acyl groups of the diester are selected from the same fatty acids acylated into said first and second glycerol fatty acid monoester.

[0066] A more preferred composition according to the instant invention is characterised in that component

[0067] D) comprises at least two, preferably at least three different glycerol fatty acid diesters.

[0068] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component D) in an amount of 5.0 wt.-% to 40 wt.-%, preferably 15 wt.-% to 35 wt.-%, more preferably 18 wt.-% to 33 wt.-%, wherein the weight percentages refer to the total composition.

[0069] A preferred composition according to the instant invention is characterised in that it comprises

[0070] E) at least one diglycerol fatty acid ester, preferably including mono-, di- and triesters, in which the fatty acid acyl groups of the diglycerol fatty acid ester are selected from the same fatty acids acylated into said first and second glycerol fatty acid monoester.

[0071] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component E) in an amount of 0.1 wt.-% to 35 wt.-%, preferably 2.0 wt.-% to 30 wt.-%, more preferably 5.0 wt.-% to 25 wt.-%, wherein the weight percentages refer to the total composition.

[0072] It is preferred according to the instant invention that the inventive composition is characterised in that it comprises component A) in an amount of 2.0 wt.-% to 50 wt.-%, preferably 3.0 wt.-% to 30 wt.-%, more preferably 4.0 wt.-% to 15 wt.-%, most preferably 6.0 wt.-% to 12 wt.-%, component B) in an amount of 10 wt.-% to 60 wt.-%, preferably 15 wt.-% to 45 wt.-%, more preferably 17 wt.-% to 37 wt.-%, and component C) in an amount of 3.0 wt.-% to 45 wt.-%, preferably 5.0 wt.-% to 35 wt.-%, more preferably 7.0 wt.-% to 25 wt.-%, component D) in an amount of 5.0 wt.-% to 40 wt.-%, preferably 15 wt.-% to 35 wt.-%, more preferably 18 wt.-% to 33 wt.-%, and component E) in an amount of 0.1 wt.-% to 35 wt.-%, preferably 2.0 wt.-% to 30 wt.-%, more preferably 5.0 wt.-% to 25wt.-%, wherein the weight percentages refer to the total composition. 202300252 Foreign Filing 7

[0073] It is more preferred according to the instant invention that the inventive composition is characterised in that it comprises component A) in an amount of 4.0 wt.-% to 15 wt.-%, most preferably 6.0 wt.-% to 12 wt.-%, component B) in an amount of 17 wt.-% to 37 wt.-%, component C) in an amount of 7.0 wt.-% to 25 wt.-%, component D) in an amount of 18 wt.-% to 33 wt.-%, and component E) in an amount of 5.0 wt.-% to 25wt.-%, wherein the weight percentages refer to the total composition.

[0074] A preferred composition according to the instant invention is characterised in that said first glycerol fatty acid monoester is selected from a glycerol fatty acid monoester in which the fatty acid acyl group is selected from fatty acids comprising 16 to 22 carbon atoms, preferably 18 carbon atoms, more preferably said first glycerol fatty acid monoester is glycerol monooleate and said second glycerol fatty acid monoester is selected from a glycerol fatty acid monoester in which the fatty acid acyl group is selected from fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms.

[0075] A more preferred composition according to the instant invention is characterised in that said first glycerol fatty acid monoester is selected from glycerol monooleate and said second glycerol fatty acid monoester is selected from a glycerol fatty acid monoester in which the fatty acid is selected from fatty acids comprising 7 to 10 carbon atoms, more preferably 9 carbon atoms and that it comprises component A) in an amount of from 4.0 wt.-% to 15 wt.-%, most preferably 6.0 wt.-% to 12 wt.-%, component B) in an amount of from 17 wt.-% to 37 wt.-%, and component C) in an amount of from 7.0 wt.-% to 25 wt.-%, wherein the weight percentages refer to the total composition.

[0076] A preferred composition according to the instant invention is characterised in that component D) comprises from 0.1 wt.-% to 25 wt.-%, preferably 3.0 wt.-% to 20 wt.-%, more preferably 6.0 wt.-% to 18 wt.- %, glycerol dioleate, from 0.1 wt.-% to 20 wt.-%, preferably 1 .0 wt.-% to 15 wt.-%, more preferably 2.0 wt.-% to 10 wt.- %, of at least one glycerol fatty acid diester, in which the fatty acid acyl group is selected from fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, and from 0.1 wt.-% to 30 wt.-%, preferably 1 .0 wt.-% to 25 wt.-%, more preferably 6.0 wt.-% to 16.0 wt.- %, of at least one glycerol fatty acid diester, which comprises an oleic acid acyl group and one acyl 202300252 Foreign Filing 8 group selected from fatty acids with 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, and in that component E) comprises from 0.1 wt.-% to 25 wt.-%, preferably 1 .0 wt.-% to 20 wt.-%, more preferably 2.0 wt.-% to 15 wt.-% of at least one diglycerol fatty acid monoester in which the fatty acid is selected from oleic acid and fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, wherein the weight percentages refer to the total composition.

[0077] The invention further provides a process for the preparation of a glycerol and glycerol fatty acid monoesters comprising composition, preferably of a composition accord to the instant invention, comprising the steps of

[0078] I) providing a glycerol and at least one fatty acyl group donor providing at least two different fatty acyl groups,

[0079] II) carrying out an esterification reaction, wherein at least a part of the fatty acyl groups of said fatty acyl group donor is transferred to said glycerol, and optional III) packaging of said prepared composition in a closed container, characterised in that the molar ratio of said glycerol to all fatty acyl groups provided by said fatty acyl group donor is in the range of from 1 .0 : 0.4 to 1 .0 : 1 .0, preferably from 1 .0 : 0.5 to 1 .0 : 0.9, more preferably from 1 .0 : 0.55 to 1 .0 : 0.8.

[0080] A preferred process according to the instant invention is characterised in that said acyl group donor is selected from fatty acids, fatty acid esters, preferably methyl-, ethyl- and glycerol esters, wherein the glycerol esters are preferably fatty acid triglycerides, preferably natural oils.

[0081] The fatty acyl group donor preferably provides the preferred fatty acids mentioned above in context with the composition according to the instant invention.

[0082] Specifically said fatty acyl group donor providing at least two different fatty acyl groups preferably provides oleic acid acyl groups and at least one selected from the group of fatty acid acyl groups comprising 7 to 10 carbon atoms, more preferably 9 carbon atoms.

[0083] A preferred process according to the instant invention is characterised in that process step II) is carried out in a temperature range of from 30 °C to 300 °C, preferably 40 °C bis 280 °C, more preferably 110 °C to 270 °C, even more preferably 180 °C to 260 °C.

[0084] Preferably in the process according to the instant invention in process step II) reaction water is removed from the reaction, preferably by distillation, more preferably under reduced pressure. 202300252 Foreign Filing 9

[0085] Since the composition according to the invention has an excellent use profile, especially in cleaning applications, the present invention further provides the use of a composition according to the invention for preparation of a formulation, preferably a cleaning formulation, preferably for cosmetic or household care.

[0086] The formulation prepared by the use according to the instant invention preferably is an aqueous formulation, preferably comprising at least one surfactant, preferably biosurfactant, wherein the biosurfactant preferably makes up for at least 80 wt.-% of all surfactants present in said formulation.

[0087] Within the context of the present invention, “biosurfactants” are understood as meaning all glycolipids produced by fermentation and their salts. The term “biosurfactant” also covers glycolipids that are chemically or enzymatically modified after fermentation, as long as structurally a glycolipid remains. When determining the amount of biosurfactant only the mass of the biosurfactant is taken into account while disregarding the counter ion of the salt, in case the biosurfactant is present as a salt.

[0088] Preferably, said biosurfactant is selected from the group comprising, preferably consisting of, rhamnolipids, in particular mono-, di- or polyrhamnolipids, glucolipids, in particular mono-, di- or polyglucolipids, mannosylerythritollipids and sophorolipids, in particular mono-, di- or polysophorolipids, preferably selected from rhamnolipids and glucolipids, most preferably rhamnolipids.

[0089] The composition according to the invention preferably is used so that it is comprised in said formulation in an amount of from 0.1 wt.-% to 10 wt.-%, preferably from 0.2 wt.-% to 5.0 wt.-%, more preferably from 0.3 wt.-% to 3.0 wt.-%, wherein the weight percentages refer to the total formulation.

[0090] Preferably the use according to the instant invention is characterized in that the cleaning household care formulation is a laundry formulation, a dish washing formulation, a car cleaning formulation, a hard floor cleaning formulation, a glass cleaner, a bathroom cleaner, a kitchen cleaner, an over cleaner, an all purpose cleaner, a wet wipe, a metal cleaner, a membrane cleaner for food and beverage applications, a CIP (cleaning in place) cleaner, a big kitchen cleaner, a traffic film remover, a carpet cleaner, an alkaline cleaner, a prespotter, a mild cleaner or a neutral cleaner.

[0091] The cosmetic formulation prepared by the use according to the instant invention preferably comprises at least one further additional component selected from the group comprising emollients, emulsifiers, co-emulsifiers, thickeners / viscosity regulators / stabilizers, antioxidants, hydrotropes (or polyols), 202300252 Foreign Filing 10 solids and fillers, pearlescent additives and opacifiers, insect repellents, self-tanning agents, preservatives, conditioning agents, perfumes, colorants, cosmetic active substances, care additives, refatting agents, solvents.

[0092] Substances that can be used as exemplary representatives of the individual groups are known to those skilled in the art and can for example be taken from German application DE102008001788.4. This patent application is hereby incorporated as reference and is thus considered to form part of the disclosure.

[0093] As regards further optional components and also the amounts used of these components, reference is expressly made to the relevant handbooks known to those skilled in the art, for example K. Schrader, “Grundlagen und Rezepturen der Kosmetika” [Fundamentals and formulations of cosmetics], 2nd edition, pages 329 to 341 , Huthig Buch Verlag, Heidelberg. The amounts of the respective additives depend on the intended use.

[0094] Typical guideline formulations for the relevant applications are known prior art and are contained for example in the brochures of the manufacturers of the relevant base materials and active substances. These existing formulations can generally be adopted unchanged. However, any desired modifications necessary for adjustment and optimization can be made in a straightforward manner through simple tests.

[0095] The examples adduced hereinafter describe the present invention by way of example, without any intention that the invention, the scope of application of which is apparent from the entirety of the description and the claims, be restricted to the embodiments specified in the examples.

[0096] Examples:

[0097] In the following examples, a technical oleic acid quality was used, which contained 5 % palmitic acid, 1 % palmitoleic acid, 2 % stearic acid, 78 % oleic acid, 13 % linoleic acid and 1 % linolenic acid. Nevertheless, the molecular weight of oleic acid was used for the calculation of the molar amount. 202300252 Foreign Filing 11

[0098] Example 1: Preparation of a composition according to the invention

[0099] 138 g (1.50 mol) of glycerol, 169 g (0.60 mol) of technical oleic acid, 71 g (0.45 mol) of n-nonanoic acid and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid, with a free glycerol content of 7.8 weight-%.

[0100] Example 1B: Preparation of a composition according to the invention

[0101] 138 g (1.50 mol) of glycerol, 197 g (0.70 mol) of technical oleic acid, 63 g (0.40 mol) of n-nonanoic acid and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid.

[0102] Example 1C: Preparation of a composition according to the invention

[0103] 138 g (1.50 mol) of glycerol, 155 g (0.55 mol) of technical oleic acid, 79 g (0.50 mol) of n-nonanoic acid and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid.

[0104] Example 2: Preparation of a composition according to the invention

[0105] 138 g (1.50 mol) of glycerol, 141 g (0.50 mol) of technical oleic acid, 79 g (0.50 mol) of caprylic acid / capric acid (56:44 = w / w) and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid with a free glycerol content of 11 .0 weight-%.

[0106] Example 2B: Preparation of a composition according to the invention 202300252 Foreign Filing 12

[0107] 138 g (1.50 mol) of glycerol, 183 g (0.65 mol) of technical oleic acid, 87 g (0.55 mol) of caprylic acid / capric acid (58:42 = w / w) and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid.

[0108] Example 2C: Preparation of a composition according to the invention

[0109] 138 g (1.50 mol) of glycerol, 212 g (0.75 mol) of technical oleic acid, 63 g (0.40 mol) of caprylic acid / capric acid (58:42 = w / w) and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish clear liquid.

[0110] Example 3: Preparation of a composition not according to the invention

[0111] 138 g (1.50 mol) of glycerol, 282 g (1 ,00 mol) of oleic acid (> 99 % pure) and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a mixture of 2 yellowish liquids.

[0112] Example 4: Preparation of a composition not according to the invention

[0113] 138 g (1.50 mol) of glycerol, 120 g (0.60 mol) of lauric acid, 71 g (0.45 mol) of n-nonanoic acid and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a slightly yellowish waxy solid.

[0114] 60 wt.-% of this product was mixed with 40 wt.-% 50 % aq. Coco-Glucoside (INCI) at 80 °C for one hour while stirring. After cooling again to 25 °C, a yellowish paste was obtained, which is only present as a liquid at temperatures of at least 40 °C.

[0115] Example 4B: Preparation of a composition not according to the invention 202300252 Foreign Filing 13

[0116] 92 g (1 .00 mol) of glycerol, 282 g (1 .00 mol) of oleic acid (91 % pure + 3.5 % palmitic acid + 1 .0 % stearic acid + 4 % linoleic acid) and 0.5 g of potassium carbonate were heated to 240 °C under nitrogen atmosphere while stirring and distilling off the reaction water. As soon as the acid value was below 2 mg KOH / g and the reaction time at 240 °C reached 15 h, the reaction mixture was cooled down to 25 °C. The product was a yellowish liquid with a free glycerol content of 5.0 weight- %.

[0117] Example 5: Glyceryl Oleate (INCI) with high monoester content, market product (not according to the invention)

[0118] Glyceryl Oleate (INCI) based on technical oleic acid containing > 95 % monoesters, > 75 % glyceryl monooleate, which is a white, waxy, almost solid paste at 25 °C.

[0119] Example 6: Mixture of Glyceryl Oleate (INCI) with high monoester content, alkyl glucosides and water (not according to the invention)

[0120] In addition to a minor part of citric acid, the product consists of approx. 33 wt.-% Glyceryl Oleate (INCI, comparable to example 5), approx. 33 wt.-% Coco-Glucoside (INCI) and approx. 33 wt.-% water. It is a yellow, viscous paste at 25°C.

[0121] In the following examples 7 and 8, the compositions of the examples 1 - 6 have been tested in cosmetic formulations. The specified formulations were prepared by mixing the individual components with water while stirring at 22 °C and filling up with water to an amount of 98 wt.-% of the desired composition of the final formulation. After 1 hour, the pH was adjusted to 5.2 with citric acid, 0.5 wt.-% of one of the examples 1 - 6 was added and each formulation was filled up with water to 100 wt.-%. Then, the formulation was stirred at 22 °C until a clear mixture was obtained. This was checked every 5 minutes by stopping the stirrer.

[0122] In the following examples, the INCI nomenclature is used to describe the ingredients of the formulation. A clear formulation in the context of this invention means a turbidity value < 20 NTU.

[0123] Example 7: Incorporation time of inventive and non-inventive compositions into formulation A

[0124] The incorporation time of 0.5 wt.-% of the examples 1 - 6 into the aqueous formulation A containing 15 % of a 32 % aq. Sodium Cocoamphoacetate solution (REMOTE RIC® AM C), 12.6% 202300252 Foreign Filing 14 of a 38% aq. Cocamidopropyl Betaine solution (TEGO® Betain F 50) and 12 % of a 30 % aq.

[0125] Sodium Lauroyl Sarcosinate solution (Perlastan L-30 MB) was determined.

[0126] * according to the invention

[0127] Example 8: Incorporation time of inventive and non-inventive compositions into formulation B

[0128] The incorporation time of 0.5 wt.-% of examples 1 - 6 into the aqueous formulation B containing 17.5 % of a 32 % aq. Sodium Cocoamphoacetate solution (REWOTERIC® AM C), 8.8% of a 50% aq. Lauryl Glucoside solution (Plantacare 1200 UP), 4.4% of a 50% aq. Coco-Glucoside solution (Plantacare 818 UP) and 14.4% of a 25% aq. Disodium / Sodium Cocoyl Glutamate solution (Perlastan SC 25 NKW) was determined.

[0129] * according to the invention

[0130] Example 9: Bubble Count

[0131] The flash foam method of a Dynamic Foam Analyzer by Kruess was applied to determine the amount of bubbles per mm2over time in a 4 % aq. solution of the formulation B that contained 0.5 wt.-% of example 1 or example 6. The bubble counts (BC) were as follows:

[0132] * according to the invention

[0133] Example 10: Skin hydration, transepidermal water loss (TEWL) and skin roughness

[0134] For the determination of skin hydration TEWL and skin roughness, aqueous formulations containing 11 % Sodium Coco Sulfate, 1.0 % Cocamidopropyl Betaine, 0.4 % Sodium Levulinate and 0.2 % Sodium Benzoate, were prepared and adjusted to pH 5.5 with citric acid. Besides for the 202300252 Foreign Filing 15 measurement of the formulation control, 4 wt.-% of one of the examples 1 and 6 were incorporated into the formulation until a clear and homogeneous system was obtained.

[0135] The formulations were applied 9 times in total over a period of 4 1 days on the inner forearm of 30 female test persons (age: 18 - 65 years). During the days 1 to 4, the formulations were applied twice daily (once in the morning and once in the afternoon), and one last time on day 5, 3 hours prior to the measurements. During each application, approx. 400 pl of the respective formulation (5 pl / cm2) were applied to the wetted skin and washed across the area in gentle zigzag movements for 15 seconds. The formulation remained on the arm for a further 15 seconds before it was removed with water and the arm was gently dried.

[0136] Skin hydration measurements were then performed with the Corneometer® MDD4 (CM 825 probe) according to the SOP “Bestimmung der Hautfeuchtigkeit mittels Corneometer® CM 825 und Multi Display Device (MDD 4)”, Version 1 of 7th July 2022 (SGS INSTITUT FRESENIUS GmbH). Therefore, the probe was placed with low pressure in a vertical manner onto the surface of the skin. The skin hydration was determined 10 times per test site. An increase in Corneometer® values indicates augmented skin hydration (i.e., improvement).The mean values were as follows:

[0137] * according to the invention

[0138] The measurement of the TEWL values was performed with the DermaLab® device according to the SOP “Bestimmung des Transepidermalen Wasserverlustes (TEWL) mit dem DermaLab®”, Version 9 of 21st May 2019 (SGS INSTITUT FRESENIUS GmbH). The predefined measurement sequence was over a period of 45 seconds. Mean values and the corresponding standard deviations of the last eight determined TEWL data of a measurement sequence were calculated. Three single measurements were performed. A decrease in TEWL values indicates a strengthened skin barrier (i.e., improvement). The mean values were as follows:

[0139] * according to the invention 202300252 Foreign Filing 16

[0140] The skin roughness was measured by using silicone replica technique (EXAMIX™ NDS) together with the optical measuring instrument PRIMOS® CR according to the SOPs M 4714 “Replikavermessung mittels Primos® CR (Phaseshift Rapid in vivo Measurement of Skin)”, Version 1 of 16 June 2023 and M 4711 “Anfertigung von Replika mittels EXAMIX”, Version 1 of 12 June 2023. Each silicone imprint, representing negative impressions of the topographic features of the skin, was measured once. The 3D height images were computed from the obtained fringe projection images according to the standard procedure using mathematical filters. These height images were used to calculate the skin roughness based on the parameter surface roughness Sq [pm]. The size of the field of view was 45 x 30 x 20 mm. A decrease in surface roughness Sq indicates lower skin roughness and thus smoother skin (i.e., improvement). The mean values were as follows:

[0141] * according to the invention

[0142] Example 11 : Hand wash test comparison of examples 1, 2, 3 and 4B

[0143] The sensory characteristics of skin feel during handwashing were evaluated by a panel of six trained experts. The test formulation comprised 5.5% Lauryl Glucoside, 3.0% Sodium Coco Sulfate, 2.7% Disodium / Sodium Cocoyl Glutamate, 0.8% Cocamidopropyl Betaine and 3.0% of a test substance.

[0144] Prior to testing, panellists performed a standardized prewash using 2 g of a reference cleansing solution applied for 10 seconds, followed by a 10-second rinse under running water. Subsequently, 2 g of the test formulation was applied to the palm and lathered between the hands to generate foam. Foam quality and immediate tactile sensation were assessed using a five-point scale, ranging from 1 (very poor) to 5 (very good).

[0145] Following foam evaluation, the formulation was rinsed off under running water for 15 seconds, and rinsability was similarly rated. Skin softness and smoothness were then assessed immediately after rinsing using the same five-point scale. All evaluations were conducted under controlled conditions in accordance with the established sensory protocol. 202300252 Foreign Filing 17

[0146] * according to the invention

Claims

202300252 Foreign Filing 18Claims1 . Composition comprisingA) glycerol,B) at least one first glycerol fatty acid monoester comprising at least one C-C double bond, andC) at least one second glycerol fatty acid monoester comprising no C-C double bond.

2. Composition according to claim 1 characterised in that the sum of glycerol and all glycerol fatty acid esters comprised in the composition make up for at least 60 wt.-%, preferably 75 wt.-% to 99 wt.-%, wherein the weight percentages refer to the total composition.

3. Composition according to claim 1 or 2 characterised in that it comprisesD) at least one glycerol fatty acid diester, in which the fatty acid acyl groups of the diester are selected from the same fatty acids acylated into said first and second glycerol fatty acid monoester.

4. Composition according to claim 3 characterised in that component D) comprises at least two, preferably at least three different glycerol fatty acid diesters.

5. Composition according to any of the preceding claims characterised in that it comprisesE) at least one diglycerol fatty acid ester in which the fatty acid acyl groups of the diglycerol fatty acid ester are selected from the same fatty acids acylated into said first and second glycerol fatty acid monoester.

6. Composition according to any of the preceding claims characterised in that it comprises component A) in an amount of 2.0 wt.-% to 50 wt.-%, preferably 3.0 wt.-% to 30 wt.-%, more preferably 4.0 wt.-% to 15 wt.-%, component B) in an amount of 10 wt.-% to 60 wt.-%, preferably 15 wt.-% to 45 wt.-%, more preferably 17 wt.-% to 37 wt.-%, and component C) in an amount of 3.0 wt.-% to 45 wt.-%, preferably 5.0 wt.-% to 35 wt.-%, more preferably 7.0 wt.-% to 25 wt.-%, wherein the weight percentages refer to the total composition.

7. Composition according to any of the preceding claims characterised in that said first glycerol fatty acid monoester is selected from a glycerol fatty acid monoester in which the fatty acid acyl group is selected from fatty acids comprising 16 to 22 carbon atoms, preferably 18 carbon atoms, more preferably said first glycerol fatty acid monoester is glycerol monooleate and said second glycerol fatty acid monoester is selected from a glycerol fatty acid monoester in202300252 Foreign Filing 19 which the fatty acid acyl group is selected from fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms.

8. Composition according to any of claims 5 to 7 characterised in that component D) comprises from 0.1 wt.-% to 25 wt.-%, preferably 3.0 wt.-% to 20 wt.-%, more preferably 6.0 wt.- % to 18 wt.-%, glycerol dioleate, from 0.1 wt.-% to 20 wt.-%, preferably 1 .0 wt.-% to 15 wt.-%, more preferably 2.0 wt.- % to 10 wt.-%, of at least one glycerol fatty acid diester, in which the fatty acid acyl group is selected from fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, and from 0.1 wt.-% to 30 wt.-%, preferably 1 .0 wt.-% to 25 wt.-%, more preferably 6.0 wt.- % to 16.0 wt.-%, of at least one glycerol fatty acid diester, which comprises an oleic acid acyl group and one acyl group selected from fatty acids with 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, and in that component E) comprises from 0.1 wt.-% to 25 wt.-%, preferably 1 .0 wt.-% to 20 wt.-%, more preferably 2.0 wt.- % to 15 wt.-% of at least one diglycerol fatty acid monoester in which the fatty acid is selected from oleic acid and fatty acids comprising 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 9 carbon atoms, wherein the weight percentages refer to the total composition.

9. Process for the preparation of a glycerol and glycerol fatty acid monoesters comprising composition comprising the steps ofI) providing a glycerol and at least one fatty acyl group donor providing at least two different fatty acyl groups,II) carrying out an esterification reaction, wherein at least a part of the fatty acyl groups of said fatty acyl group donor is transferred to said glycerol, and optional III) packaging of said prepared composition in a closed container, characterised in that the molar ratio of said glycerol to all fatty acyl groups provided by said fatty acyl group donor is in the range of from 1 .0 : 0.4 to 1 .0 : 1 .0, preferably from 1 .0 : 0.5 to 1 .0 : 0.9, more preferably from 1 .0 : 0.55 to 1 .0 : 0.8.

10. Process according to claim 9 characterised in that said acyl group donor is selected from fatty acids, fatty acid esters, preferably methyl-, ethyl- and glycerol esters, wherein the glycerol esters are preferably fatty acid triglycerides, preferably natural oils.11 . Process according to claim 9 or 10 characterised in that process step II) is carried out in a temperature range of from 30 °C to 300 °C, preferably 40 °C bis 280 °C, more preferably 1 10 °C to 270 °C, even more preferably 180 °C to 260 °C.202300252 Foreign Filing 2012. Process according to any of the claims 9 to 11 characterised in that in process step II) reaction water is removed from the reaction, preferably by distillation, more preferably under reduced pressure.

13. Use of a composition according to any of the claims 1 to 9 for preparation of a formulation, preferably a cleaning formulation, preferably for the cosmetic or household care use.

14. Use according to claim 13 characterised in that said composition is comprised in said formulation in an amount of from 0.1 wt.-% to 10 wt.-%, preferably from 0.2 wt.-% to 5.0 wt.-%, more preferably from 0.3 wt.-% to 3.0 wt.-%, wherein the weight percentages refer to the total formulation.

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