Mixed compositions comprising 1,3-propanediol esters for cosmetic formulations in particular

Abstract

The present invention relates to mixed compositions of 1,3-propanediol esters which have thickening and / or antimicrobial properties in cosmetic formulations in particular, and to the preparation and use thereof.

Description

Mixed compositions comprising 1,3-propanediol esters for cosmetic formulations in particularField of the inventionThe present invention relates to a mixed composition of 1 ,3-propanediol esters which, in particular, have thickening and / or antimicrobial properties in cosmetic formulations, and to the preparation and use thereof.Prior artMany of the thickeners and preservatives for cosmetic formulations that are widely used on the market no longer meet the demands of industry and consumers in terms of sustainability. The trend is towards toxicologically safe, readily biodegradable and completely naturally based products. Such thickeners include glyceryl and sorbitan fatty acid esters. With regard to antimicrobial additives, glyceryl caprylate, p-anisic acid and levulinic acid are among those that meet the requirements.In addition, a completely natural-based 1 ,3-propanediol caprylate (Crinipan PMC green, Symrise) as a pure monoester is also available as an antimicrobial active ingredient. GB2597354A discloses that, in addition to antimicrobial properties, this substance also has viscosity-increasing and hence thickening properties.However, this 1 ,3-propanediol caprylate has the disadvantage that it is not suitable for a use as thickening agent in low- to medium-priced cosmetic surfactant formulations for the mass market due to an inadequate cost / performance ratio.WO2012080231 A1 discloses the use of 1 ,3-propanediol dicaprylate in a process for permanently modifying the shape of keratinic fibers.WO2008123845A2 discloses compositions comprising esters of 1 ,3-propanediol, wherein the 1,3- propanediol has a biological origin.The disadvantage of the disclosed production processes is the use of problematic catalysts. In formulation, the esters result in insufficiently thickened formulations and require the addition of polymer thickeners to increase viscosity.WO 2007095262 discloses compositions comprising esters of 1 ,3-propanediol and an extraction product.WO 20201 7934 discloses diesters of 1,3-propanediol with linear fatty acids having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, with the proviso that both the 1 ,3-propanediol and the fatty acids originate exclusively from plant sources.WO 2010100887 discloses cosmetic preparations comprising an emulsifier, 1 ,3-propanediol and a 1,3-propanediol difatty acid ester, wherein the fatty acids constituting the 1 ,3-propanediol difatty acid ester are selected from isostearic acid, n-octanoic acid and n-decanoic acid.WO 2020160743 discloses the use of a fatty acid ester or a mixture of two or more fatty acid esters, wherein the fatty acid ester or one, two, three or more, preferably all, of the fatty acid esters are selected from the group consisting of 3-hydroxypropyl caprylate, glyceryl monocaprylate, 3- hydroxypropyl undecylenate and glyceryl monoundecylenate, to modify the physicochemical properties of a skincare product.WO 2020160905 discloses the use of a fatty acid ester or a mixture comprising or consisting of two or more fatty acid esters in a cosmetic product for (i) and / or (ii):(I) inhibition of the growth of microorganisms on the skin or mucous membrane of a mammal;(II) preserving the cosmetic product against microbial growth; wherein the fatty acid ester or at least one of the two or more fatty acid esters in the mixture is selected from the group consisting of:3-hydroxypropyl caprylate, 3-hydroxypropyl undecylenate and glyceryl monoundecylenate.WO 2020160904 discloses the use of a fatty acid ester or a mixture of two or more fatty acid esters or a mixture of one or more fatty acid esters, wherein the fatty acid ester or one, two or more of the fatty acid esters is / are selected from the group consisting of 3-hydroxypropyl caprylate, 3- hydroxypropyl undecylenate and glyceryl monoundecylenate for modifying the physicochemical properties of a skincare product.W020160742 discloses the use of a fatty acid ester or a mixture of two or more fatty acid esters or a mixture of one or more fatty acid esters, wherein the fatty acid ester or one, two, three or more of the fatty acid esters is / are selected from the group consisting of 3-hydroxypropyl caprylate, glyceryl monocaprylate, 3-hydroxypropyl undecylenate and glyceryl monoundecylenate, to modify the sensory properties of a skincare product.W020160741 discloses fatty acid esters or mixtures of two or more fatty acid esters or mixtures comprising one or more fatty acid esters, wherein the fatty acid ester or one, two, three or more of the fatty acid esters is / are selected from the group consisting of 3-hydroxypropyl caprylate, glyceryl monocaprylate, 3-hydroxypropyl undecylenate and glyceryl monoundecylenate for use in the treatment of an excess of Malassezia on the surface of the skin of mammals.of the inventionIt was therefore an object of the present invention to provide 1,3-propanediol carboxylic acid esters which can be prepared by a simple process, ideally without a distillation step, and which possess equivalent or better performance in terms of thickening and / or antimicrobial properties compared to the prior art.Surprisingly, it has been found that certain mixed compositions comprising 1 ,3-propanediol carboxylic acid esters as a mixture of 1 ,3-propanediol, 1 ,3-propanediol monocarboxylic acid esters and 1,3-propanediol dicarboxylic acid esters can overcome the disadvantage of the prior art.One advantage of the 1,3-propanediol carboxylic acid esters according to the invention is the more effective thickening performance, in particular in surfactant-containing formulations.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention are the effective antimicrobial properties.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is the high preservation efficiency in aqueous systems.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is the ease of processing for these low- viscous liquids.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is the good solubility in aqueous surfactant systems, whereby clear formulations can be obtained.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is the almost non-existent colour, whereby non-discoloured surfactant formulations can be produced. Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is that they can be produced entirely from renewable raw materials.Another advantage of the 1 ,3-propanediol carboxylic acid esters according to the invention is that they can be produced cost-effectively, whereby they are suitable as alternatives for less sustainable substances in many formulations.The present invention therefore relates to a mixed composition comprisingA) 1 ,3-propanediol,B) 1 ,3-propanediol monocarboxylic acid esters, andC) 1 ,3-propanediol dicarboxylic acid esters, characterized in that, based on all acyl groups present in components B) and C), at least 60 mol%, preferably at least 75 mol%, particularly preferably at least 80 mol%, are selected from acyl groups of carboxylic acids comprising 7 to 12 carbon atoms.The term "1,3-propanediol carboxylic acid ester" used in relation with the invention is a mixture comprising 1 ,3-propanediol and mono- and dicarboxylic acid esters thereof.The “pH” in connection with the present invention is defined as the value which is measured for the relevant composition at 22°C after stirring for five minutes using a pH electrode calibrated in accordance with ISO 4319 (1977).Unless stated otherwise, all stated percentages (%) are percentages by mass.A preferred mixed composition according to the invention is characterized in that, based on all acyl groups present in components B) and C), at least 60 mol%, preferably at least 75 mol%, particularly preferably at least 80 mol%, are selected from acyl groups of carboxylic acids, particularly fatty acids, comprising 8 to 10 carbon atoms.This preferred mixed composition according to the invention is particularly suitable for a use as a thickener, in particular a surfactant-containing formulation.It is preferred according to the invention if the acyl groups present in components B) and C) are selected from acyl groups of fatty acids, in particular unsubstituted, linear, saturated fatty acids.A particularly preferred mixed composition according to the invention is characterized in that, based on all acyl groups present in components B) and C), at least 35 mol% are selected from capryloyl groups, i.e. 1-octanoyl groups, and at least 30 mol% are selected from caproyl groups, i.e. 1- decanoyl groups.This particularly preferred mixed composition according to the invention is particularly suitable for a use as antimicrobial active ingredient.An alternative particularly preferred mixed composition according to the invention is characterized in that, based on all acyl groups present in components B) and C), at least 75 mol%, preferably at least 90 mol%, particularly preferably at least 98 mol%, are selected from pelargonoyl groups, i.e. 1-nonanoyl groups.This alternatively particularly preferred mixed composition according to the invention is also particularly suitable for a use as antimicrobial active ingredient.An alternative particularly preferred mixed composition according to the invention is characterized in that, based on all acyl groups present in components B) and C), from 10 mol% to 80 mol% are selected from capryloyl groups, from 10 mol% to 80 mol% are selected from caproyl groups, and from 10 mol% to 80 mol% are selected from pelargonoyl groups.A particularly preferred mixed composition according to the invention is characterized in that the number-average carbon number of all acyl groups present in components B) and C) is 8.5 to 9.5.A preferred mixed composition according to the invention is characterized in thatA) from 0.1% to weight to 40.0% by weight,B) from 10.0% by weight to 65.0% by weight, andC) from 15.0% by weight to 75.0% by weight, are present in the mixed composition, wherein the percentages by weight refer to the total mixed composition.A preferred mixed composition according to the invention is characterized in that the components A), B) and C) are present in a total amount of at least 90% by weight, wherein the percentages by weight refer to the total mixed composition.The percentages by weight of components A), B) and C) are determined according to the following GC determination method:The mass fraction of 1 ,3-propanediol, fatty acids, and the fatty acid propanediol esters can be determined in the context of the present invention by a GC method.For this purpose, 0.05 g of the mixed composition according to the invention and 0.025 g of 1- pentadecanol as internal standard are dissolved in 5 ml of pyridine:chloroform (4:1 ). To 0.25 ml of this solution are added 0.5 ml of MSTFA [N-methyl-N-(trimethylsilyl)trifluoroacetamide]. The acids and alcohols are quantitatively converted to their trimethylsilyl ethers or esters by reaction at 80°C (30 minutes) and then investigated by GC / FID.This is performed in a gas chromatograph equipped with a split / splitless injector, a capillary column and a flame ionization detector, under the following conditions:Injector: 290 °C, split 40 mlInjection volume: 1 plColumn: 30 m * 0.32 mm HP1 0.25 pmCarrier gas: Hydrogen, const, flow, 2 ml / minTemperature programme: 80°C - 300°C at 8°C / min, then conditioning at 300°C for 10 minutes.Detector: FID at 310 °CHydrogen 35 ml / minAir 240 ml / minMake-up gas 12 ml / min1 ,3-Propanediol, the propanediol monoesters and propanediol diesters and 1 -pentadecanol as internal standard are separated.By evaluating the peak areas compared to the peak areas of the 1 -pentadecanol added as internal standard, the mass fraction of 1,3-propanediol, the carboxylic acids and the propandiol esters can be determined.For this purpose, the GC system is calibrated by measuring mixtures of the substances to be tested and the internal standard with a known composition.A particularly preferred mixed composition according to the invention is characterized in thatA) from 1.1% to weight to 20.0% by weight,B) from 17.0% by weight to 57.0% by weight, andC) from 22.0% by weight to 72.0% by weight, are present in the mixed composition, wherein the percentages by weight refer to the total mixed composition.A preferred mixed composition according to the invention has a saponification number of 150 mg KOH / g to 400 mg KOH / g, preferably 175 mg KOH / g to 375 mg KOH / g, particularly preferably 200 mg KOH / g to 350 mg KOH / g.In one preferred mixed composition according to the invention, the components A) to C) have in total a saponification number of 160 mg KOH / g to 360 mg KOH / g, preferably 180 mg KOH / g to 340 mg KOH / g, particularly preferably 200 mg KOH / g to 320 mg KOH / g.A preferred mixed composition according to the invention additionally comprisesD) free carboxylic acid or a salt thereof, preferably in an amount of 0.05% by weight to 5.0% by weight, wherein the percentages by weight refer to the total mixed composition.When determining the content of free fatty acids or salts thereof, only the weight of the fatty acid itself is taken into account; the weight of the corresponding anion is ignored.Preferably, the acyl groups of the carboxylic acids of component D) correspond to those mentioned above as preferably "all acyl groups present in components B) and C)", also with respect to the preferred amount distributions.A preferred mixed composition according to the invention has an acid number of less than 80 mg KOH / g, preferably less than 50 mg KOH / g, particularly preferably from 0.1 mg KOH / g to 20 mg KOH / g.A preferred mixed composition according to the invention has an hydroxyl number of 50 mg KOH / g to 1000 mg KOH / g, preferably from 75 mg KOH / g to 500 mg KOH / g, particularly preferably 100 mg KOH / g to 400 mg KOH / g.In one preferred mixed composition according to the invention, components A) to C) have in total an hydroxyl number of 80 mg KOH / g to 460 mg KOH / g, preferably 100 mg KOH / g to 420 mg KOH / g, particularly preferably 120 mg KOH / g to 380 mg KOH / g.In a preferred mixed composition according to the invention, components A) to C) have in total a degree of esterification of 0.7 to 1.6, preferably of 0.75 to 1.5, particularly preferably of 0.8 to 1.4. The degree of esterification is the molarmolar ratio of fatty acids to 1,3 propanediol used in the synthesis. Analytically, the determination may be carried out after complete ester hydrolysis of the mixed composition of components A) to C) using all common standard methods including the GC method described in this document.The present invention also relates to an enzyme-catalysed process for preparing a mixed composition comprising 1 ,3-propanediol, 1 ,3-propanediol monocarboxylic acid esters and 1 ,3- propanediol dicarboxylic acid esters comprising the process step ofI) reacting 1 ,3-propanediol with at least one acyl group donor, preferably a fatty acid acyl group donor, selected in particular from fatty acid esters and fatty acids, particularly preferably fatty acids, to obtain the mixed composition, in the presence of a lipase.It is preferred in accordance with the invention that the 1 ,3-propanediol and the at least one acyl group donor make up at least 90% by weight, in particular at least 95% by weight, of the total reaction mixture. As a result, the process according to the invention is preferably carried out with only small amounts of solvent or without solvent.Any acyl group donors may be used according to the invention. These are, for example, carboxylic acid esters or free carboxylic acids and mixtures thereof.Carboxylic esters used with preference in accordance with the invention as acyl group donor are selected from esters based on alkanols and polyols having up to 6 carbon atoms, particularly preferably having up to 3 carbon atoms, very particularly preferably glycerol esters.Carboxylic esters used with particular preference in accordance with the invention as acyl group donor are selected from triglycerides, especially natural fats and oils, particularly preferably selected from the group comprising, preferably consisting of, coconut oil, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algal oils, sesame oil, soya oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuapubutter and oils having a high proportion of polyunsaturated fatty acids (PUFAs). Preference may likewise be given to using sorbitan esters, monoglycerides and diglycerides, particularly ones containing the acyl groups described hereinbelow.Preferably in accordance with the invention, the acyl group donor is selected from fatty acid acyl group donors which in particular provide an acyl group selected from the group of acyl groups of natural fatty acids. Natural fatty acids can be produced on the basis of naturally occurring vegetable or animal oils and have preferably 6 to 30 carbon atoms, in particular 7 to 22, here in particular 8 to 11 carbon atoms. Natural fatty acids are generally unbranched and usually consist of an even number of carbon atoms. Any double bonds have cis configuration. Examples are: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable from the oxidation of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenoic acid (obtainable from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid, particularly preferably caprylic acid, pelargonic acid, capric acid and undecylenoic acid, especially preferably caprylic acid, pelargonic acid and capric acid.Preferably in accordance with the invention, acyl group donors used are carboxylic acids, especially fatty acids, with particular preference being given to using the fatty acids specifically mentioned hereinabove.A preferred process according to the invention is characterized in that in process step I) the molar ratio of 1,3-propanediol to acyl groups present in all acyl group donors is within a range from 1.0:0.7 to 1.0:1.6, preferably from 1.0:0.75 to 1.0:1.5, particularly preferably from 1.0:0.8 to 1.0:1.4.Lipases used with preference in accordance with the invention in process step I) are lipases selected from the group comprising the lipase from Thermomyces lanuginosus (accession number 059952), lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei (accession number P19515), the lipase from Humicola sp. (accession number 059952), the lipase from Rhizomucorjavanicus (accession number S32492), the lipase from Rhizopus oryzae (accession number P61872), the lipases from Candida rugosa (accession number P20261 , P32946, P32947, P3294 and P32949), the lipase from Rhizopus niveus (accession number P61871), the lipase from Penicillium camemberti (accession number P25234), the lipases from Aspergillus niger (ABG73613, ABG7361 and ABG37906) and the lipase from Penicillium cyclopium (accession number P61869), and their respective at least 60%, with preference at least 80%, preferably at least 90%, particularly preferably at least 95%, 98% or 99%, homologues at the amino acid level.Enzymes that are homologous at the amino acid level preferably exhibit, by comparison with the reference sequence, at least 50%, especially at least 90%, of the enzyme activity in propyl laurate units as defined in the context of the present invention.To determine the enzyme activity in PLU (propyl laurate units), 1-propanol and lauric acid are mixed homogeneously in an equimolar ratio at 60°C. The reaction is started with addition of enzyme and the reaction time is measured. Samples are taken from the reaction mixture at intervals and the content of converted lauric acid is determined by titration with potassium hydroxide solution. The enzyme activity in PLU results from the rate at which 1 g of the enzyme concerned synthesizes 1 mol of propyl laurate per minute at 60°C; cf. in this regard also US20070087418, in particular

[0185] ,The accession numbers listed in the context of the present invention correspond to the NCBI Protein database entries with a date of 01.01.2017; the version number of the entry is in the present context generally identified by “.digit”, for example “.1”.Commercial examples, and carboxylic ester hydrolases that are likewise used with preference in processes according to the invention, are the commercial products Lipozyme TL IM, Novozyme 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all commercial products from Novozymes A / S, Bagsvaerd, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercial products from Roche Molecular Biochemicals, Mannheim, Germany), CALB Immo Plus TM from Purolite, and Lipase M “Amano”, Lipase F-AP 15 “Amano”, Lipase AY “Amano”, Lipase N “Amano”, Lipase R “Amano”, Lipase A “Amano”, Lipase D “Amano”, Lipase G “Amano” (all commercial products from Amano, Japan).“Homology at the amino acid level” is for the purposes of the present invention understood as meaning “amino acid identity”, which can be determined with the aid of known methods. In general, use is made of special computer programs with algorithms taking into account specific requirements. Preferred methods for determining the identity first generate the greatest alignment between the sequences to be compared. Computer programs for determining the identity include, but are not limited to, the GCG program package includingGAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), page 387, Genetics Computer Group University of Wisconsin, Medicine (Wl), andBLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pages 403-410. The BLAST program can be obtained from the National Center For Biotechnology Information (NCBI) and from other sources (BLAST Handbook, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., above).Those skilled in the art are aware that various computer programs are available for the calculation of similarity or identity between two nucleotide or amino acid sequences. For instance, the percentage identity between two amino acid sequences can be determined for example by the algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which has been integrated into the GAP program in the GCG software package (available at http: / / www.gcg.com), using either a Blossom 62 matrix or a PAM250 matrix, a gap weight of 16, 14, 12, 10, 8, 6 or 4 and a length weight of 1, 2, 3, 4, 5 or 6. Those skilled in the art will recognize thatthe use of different parameters will lead to slightly different results, but that the percentage identity between two amino acid sequences overall will not be significantly different. The Blossom 62 matrix is typically employed, using the default settings (gap weight: 12, length weight: 1).In the context of the present invention, an identity of 60% according to the above algorithm means 60% homology. The same applies to higher identities.Lipases used with preference in accordance with the invention are present immobilized on a solid carrier.It is preferable according to the invention to use 25 PLU to 1500 PLU, preferably from 50 PLU to 1000 PLU, particularly preferably from 75 PLU to 500 PLU, of lipase per gram of the sum of applied 1,3-propanediol and fatty acid.Process step I) is preferably carried out according to the invention at reaction temperatures in the range between 20°C and 100°C, preferably 30°C and 80°C, in particular between 35°C and 70°C.Process step I) is preferably carried out according to the invention at a pressure of less than 1 bar, preferably less than 0.5 bar and particularly preferably less than 0.2 bar.Process step I) is alternatively preferably carried out according to the invention in a bubble column reactor, with at least one inert gas being passed through the reaction mixture; this gas is preferably selected from the group comprising, preferably consisting of, nitrogen and argon. In this connection, it is preferable in accordance with the invention for the gas stream to be 1 to 60 kg / h, preferably 5 to 25 kg / h, even more preferably 10 to 14 kg / h.A preferred process according to the invention is characterized in that in process step I) the 1 ,3- propanediol and the acyl group donor make up in total at least 10% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, of the overall reaction mixture.Preferably in accordance with the invention, process step I) is carried out without additional solvent.A process that is preferred in accordance with the invention is characterized in that by-products formed in process step I), for example water when the acyl group donor used is a carboxylicacid,and the corresponding alcohol when the acyl group donor used is an carboxylic acid ester, are removed.This is possible for example by distillation.Process step I) is preferably stopped according to the invention not more than 120 hours, in particular 48 hours, after combining the 1 ,3-propanediol, the at least one acyl group donor and the lipase.Preferably in accordance with the invention, the process according to the invention comprises process step II) removing the lipase.In the case that the lipase is immobilized on a carrier, it is preferred according to the invention that the lipase is separated off by filtration.Likewise preferably in accordance with the invention, the process according to the invention comprises process step III) filtering the mixed composition comprising 1 ,3-propanediol, 1 ,3- propanediol monocarboxylic acid ester and 1,3-propanediol dicarboxylic acid ester through a filter, especially a bag filter, having a fineness of 0.1 to 1250 , preferably from 0.5 p to 100 p.Process step III) is preferably carried out according to the invention in a temperature range of 20°C to 150°C, in particular 40°C to 80°C.Process step III) is preferably carried out according to the invention in a pressure range from 0.9 bar to 25 bar, in particular from 1.1 bar to 10 bar.Preferably in accordance with the invention, the process according to the invention does not comprise any further purification step besides process steps II) and III), if these are present.The present invention also relates to a mixed composition comprising 1,3-propanediol, 1 ,3- propanediol monocarboxylic acid ester and 1,3-propanedioldicarboxylic acid ester obtainable by the process according to the invention.The mixed composition according to the invention and / or mixed composition obtainable by the process according to the invention may be used advantageously in formulations.Therefore, the present invention still further relates to a formulation, in particular a cosmetic, pharmaceutical or dermatological formulation, comprising a mixed composition according to the invention and / or a mixed composition obtainable by the process according to the invention.Preferred formulations according to the invention are characterized in that they comprise components A), B) and C) in a total amount of 0.01% by weight to 79% by weight, preferably 0.05% by weight to 5.0% by weight, particularly preferably 0.1% by weight to 3.0% by weight, based on the total formulation, and are particularly preferably cosmetic, pharmaceutical or dermatological formulations.The formulations of the invention can further comprise at least one additional component selected from the group of emollients, surfactants, emulsifiers, thickeners / viscosity regulators / stabilizers, UV light protection filters, antioxidants, hydrotropes (or polyols), solids and fillers, film formers, pearlescence additives, deodorant and antiperspirant active ingredients, insect repellents, self-tanning agents, preservatives, conditioning agents, perfumes, colorants, odour absorbers, cosmetic active substances, care additives, superfatting agents, solvents.Substances which can be used as exemplary representatives of the individual groups are known to those skilled in the art and can be taken, for example, from German patent application DE 102008001788.4. This patent application is hereby incorporated by reference and is thus considered to form part of the disclosure.With regards to further optional components and also the amounts of these components employed, 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.Typical starting 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, if necessary, for adjustment and optimization, the desired modifications can be made in a straightforward manner by simple tests.Preferred formulations according to the invention comprise in particular at least one surfactant and also particularly preferably additionally water.In the context of these preferred aqueous surfactant formulations according to the invention, it is particularly preferred that these formulations are clear.In this context, "clear" signifies that values of less than 100 NTU can be determined using a turbidimeter.According to the invention, the production of clear formulations is preferred.A particularly preferred formulation according to the invention is characterized in that said formulation has a pH in the range of 3.5 to 8.0, preferably 4.0 to 7.4, particularly preferably 4.5 to 7.2.The present invention further relates to the use of a mixed composition according to the invention and / or a mixed composition obtainable by the process according to the invention as antimicrobial active ingredient, in particular in a formulation, preferably a cosmetic, pharmaceutical or dermatological formulation.An antimicrobial active ingredient is understood to mean a substance that, in low concentration, acts against and either destroys or inhibits the growth of microorganisms.The present invention further relates to the use of a mixed composition according to the invention and / or a mixed composition obtainable by the process according to the invention as thickener, in particular in a formulation, preferably a cosmetic, pharmaceutical or dermatological formulation, which moreover preferably contains at least one surfactant. In the context of the present invention, the term "thickener" refers to the ability of a substance to increase the viscosity of a given composition when added.The examples adduced below describe the present invention by way of example without any intention to limit the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.All percentages (%) listed below are percent by weight (% by weight).Example 1 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), caprylic / capric acid (58:42 (w / w), 158 g, 1.00 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 4.67 g, 33437 PLU) was stirred at 50°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 7.33% 1,3-propanediol, 47.0% 1,3-propanediol monocarboxylic acid esters consisting of 28.3% 1,3-propanediol monocaprylate and 18.7% 1 ,3-propanediol monocaprate, 43.8% 1,3-propanediol dicarboxylic acid esters consisting of 16.3% 1 ,3-propanediol dicaprylate, 20.8% 1 ,3-propanediol caprylate / caprate (mixed ester) and 6.77% 1 ,3-propanediol dicaprate and 0.2% unreacted caprylic / capric acid.Example 2 (inventive):Chemically catalysed reaction of 1 ,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (89.8 g, 1.18 mol), caprylic / capric acid (58:42 (w / w), 186 g, 1.18 mol) and para-toluenesulfonic acid (1.39 g, 7.31 mmol) was heated at a heating rate of 20°C per hour and then stirred at 120°C for 7 h. During this time, the water of reaction was distilled off. After cooling to 22°C, the product was a clear, yellowish liquid and comprised 7.01% 1,3-propanediol, 46.2% 1 ,3-propanediol monocarboxylic acid esters consisting of 27.8% 1 ,3-propanediol monocaprylate and 18.4% 1 ,3-propanediol monocaprate, 44.2% 1 ,3-propanediol dicarboxylic acid esters consisting of 16.2% 1,3-propanediol dicaprylate, 21.2% 1 ,3-propanediol caprylate / caprate (mixed ester) and 6.80% 1 ,3-propanediol dicaprate and 0.2% unreacted caprylic / capric acid.Example 3 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 1.2:A mixture of 1 ,3-propanediol (51.6 g, 0.68 mol), caprylic / capric acid (58:42 (w / w), 128 g, 0.82 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 3.6 g, 25776 PLU) was stirred at 50°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 3.87% 1,3-propanediol, 40.1% 1,3-propanediol monocarboxylic acid esters consisting of 23.3% 1,3-propanediol monocaprylate and 16.8% 1 ,3-propanediol monocaprate, 54.9% 1,3-propanediol dicarboxylic acid esters consisting of 19.3% 1 ,3-propanediol dicaprylate, 26.7% 1 ,3-propanediol caprylate / caprate (mixed ester) and 8.90% 1 ,3-propanediol dicaprate and 0.3% unreacted caprylic / capric acid.Example 4 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 1.4:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), caprylic / capric acid (58:42 (w / w), 221 g, 1.40 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 8.91 g, 63795 PLU) was stirred at 50°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 2.22% 1,3-propanediol, 32.3% 1,3-propanediol monocarboxylic acid esters consisting of 19.5% 1,3-propanediol monocaprylate and 12.8% 1 ,3-propanediol monocaprate, 63.4% 1,3-propanediol dicarboxylic acid esters consisting of 23.5% 1 ,3-propanediol dicaprylate, 30.3% 1 ,3-propanediol caprylate / caprate (mixed ester) and 9.55% 1 ,3-propanediol dicaprate and 0.3% unreacted caprylic / capric acid.Example 5 (inventive):Chemically catalysed reaction of 1 ,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 1.4:A mixture of 1 ,3-propanediol (73.1 g, 0.96 mol), caprylic / capric acid (58:42 (w / w), 212 g, 1.34 mol) and para-toluenesulfonic acid (1.43 g, 7.53 mmol) was heated at a heating rate of 20°C per hour and then stirred at 120°C for 9 h. During this time, the water of reaction was distilled off. After cooling to 22°C, the product was a clear, yellowish liquid and comprised 1.66% 1,3-propanediol, 29.3% 1 ,3-propanediol monocarboxylic acid esters consisting of 17.6% 1 ,3-propanediol monocaprylate and 11.7% 1 ,3-propanediol monocaprate, 67.6% 1 ,3-propanediol dicarboxylic acid esters consisting of 24.9% 1,3-propanediol dicaprylate, 32.4% 1 ,3-propanediol caprylate / caprate (mixed ester) and 10.3% 1 ,3-propanediol dicaprate and 0.3% unreacted caprylic / capric acid.Example 6 (inventive):Enzyme-catalysed reaction of 1,3-propanediol with caprylic / capric acid in the molar ratio 1.0 to 0.8:A mixture of 1 ,3-propanediol (67.8 g, 0.89 mol), caprylic / capric acid (58:42 (w / w), 112 g, 0.71 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 3.60 g, 25776 PLU) was stirred at 45°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 13.2% 1,3-propanediol, 51.7% 1,3-propanediol monocarboxylic acid esters consisting of 31.2% 1,3-propanediol monocaprylate and 20.5% 1 ,3-propanediol monocaprate, 33.8% 1,3-propanediol dicarboxylic acid esters consisting of 12.3% 1 ,3-propanediol dicaprylate, 16.1% 1 ,3-propanediol caprylate / caprate (mixed ester) and 5.36% 1 ,3-propanediol dicaprate and 0.3% unreacted caprylic / capric acid.Example 7 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with caprylic acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (86.4 g, 1.13 mol), caprylic acid (164 g, 1.13 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 7.50 g, 53700 PLU) was stirred at 60°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 8.18% 1 ,3-propanediol, 47.7% 1 ,3-propanediol monocaprylate and 42.7% 1,3- propanediol dicaprylate and 0.4% unreacted caprylic acid.Example 8 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with pelargonic acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), pelargonic acid (158 g, 1.00 mol) and immobilized enzyme of the Candida antarctica lipase B type(Purolite D5619, 7.02 g, 51552 PLU) was stirred at 60°C and 50 mbar for 11 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 7.71% 1 ,3-propanediol, 46.9% 1 ,3-propanediol monopelargonate and 41.7% 1,3- propanediol dipelargonate and 0.1% unreacted pelargonic acid.Example 9 (inventive):Chemically catalysed reaction of 1 ,3-propanediol with pelargonic acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), pelargonic acid (158 g, 1.00 mol) and para- toluenesulfonic acid (0.24 g, 1.26 mmol) was heated at a heating rate of 20°C per hour and thenstirred at 140°C for 9 h. During this time, the water of reaction was distilled off. After cooling to 22°C, the product was a clear, yellowish liquid and comprised 6.93% 1 ,3-propanediol, 46.5% 1 ,3- propanediol monopelargonate and 42.5% 1 ,3-propanediol dipelargonate and 0.1% unreacted pelargonic acid.Example 10 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with pelargonic acid in the molar ratio 1.0 to 1.2:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), pelargonic acid (190 g, 1.20 mol) and immobilized enzyme of the Candida antarctica lipase B type(Purolite D5619, 7.98 g, 57136 PLU) was stirred at 60°C and 50 mbar for 11 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 4.42% 1 ,3-propanediol, 40.0% 1 ,3-propanediol monopelargonate and 51.2% 1,3- propanediol dipelargonate and 0.3% unreacted pelargonic acid.Example 11 (inventive):Enzyme-catalysed reaction of 1 ,3-propanediol with undecylenoic acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (76.1 g, 1.00 mol), undecylenoic acid (184 g, 1.00 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 7.81 g, 55919 PLU) was stirred at 60°C and 50 mbar for 7 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was a clear, almost colourless liquid and comprised 3.80% 1,3-propanediol, 53.7% 1,3-propanediol monoundecylenate and 40.5% 1 ,3-propanediol diundecylenate and 0.8% unreacted undecylenoic acid.Example 12 (non-inventive): 1,3-propanediol monocaprylate Crinipan® PMC greenAs a pure 1,3-propanediol monocarboxylic acid ester, Crinipan® PMC green from Symrise was used.Example 13:Enzyme-catalysed reaction of 1 ,3-propanediol with stearic acid acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (53.5 g, 0.70 mol), stearic acid (200 g, 0.70 mol) and immobilized enzyme of the Candida antarctica lipase B type (Purolite D5619, 5.00 g, 35800 PLU) was stirred at70°C and 50 mbar for 6 h. During this time, the water of reaction was distilled off. The reaction mixture was then filtered. After cooling to 22°C, the product was an almost colourless solid and comprised 3.43% 1 ,3-propanediol, 50.5% 1 ,3-propanediol monostearate and 43.1% 1 ,3- propanediol distearate and 0.7% unreacted stearic acid.Example 14 (non-inventive):Chemically catalysed reaction of 1 ,3-propanediol with stearic acid in the molar ratio 1.0 to 1.0:A mixture of 1 ,3-propanediol (53.5 g, 0.70 mol), stearic acid (200 g, 0.70 mol) and para- toluenesulfonic acid (0.25 g, 1 .33 mmol) was stirred at 140°C for 7 h. During this time, the water of reaction was distilled off. After cooling to 22°C, the product was an almost colourless solid and comprised 3.62% 1 ,3-propanediol, 49.2% 1 ,3-propanediol monostearate and 43.4% 1 ,3- propanediol distearate and 0.8% unreacted stearic acid.The examples described above were tested hereinafter in cosmetic formulations.The formulation constituents are named according to the generally accepted INCI nomenclature. All concentrations in the application examples are given in percent by weight.Example 15: Thickening performance:For comparing the thickening performance of the examples, these were incorporated in equal amounts into an aqueous cosmetic formulation and the viscosity was then measured.The formulation consisted of 5.6% Sodium Cocoamphoacetate, 4.4% Lauryl Glucoside, 1.2% Coco-Glucoside, 3.6% Disodium / Sodium Cocoyl Glutamate, 0.5% example and the remainder was water.The pH of the formulation was adjusted to 5.2 with citric acid before the examples were incorporated by stirring at 60°C for 30 min.The viscosities were determined using a Brookfield viscometer (spindle 62, 30 rpm) at 22°C. The results of the measurement are shown in the following table.* inventive **non-inventiveExample 16: Antimicrobial efficacyFor the determination of antimicrobial efficacy, aqueous solutions of the examples according to the invention and those not according to the invention were prepared. For this purpose, 0.5% of the example compounds were in each case dissolved in 0.75% TEGO Solve 90 (Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate). This solution is then gradually filled up to 100% with water. The pH of the solutions is then adjusted to 5.0 ± 0.2 with citric acid (20%).The antimicrobial efficacy of the solutions prepared in the manner described was then investigated as follows:Preparation of the inoculum:To prepare for the test, the surface of soybean casein digest agar for bacteria, or Saboraud dextrose agar without addition of antibiotics for fungi, is inoculated with the recently cultured stock strain of each of the specified microorganisms. The bacterial cultures are inoculated at 30-35°C for 18-24 hours, the culture of Candida albicans at 20-25°C for 48 hours and the culture of Aspergillus brasiliensis at 20-25°C for 1 week or until good spore formation has been achieved.Procedure:The agar medium used for the original culturing of the respective microorganism was used to count the viable microorganisms in the inoculated products. The test sample is inoculated with a suspension of the test organism to obtain an inoculum of 105to 106microorganisms per millilitre of the preparation. The volume of the inoculum suspension is not more than 1% of the volume of the product. To ensure a homogeneous distribution, the suspension is thoroughly mixed. The inoculated product is stored at 20-25°C in the dark. At zero hours and after 2, 7, 14 and 28 days, 1 ml is withdrawn from the sample and the number of viable microorganisms is determined by counting the plates.The results of the evaluation of antimicrobial efficacy are shown in the following table. The higher the logarithmic decrease in the bacterial count, the greater the antimicrobial efficacy.The following tables show the logarithmic decrease in the bacterial count 28 days after incubation; higher values signify better efficacy:* inventive **non-inventive* inventive **non-inventiveThe following table shows the logarithmic decrease in the bacterial count 2 days after incubation; higher values signify better efficacy:* inventive **non-inventiveThe examples show that the formulations according to the invention have good antimicrobial efficacy compared to the "blank” solution, which does not comprise any composition according to the invention, corresponding at least to the commercial product Crinipan PMC green ("12").Example 17: Sensory feel in handwash testSkin feel during a handwash test was assessed by a trained panel of six experts. A formulation consisting of 5.6% Sodium Cocoamphoacetate, 4.4% Lauryl Glucoside, 1.2% Coco-Glucoside, 3.6% Disodium / Sodium Cocoyl Glutamate, 0.5% substance from the examples above and water as the remainder was investigated in a handwash test for foam behaviour and sensory feel thereof. For this purpose, the six trained panelists were instructed to wash their hands according to a protocol. Before using the formulations, the hands were washed with 2 g of a standard cleansing solution for 10 s. The cleansing solution was then washed off for 10 s. After prewashing the hands, 2 g of the test formulation was applied to the palm of the hand. Foam was generated between the palms of the hands and the foam and skin feeling was evaluated on a scale of 1 (very poor) to 5 (very good). The formulation was washed off under running water for 15 s and the rinsability was evaluated. Skin softness and smoothness were then assessed on a scale of 1 (very poor) to 5 (very good). This assessment was made directly after washing off the formulation and 3 minutes after the washing process.

Claims

Claims1. Mixed composition comprisingA) 1,3-propanediol,B) 1,3-propanediol monocarboxylic acid esters, andC) 1,3-propanediol dicarboxylic acid esters, characterized in that, based on all acyl groups present in components B) and C), at least 80 mol% are selected from acyl groups of carboxylic acids comprising 7 to 12 carbon atoms.

2. Mixed composition according to Claim 1, characterized in that, based on all acyl groups present in components B) and C), at least 60 mol% are selected from acyl groups of carboxylic acids comprising 8 to 10 carbon atoms.

3. Mixed composition according to Claim 1 or 2, characterized in that, based on all the acyl groups present in components B) and C), at least 35 mol% are selected from capryloyl groups and at least 30 mol% are selected from caproyl groups.

4. Mixed composition according to at least one of the preceding claims, characterized in thatA) from 0.1% to weight to 40.0% by weight,B) from 10.0% by weight to 65.0% by weight, andC) from 15.0% by weight to 75.0% by weight, are present in the mixed composition, wherein the percentages by weight refer to the total mixed composition.

5. Mixed composition according to at least one of the preceding claims, characterized in that said composition has a saponification number of 150 mg KOH / g to 400 mg KOH / g, preferably 175 mg KOH / g to 375 mg KOH / g, particularly preferably 200 mg KOH / g to 350 mg KOH / g.

6. Mixed composition according to at least one of the preceding claims, characterized in that said composition has an acid number of less than 80 mg KOH / g, preferably less than 50 mg KOH / g, particularly preferably from 0.1 mg KOH / g to 20 mg KOH / g.

7. Mixed composition according to at least one of the preceding claims, characterized in that said composition has a hydroxyl number of 50 mg KOH / g to 1000 mg KOH / g, preferably from 75 mg KOH / g to 500 mg KOH / g, particularly preferably 100 mg KOH / g to 400 mg KOH / g.

8. Enzyme-catalysed process for preparing a mixed composition comprising 1 ,3-propanediol, 1,3-propanediol monocarboxylic acid esters and 1,3-propanediol dicarboxylic acid esters comprising the process step ofI) reacting 1 ,3-propanediol with at least one acyl group donor, preferably a fatty acid acyl group donor, selected in particular from fatty acid esters and fatty acids, particularly preferably fatty acids, to obtain the mixed composition, in the presence of a lipase.

9. Process according to Claim 8, characterized in that the acyl group donor is selected from fatty acid acyl group donors which in particular provide an acyl group selected from the group of the acyl groups of caproic acid, caprylic acid, pelargonic acid, capric acid, undecylenoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid, particularly preferably caprylic acid, pelargonic acid, capric acid and undecylenoic acid.

10. Process according to claim 8 or 9, characterized in that in process step I) the molar ratio of 1,3-propanediol to acyl groups present in all acyl group donors is within a range from 1.0:0.7 to 1.0:1.6, preferably from 1.0:0.75 to 1.0:1.5, particularly preferably from 1.0:0.8 to 1.0:1.4.11 . Process according to at least one of Claims 8 to 10, characterized in that the lipase is selected from the group comprising the lipase from Thermomyces lanuginosus (accession number 059952), lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei (accession number P19515), the lipase from Humicola sp. (accession number 059952), the lipase from Rhizomucorjavanicus (accession number S32492), the lipase from Rhizopus oryzae (accession number P61872), the lipases from Candida rugosa (accession number P20261, P32946, P32947, P3294 and P32949), the lipase from Rhizopus niveus (accession number P61871), the lipase from Penicillium camemberti (accession number P25234), the lipases from Aspergillus niger (ABG73613, ABG7361 and ABG37906) and the lipase from Penicillium cyclopium (accession number P61869), and their respective at least 60% homologues at the amino acid level.

12. Process according to at least one of Claims 8 to 11 , characterized in that process step I) is conducted at reaction temperatures in the range between 20°C and 100°C, preferably 30°C and 80°C, in particular between 35°C and 70°C.

13. Process according to at least one of Claims 8 to 12, characterized in that in process step I) the 1 ,3-propanediol and the acyl group donor make up in total at least 10% by weight,preferably at least 80% by weight, particularly preferably at least 90% by weight, of the overall reaction mixture.

14. Mixed composition comprising 1,3-propanediol, 1 ,3-propanediol monocarboxylic acid esters and 1,3-propanediol dicarboxylic acid esters obtainable by the process according to at least one of Claims 8 to 13.

15. Formulation, in particular a cosmetic, pharmaceutical or dermatological formulation, comprising a mixed composition according to at least one of Claims 1 to 7 or 14.

16. Use of a mixed composition according to at least one of Claims 1 to 7 or 14 as an antimicrobial active ingredient and / or thickener.

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