Sorbitan ester and enzymatic preparation method thereof

Abstract

The present invention relates to a process for the enzymatic preparation of sorbitan carboxylic acid esters, and to the sorbitan carboxylic acid esters obtainable by this process.

Description

Field of the Invention

[0001] The present invention relates to a process for the enzymatic preparation of sorbitan carboxylic acid esters, and to the sorbitan carboxylic acid esters obtainable by this process. Prior art

[0002] Sorbitol carboxylates are products of interest to the food and cosmetics industries, on the one hand because of their surfactant properties and on the other hand because they can be obtained from natural and renewable raw materials.

[0003] DE 10 2009 001 748 A describes sorbitan esters obtained by the solvent-free reaction of 1 mol of sorbitol (also called glucitol) with 1.55 mol of octanoic acid, and the use of the sorbitan esters obtained therefrom as thickeners for aqueous surfactant systems. A disadvantage of this process is that under the reaction conditions described, sorbitol is almost completely dehydrated, but at least partially, so that so-called sorbitan esters (product mixture) are formed.

[0004] The degradation products of sorbitol that often appear under such conditions are the anhydrohexitols 1,4-sorbitan, 2,5-sorbitan, 1,5-sorbitol (Advances in Carbohydrate Chemistry and Biochemistry, 1983, 41, 27-66) and isosorbide (1,4:3,6-dianhydrosorbitol; ChemSusChem.5 (1): 167–176).

[0005] A further disadvantage of these sorbitan esters is their dark color, which requires post-treatment, for example using activated carbon, in order to achieve a product quality that can be used in the cosmetic sector.

[0006] JP63133991 describes the reaction of 1.0 equivalent of oleic acid with 1.0 equivalent of sorbitol in the presence of >9% lipase (Candida) at 40-50°C and 100 mmHg (133 mbar). A disadvantage of the process described in the prior art is that only about 70% esterification is obtained. Another disadvantage is that only pure oleic acid is used, which is too expensive for industrial applications in the food and cosmetics sectors and is therefore uneconomical.

[0007] DE3430944 describes the reaction of ≥ 4.0 equivalents of oleic acid or stearic acid with 1.0 equivalents of sorbitol in the presence of about 7% lipase at 40 ° C for 72 hours, wherein the reactants and enzyme react with each other in an aqueous buffer system with a mass concentration of about 28 g per 1000 ml. The disadvantage of the method described in the prior art is the use of aqueous phosphate buffer, and the salt load in its product is not suitable for use in cosmetics. Another disadvantage is that the mass concentration of reactants and lipase in the buffer system is only about 3%, which means that the space-time yield of industrial-scale conversion is far too low. Another disadvantage is that only pure oleic acid and pure stearic acid are used.

[0008] Lorie et al., Biotechnol. Bioeng. 1995, 48, 214–221, describe the reaction of sorbitol with 1.0 equivalent of oleic acid in the presence of 15% Novozym 435 (lipase from Candida antarctica; about 494,000 PLU per mole of fatty acid) at 90° C. and a pressure of < 0.7 kPa (< 7 mbar). A disadvantage of the process described in the prior art is that the sorbitol used remains as a highly viscous semisolid at the bottom of the reaction vessel, while the oleic acid is a layer above it. This behavior additionally makes it difficult to mix the reactants thoroughly, which is already difficult.

[0009] EP1755545B1 describes a mixture of sorbitan esters and sorbitol esters, wherein the chain length of the fatty acids of the sorbitan esters is greater than the chain length of the fatty acids of the sorbitol esters, and more than 80% of saturated fatty acids are always used. The sorbitan esters here account for at least 50% of the mixture. The sorbitol esters here consist only of monoesters and diesters, of which at least 40% of monoesters and less than 60% of diesters are used to influence the emulsion stability and viscosity. Starting from lauric acid, a mixture consisting of 7% sorbitan esters, 68% C12 sorbitol esters and 25% polyols is obtained. The disadvantage of the preparation method described in the prior art is that sorbitan esters are also formed here, whereby the hydrophilic part of the surfactant becomes smaller and the resulting color is poor.

[0010] It is an object of the present invention to provide a process for preparing sorbitan esters which overcomes at least one disadvantage of the prior art processes.

[0011] Description of the invention

[0012] It has surprisingly been found that the objects set forth in the present invention can be achieved by the sorbitol carboxylic acid esters described below and by the process described below.

[0013] The advantage of the present invention is that, compared with the prior art, the sorbitol carboxylic acid ester of the present invention is an excellent thickener for aqueous surfactant systems. Another advantage is that, compared with the prior art, the sorbitol carboxylic acid ester of the present invention also has excellent color and very good odor. The advantage of the present invention is that only a very small amount of sorbitol degradation products or esters of degradation products are obtained as reaction products. The advantage of the present invention is that the method of the present invention can be carried out in the absence of a solvent. Another advantage of the present invention is that the sorbitol carboxylic acid ester is obtained in a uniform reaction mixture, so no additional method steps are required, such as extraction, crystallization, filtration or distillation. The advantage of the present invention is that the method can be carried out at an elevated temperature. This causes the co-reactant to have better miscibility, and the recyclability of the enzyme used is surprisingly high. Another advantage of the present invention is that the sorbitol carboxylic acid ester obtained can be incorporated into a formulation very easily, particularly into a cosmetic formulation.

[0014] The subject of the present invention is therefore a process for the enzymatic preparation of sorbitol carboxylate, comprising the following process steps:

[0015] A) providing sorbitol and at least one acyl donor, preferably a fatty acid acyl donor, in particular selected from fatty acid esters and fatty acids, more preferably fatty acids,

[0016] B) reacting sorbitol with said at least one acyl donor in the presence of a lipase at a temperature of 75°C to 110°C, preferably 77°C to 100°C, even more preferably 80°C to 95°C to obtain sorbitol carboxylate, and optionally

[0017] C) purifying the sorbitol carboxylate,

[0018] Characterized in that process step A) comprises blending sorbitol and the at least one acyl donor for at least 10 minutes, preferably at least 30 minutes, even more preferably at least 60 minutes, in a temperature range of 80°C to 120°C, preferably 90°C to 120°C, even more preferably 95°C to 120°C, even more preferably 100°C to 120°C.

[0019] The term "sorbitan carboxylate" in the context of the present invention includes compositions which contain a major portion, in particular at least 40% by weight, preferably at least 50% by weight, even more preferably at least 60% by weight, of sorbitan carboxylate, based on the entire composition. Optionally, however, by-products from the respective preparation processes, such as 1,4-sorbitan carboxylate, 2,5-sorbitan carboxylate, 1,5-sorbitan carboxylate and isosorbide carboxylate, and also unreacted reactants may also be contained.

[0020] The terms "sorbitan carboxylate" and "sorbitan carboxylate" are used synonymously in the context of the present invention.

[0021] The use of this term is based on the general nomenclature of polyol esters; it is known that said polyol esters are easily dehydrated during their synthesis, so that the product is a mixed composition. The person skilled in the art therefore understands the term "sorbitan ester" to mean a mixture which comprises not only esters of 1,4-sorbitan and 1,5-sorbitan, but also esters of isosorbide and sorbitol, as well as free sorbitol, for which see e.g. Food emulsifiers and their applications , 1997, p. 26.

[0022] The term "carboxylic acid ester of sorbitol" in the context of the present invention refers to the pure sorbitol compound.

[0023] The term "carboxylic acid ester of 1,4-sorbitan" in the context of the present invention refers to the pure 1,4-sorbitan compound.

[0024] The term "carboxylic acid ester of 2,5-sorbitan" in the context of the present invention refers to the pure 2,5-sorbitan compound.

[0025] The term "carboxylic acid ester of 1,5-sorbitan" in the context of the present invention refers to the pure 1,5-sorbitan compound.

[0026] The term "carboxylic acid ester of isosorbide" in the context of the present invention refers to the pure isosorbide compound.

[0027] Unless otherwise stated, all percentages (%) shown are mass percentages.

[0028] According to the invention, all acyl donors can be used according to the invention. These include, for example, carboxylic acid esters or carboxylic acids themselves, and also mixtures thereof.

[0029] It is preferred according to the invention that the acyl donor provided in process step A) provides an acyl group which is derived from a carboxylic acid having 2 to 34, preferably 4 to 24, more preferably 6 to 22 carbon atoms, in particular a natural fatty acid or a mixture thereof.

[0030] The carboxylic acid esters preferably used according to the invention as acyl donors 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.

[0031] The carboxylic acid esters particularly preferably used as acyl donors according to the invention are selected from triglycerides, in particular natural fats and oils, particularly preferably from the group comprising, preferably consisting of, coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algae oil, sesame oil, soybean oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuaçu oil and oils with a high proportion of polyunsaturated fatty acids (PUFA). Sorbitan esters, mono- and diglycerides, in particular those containing the acyl groups described below, can likewise be preferably used.

[0032] More preferably according to the present invention, the acyl donor is selected from fatty acid acyl donors, which in particular provide acyl groups selected from acyl groups of natural fatty acids, or mixtures thereof.

[0033] Fatty acids preferred in this connection are mixtures of natural fatty acids, in particular mixtures in which no carboxylic acid chain length has a proportion of more than 95% by weight, in particular more than 99% by weight, in the overall chain length distribution.

[0034] Natural fatty acids can be produced based on naturally occurring vegetable oils or animal oils, and preferably have 6 to 30 carbon atoms, especially 8 to 22 carbon atoms. Natural fatty acids are usually unbranched, mostly composed of an even number of carbon atoms. Possible double bonds all have cis configurations. Examples are: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, nonanoic acid (e.g., can be obtained from the ozonolysis or oxidative cracking of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (can be obtained from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0035] More preferably according to the invention, the acyl donors are selected from fatty acid acyl donors, characterized in that they provide an acyl mixture comprising at least two carboxylic acid acyl groups selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, nonanoic acid (obtainable, for example, from ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecenoic acid (obtainable, for example, from pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0036] Acyl donors preferably used according to the invention are carboxylic acids, in particular fatty acids. Preferred fatty acids in this context are those mentioned above in connection with the preferred fatty acids provided.

[0037] Alternatively, acyl donors preferably used according to the invention are mixtures of fatty acids and glycerol fatty acid esters, preference being given to using those mentioned above in connection with the preferably provided fatty acids, both in the case of the fatty acids and in the case of the glycerol fatty acid component with the same degree of preference.

[0038] The mixture of fatty acids and glycerol fatty acid esters used preferably has a weight ratio of fatty acids to glycerol fatty acid esters of 80:20 to 99:1, preferably 90:10 to 99:1, more preferably 95:5 to 99:1.

[0039] A preferred process according to the invention is characterized in that the sorbitol and the at least one acyl donor constitute at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, based on the entire reaction mixture at the start of process step B).

[0040] Since the overall reaction mixture in this case consists largely of the reactants, i.e. sorbitol and the acyl donor, only very little solvent, if any, can be contained in the overall reaction mixture. Based on what has been described above, it is obvious that the acyl donor is not covered by the term "solvent" in the process of the present invention.

[0041] Possible solvents are, for example, ketones, such as methyl isobutyl ketone or cyclohexanone, sterically hindered secondary alcohols, such as 2-butyl-1-octanol, methylcyclohexanol, 1-methoxy-2-propanol, butane-2,3-diol, 2-octanol, diacetone alcohol, 2-methyl-2-butanol, and ethers, such as 1,4-dioxane, tetrahydrofuran and Varonic APM.

[0042] Based on the entire reaction mixture, the solvent is contained in total up to less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight. The expression "contains up to less than X% by weight" can be equated with "having a content of less than X% by weight".

[0043] With particular preference, the process according to the invention is carried out in the absence of solvents.

[0044] The process preferred according to the invention is therefore characterized in particular in that the water content in process step B) is less than 15% by weight, preferably less than 5.0% by weight, more preferably less than 1.0% by weight, based on the entire reaction mixture.

[0045] The lipase preferably used according to the invention in process step B) is present in the form of an immobilized solid support.

[0046] According to the invention, the lipase preferably used in process step B) is a lipase selected from the group consisting of: Thermomyces lanuginosus), lipases A and B from Candida antarctica (Accession No. P41365) and lipases from Mucor miehei (Accession No. P19515), lipases from Humicola sp. (Accession No. O59952), lipases from Rhizomucor javanicus (Accession No. S32492), lipases from Rhizopus oryzae (Accession No. P61872), lipases from Candida rugosa (Accession Nos. P20261, P32946, P32947, P3294 and P32949), lipases from Rhizopus nivalis (Accession No. P32947, P3294 and P32949), lipases from Rhizopus spp. (Accession No. S32947, S3294 and S ... niveus (Accession No. P61871), a lipase from Penicillium camemberti (Accession No. P25234), a lipase from Aspergillus niger (ABG73613, ABG73614 and ABG37906) and a lipase from Penicillium cyclopium (Accession No. P61869), of which lipases A and B from Candida antarctica (Accession No. P41365) are particularly preferred, and at least 60%, preferably at least 80%, preferably at least 90%, especially preferably at least 95%, 98% or 99% homologs thereof at the amino acid level.

[0047] The accession numbers listed in the context of the present invention correspond to the NCBI ProteinBank database entry dated 2017.01.01; the version number of an entry in this context is usually identified by a ".number", such as ".1".

[0048] Compared to the reference sequence, an enzyme which is homologous at the amino acid level preferably has at least 50%, in particular at least 90% of the enzyme activity expressed in propyl laurate units (PLU) as defined in the context of the present invention.

[0049] To determine the enzyme activity expressed in PLU (propyl laurate units), 1-propanol and lauric acid are homogeneously mixed in an equimolar ratio at 60° C. The reaction is started by adding the enzyme and the reaction time is measured. Samples are taken from the reaction mixture at regular intervals and the content of converted lauric acid is determined by titration with potassium hydroxide solution. The enzyme activity expressed in PLU is derived from the rate at which 1 g of the relevant enzyme synthesizes 1 µmol of propyl laurate per minute at 60° C.; see US20070087418, in particular

[0185] .

[0050] Commercial examples and lipases which are likewise preferably used in the process according to the invention are the commercial products Lipozyme TL IM, Novozym 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all products from Novozymes A / S, Bagsvaerd, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all 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 products from Amano, Japan).

[0051] "Homology at the amino acid level" is understood for the purposes of the present invention to mean "amino acid identity", which can be determined by known methods. Usually, special computer programs are used, in which the algorithm takes into account specific requirements. A preferred method for determining identity first produces the closest correspondence between the sequences to be compared. Computer programs for determining identity include, but are not limited to, the GCG program package, including

[0052] - GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), p. 387, Genetics Computer Group University of Wisconsin, Medicine (WI), and

[0053] - BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pp. 403-410. The BLAST programs are available from the National Center for Biotechnology Information (NCBI) and other sources (BLAST Manual, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., supra).

[0054] Those skilled in the art will appreciate that various computer programs can be used to calculate the similarity or identity between two nucleotide or amino acid sequences. For example, the percent identity between two amino acid sequences can be determined, for example, by an algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which is incorporated into the GAP program of the GCG software package (available from http: / / www.gcg.com), using a Blossom 62 matrix or a PAM250 matrix with 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 that using different parameters will result in slightly different results, but the percent identity between two amino acid sequences will not be significantly different overall. The Blossom 62 matrix is ​​typically used with the default settings (gap weight: 12, length weight: 1).

[0055] In the context of the present invention, 60% identity means 60% homology according to the above algorithm. The same applies to higher identities.

[0056] In process step B), preferably from 500 PLU to 2000 PLU, preferably from 200 PLU to 1500 PLU, more preferably from 25 PLU to 1250 PLU of lipase are used according to the invention per gram of sorbitol to be converted.

[0057] According to the invention, process step B) is preferably carried out at a pressure of less than 1 bar, preferably less than 0.5 bar, more preferably less than 0.1 bar.

[0058] According to the invention, process step B) is alternatively preferably carried out in a bubble column reactor, wherein at least one inert gas is passed through the reaction mixture; the inert gas is preferably selected from the group comprising, preferably consisting of, nitrogen and argon. In this respect, it is preferred according to the invention that the gas feed amount is 1 to 60 kg / h, preferably 5 to 25 kg / h, even more preferably 10 to 14 kg / h.

[0059] According to the invention, process step B) is preferably characterized in that process step B) is ended at the latest 180 hours, preferably 120 hours, particularly preferably 100 hours after the addition of the lipase.

[0060] A preferred process according to the invention is characterized in that the molar ratio of sorbitol provided to the acyl groups contained in all acyl donors provided is 1.00:0.50 to 1.00:5.00, preferably 1.00:0.70 to 1.00:3.00, particularly preferably 1.00:1.00 to 1.00:2.25, alternatively particularly preferably 1.00:2.3 to 1.00:4.50.

[0061] A preferred process according to the invention is characterized in that by-products formed in process step B), such as water when the acyl donor used is an acid and the corresponding alcohol when the acyl donor used is an ester, are removed. This can be achieved, for example, by distillation.

[0062] Process step C) of the process according to the invention comprises purifying the sorbitol carboxylate.

[0063] For this purpose, all methods which allow sorbitol carboxylate to be obtained in higher concentrations can be used.

[0064] Preferably according to the invention, the process according to the invention comprises isolating the lipase used in the process according to the invention in process step C).

[0065] When the lipase is present in a form immobilized on a carrier, the lipase is preferably separated according to the invention by filtration through a filter, in particular a bag filter, having a fineness of 0.1 μ to 1250 μ, preferably 0.5 μ to 100 μ.

[0066] Preferably according to the invention, the process according to the invention is characterized in that no molecular sieves are used therein.

[0067] Preferably according to the invention, the process according to the invention is characterized in that the substrate is used in a form which is not immobilized on a solid support, such as silica.

[0068] A further subject of the present invention are sorbitol carboxylic acid esters obtainable by the process according to the invention.

[0069] According to the present invention, sorbitol carboxylate is preferred, which contains

[0070] carboxylic acid esters of sorbitol, carboxylic acid esters of 1,4-sorbitan, carboxylic acid esters of 2,5-sorbitan, carboxylic acid esters of 1,5-sorbitan and carboxylic acid esters of isosorbide, wherein the weight ratio of the sorbitol residues contained in the sorbitol carboxylic acid esters to the sum of all the 1,4-sorbitan residues, 2,5-sorbitan residues, 1,5-sorbitan residues and isosorbide residues contained in the sorbitol carboxylic acid esters is greater than 90:10, preferably greater than 93:7, more preferably greater than 95:5, most preferably greater than 96:4,

[0071] The invention is characterized in that the molar ratio of the esterified primary hydroxyl group to the esterified secondary hydroxyl group in the carboxylic acid ester of sorbitol is 80:20 to 20:80, preferably 70:30 to 30:70, even more preferably 60:40 to 40:60, even more preferably 55:45 to 45:55.

[0072] It is clear and obvious from the expression “sorbitan carboxylates containing sorbitan carboxylates, 1,4-sorbitan carboxylates, 2,5-sorbitan carboxylates, 1,5-sorbitan carboxylates and isosorbide carboxylates, wherein the weight ratio of the sorbitol residues contained in the carboxylates to the sum of all 1,4-sorbitan residues, 2,5-sorbitan residues, 1,5-sorbitan residues and isosorbide residues contained in the carboxylates is greater than 90:10” that, in the sorbitan carboxylates of the present invention, the content of at least one selected from 1,4-sorbitan carboxylates, 2,5-sorbitan carboxylates, 1,5-sorbitan carboxylates and isosorbide carboxylates must be non-0 (zero) because the divisor 0 is not defined.

[0073] The weight ratio of the sorbitol residue contained in the sorbitol carboxylate of the present invention to the sum of all 1,4-sorbitan residues, 2,5-sorbitan residues, 1,5-sorbitan residues and isosorbide residues contained in the sorbitol carboxylate of the present invention is determined by high performance liquid chromatography (HPLC). The method comprises carrying out alkaline hydrolysis of the analyzed sorbitol carboxylate, removal of carboxylic acid and analysis of sorbitol and its degradation products 1,4-sorbitan, 2,5-sorbitan and 1,5-sorbitan and isosorbide. For this purpose, 150 mg of the analyzed sorbitol carboxylate are pre-loaded in 2.00 ml of 1M KOH aqueous solution and hydrolyzed at 95° C. for 30 minutes under stirring. The reaction solution is then cooled to room temperature and adjusted to pH 2-3 with 2M HCl aqueous solution. The resulting precipitated carboxylic acid was then extracted with diethyl ether (3 x 3.00 ml), wherein the organic supernatant was removed with a pipette after each extraction. After extraction, the aqueous solution was heated to 50° C. for 20 minutes with stirring, wherein the remaining ether (boiling point of diethyl ether: 34.6° C.) was removed. The solution obtained above was made up to 10.0 ml with redistilled H2O, then diluted 1:10, and an aliquot of the solution was analyzed by HPLC. The analysis was performed under the following conditions:

[0074] Column: Aminex HPX-87C column 300 x 7.8 mm

[0075] Eluent: H2O

[0076] Injection volume: 10.0 µl

[0077] Flow rate: 0.60 ml / min

[0078] Column temperature: 50℃

[0079] Detector: G1362A / 1260 RID (from Agilent), 35°C

[0080] Run time: 30.0 min

[0081] Sorbitol and its degradation products were separated by ion exchange. For evaluation, the ratio of the peak area of ​​sorbitol to the sum of the peak areas of 1,4-sorbitan, 2,5-sorbitan, 1,5-sorbitan and isosorbide was calculated. Reference materials for sorbitol degradation products are commercially available or can alternatively be obtained by heating pure sorbitol in the presence of an acidic (>140°C) or basic (>180°C) catalyst.

[0082] The molar ratio of esterified primary hydroxyl group to esterified secondary hydroxyl group in the carboxylic acid ester of sorbitol is determined by 13 C-NMR spectroscopy. For sample preparation, 50-70 mg of the substance are dissolved in 1 ml of a deuterated solvent to which a relaxation promoter (chromium(III) acetylacetonate, 1%) has been added. Based on the product properties, DMSO-d6, CDCl3 and methanol-d4 have been found to be suitable solvents. If the sample does not completely dissolve in one of these solvents, a solvent mixture must be found. The prepared sample solution is transferred to a 5 mm NMR tube and introduced into the NMR spectrometer.

[0083] NMR spectroscopy studies can in principle be carried out using any commercial NMR instrument. For the present NMR spectroscopy studies, an Avance 400 instrument from Bruker was used. The spectra were recorded with the following parameters:

[0084] Temperature: T = 295 K, time delay: D1 = 2 s, number of scans: NS = 2048, transmitter frequency offset: O1P = 110 ppm, sweep width: SW = 300 ppm, probe: PA BBI 400 S1 H-BB-D-05-Z.

[0085] Resonance signals were recorded relative to the chemical shift of tetramethylsilane (TMS = 0 ppm) as an internal standard. Other commercial NMR instruments obtained comparable results under the same operating parameters. The area under each resonance signal was measured, that is, the area surrounded by the signal from the baseline was quantified. In the current NMR spectrum study, "TOPSPIN" software (version 3.0) was used for integration.

[0086] In order to more accurately identify the esterified primary hydroxyl and esterified secondary hydroxyl, the DEPT spectrum is first recorded. The molar ratio of the esterified primary hydroxyl to the esterified secondary hydroxyl is determined by subtracting the integral value P (the signal group of the esterified primary hydroxyl) from the integral value C (the signal group of the ester carbonyl). The integral value S of the signal group of the esterified secondary hydroxyl is thus obtained, which cannot be directly determined due to overlap with other signals.

[0087] P = esterified primary hydroxyl group [R- C H2-OC(O)R group]

[0088] C = integral value of the ester carbonyl group

[0089] S = C – P = esterified secondary hydroxyl group [R2- C H-OC(O)R group]

[0090] The determined ratio of P to S corresponds to the molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic acid ester of sorbitol.

[0091] According to the invention, sorbitol carboxylic acid esters are preferred, characterized in that the average degree of esterification of the contained sorbitol carboxylic acid esters is 0.3 to 4.0, preferably 1.0 to 3.0, more preferably 1.1 to 2.7, particularly preferably 1.3 to 2.6. According to the invention, sorbitol carboxylic acid esters are alternatively preferred, characterized in that the average degree of esterification of the contained sorbitol carboxylic acid esters is 2.7 to 4.0.

[0092] The average degree of esterification of the carboxylic acid esters of sorbitol contained in the sorbitol carboxylic acid esters according to the invention is determined, for example, by first determining the content of free sorbitol and its degradation products 1,4-sorbitan, 2,5-sorbitan, 1,5-sorbitan and isosorbide in the sorbitol carboxylic acid ester sample in question via GC or HPCL. It is necessary to additionally determine the saponification value, acid value and content of free and neutralized fatty acids (for example by GC, as described below in "Determination of the free carboxylic acid content"). Determination of the carboxylic acid composition after alkaline saponification provides the average molar mass of the esterified carboxylic acid mixture. The average degree of esterification can then be calculated from this value.

[0093] According to the invention, the preferred sorbitol carboxylic acid esters are characterized in that the sorbitol carboxylic acid esters contained contain sorbitol monoesters, sorbitol diesters and sorbitol triesters, wherein the sorbitol triesters are preferably contained in an amount of 10% to 50% by weight, preferably 15% to 45% by weight, more preferably 20% to 40% by weight, based on all the sorbitol carboxylic acid esters contained. In this respect, according to the invention, it is further preferred that the sorbitol carboxylic acid esters contained contain sorbitol monoesters, sorbitol diesters, sorbitol triesters and sorbitol tetraesters.

[0094] According to the invention, sorbitan carboxylates are preferred, characterised in that they contain 0.05 to 40% by weight, preferably 0.2 to 25% by weight, more preferably 0.5 to 10% by weight, of free sorbitol, the weight percentages being based on the entire sorbitan carboxylate.

[0095] A portion of the sample was dissolved in pyridine: chloroform (4: 1) to determine the sorbitol contained in the carboxylic acid ester of sorbitol of the present invention by GC. To 0.25 ml of this solution, 0.5 ml of MSTFA [N-methyl-N-(trimethylsilyl)trifluoroacetamide] and 0.5 ml of a mixture of N-trimethylsilyl imidazole and pyridine (11: 39) were added. The alcohol was quantitatively converted into its trimethylsilyl ether by reaction at 80° C. (30 minutes) and then detected by GC / FID. This was performed in a gas chromatograph equipped with a split / splitless injector, a capillary column and a flame ionization detector under the following conditions:

[0096] Syringe: 290℃, split 30ml

[0097] Injection volume: 1 µl

[0098] Column: 50 m * 0.32 mm HP5 1.05 µm

[0099] Carrier gas: Hydrogen, constant flow, 2 ml / min

[0100] Temperature program: 100°C to 140°C at 10°C / min, then

[0101] 140℃ to 300℃ at 5℃ / min, then

[0102] Condition at 300°C for 5 minutes.

[0103] Detector: FID, 310℃

[0104] Hydrogen 30 ml / min

[0105] Air 400ml / min

[0106] Make-up gas 12 ml / min

[0107] Sorbitol was separated and its mass proportion was determined by the internal standard method. To this end, the GC system was calibrated by measuring a mixture of sorbitol and an internal standard of known composition.

[0108] According to the invention, sorbitol carboxylates are preferred which are characterized in that they contain less than 25% by weight, preferably 0.01% to 20% by weight, more preferably 0.05% to 10% by weight, of at least one free carboxylic acid, the percentages by weight being based on the entire sorbitol carboxylate.

[0109] The at least one free carboxylic acid may be present in protonated or neutralized form.

[0110] In order to determine the free carboxylic acid content in the sorbitol carboxylate of the present invention, the acid number is first determined. By the acid number and molecular weight of the fatty acid involved, the weight ratio can be determined. Suitable methods for determining the acid number are especially those according to DGF C-V2, DIN EN ISO 2114, Ph.Eur. 2.5.1, ISO 3682 and ASTM D 974. It is known to those skilled in the art that in the case of a carboxylic acid mixture, a GC analysis can also be supplemented after the saponification of the sorbitol carboxylate to determine the mean molecular weight of the carboxylic acid mixture thus contained. For this reason, 0.6g of the sorbitol carboxylate of the present invention was boiled under reflux for 4 hours in a 0.5M KOH ethanolic solution of 25ml. The pH value is then adjusted to pH 2-3 with sulfuric acid, and the released carboxylic acid is isolated by extracting three times with each certain volume of petroleum ether. The combined extract is concentrated to about 10ml by evaporation.

[0111] Suitable methods for determining the fatty acid distribution are in particular those according to DGF C VI 11a, DGF C-VI 10 a and GATRingtest 7 / 99.

[0112] To a 0.5 ml aliquot of the petroleum ether extract obtained as described above was added 0.5 ml MTBE and 1 ml trimethylaniline hydroxide (0.2 M in methanol) in an autosampler vial and analyzed by GC. This was performed in a gas chromatograph equipped with a split / splitless injector, a capillary column and a flame ionization detector under the following conditions:

[0113] Syringe: 290℃, split 30ml

[0114] Injection volume: 1 µl

[0115] Column: 30 m * 0.32 mm HP1 0.25 µm

[0116] Carrier gas: Helium, head pressure 70 kPa

[0117] Temperature program: 80℃ - 300℃ at 8℃ / min, then

[0118] Condition at 300°C for 20 minutes.

[0119] Detector: FID, 320℃

[0120] Hydrogen 35 ml / min

[0121] Air 240 ml / min

[0122] Make-up gas 12 ml / min

[0123] Described carboxylic acid is separated with the form of their methyl esters according to its carbon chain length.Through the assessment peak area, can determine the mass ratio of these carboxylic acid methyl esters each other, and thus determine their mol ratio by their molecular weight separately, and this corresponds to the mol ratio of the relevant carboxylic acid.In addition, can also determine the mean molecular weight of this fatty acid mixture:

[0124] where a i = the normalized mass proportion of methyl carboxylate i in the mixture of all methyl carboxylates [%). i = Peak area of ​​methyl carboxylate i in the GC chromatogram [%].

[0125] where n i = the molar amount of methyl carboxylate i in 100 g of methyl carboxylate mixture [mol]; thus, each n is obtained i The ratio of the values ​​to each other corresponds to the molar ratio of the relevant carboxylic acids in the sorbitan carboxylate; thus, the total molar amount of carboxylic acids in 1 g of sorbitan carboxylate, as obtained from the saponification value (see below), is n s [mol] can be divided into its components according to the ratios mentioned. Mi = molecular weight of carboxylic acid i corresponding to the methyl ester [g / mol].

[0126] in = Average molecular weight of the carboxylic acid mixture. n i = molar amount of methyl carboxylate i in 100 g of methyl carboxylate mixture [mol]. i = molecular weight of carboxylic acid i [g / mol].

[0127] According to the invention, sorbitol carboxylates are preferred, characterized in that the total monoester portion of the sorbitol carboxylic acid ester contains 5 to 25 wt. %, preferably 7 to 15 wt. %, more preferably 9 to 13 wt. % of secondary ester regioisomers.

[0128] According to the present invention, sorbitan carboxylic acid esters are preferred, characterized in that the entire monoester portion of the sorbitan carboxylic acid ester and the entire diester portion of the sorbitan carboxylic acid ester each contain at least two regioisomers.

[0129] According to the invention, sorbitol carboxylates are preferred, characterized in that the total diester fraction of the sorbitol carboxylates contains 25 to 45% by weight, preferably 28 to 39% by weight, more preferably 30 to 37% by weight of regioisomers, wherein at least one secondary hydroxyl group is esterified.

[0130] The determination of the secondary ester regioisomer content in the entire monoester fraction of the carboxylic acid esters of sorbitol according to the invention, the determination of the triester species content based on the sum of all contained carboxylic acid esters of sorbitol, and the determination of the regioisomer content in the entire diester fraction in which at least one secondary hydroxyl group has been esterified can be carried out by gas chromatography, optionally coupled to mass spectrometry (GC-FID and GC-MS):

[0131] First, a sample of 10 mg of the corresponding sorbitol carboxylate was dissolved in 1.5 ml of chloroform, and then 0.15 ml of N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) was added. The derivatization was carried out at 80° C. for 30 minutes. A sample of the clear solution thus obtained was analyzed by GC-FID and GC-MS. The parameters of the measurement method are as follows:

[0132] Gas chromatograph: Agilent MSD 7890

[0133] Column: Agilent HP-5 (50 m, 0.32 mm, 0.5 µm),

[0134] Flow rate: Constant 2 ml / min with hydrogen (GC-MS: helium)

[0135] Temperature adjustment: 80℃, 8℃ / min; 300℃, 30 minutes, syringe 1 µl, split 1:20, detector 310℃

[0136] Detector: FID, 310℃ / GC-MS scan 35-650 d

[0137] In the GC-FID analysis, the esters contained in the sample are separated according to their total chain length. The ratio of the individual esters to each other is determined by the respective area percentages of the GC-FID peaks. The peaks are identified / assigned to the individual esters by GC-MS, optionally also compared by the retention times of the standards prepared and separated separately (e.g., for the monoesters and diesters esterified only on the primary hydroxyl group). By this method, the content of free protonated and free neutralized carboxylic acids can also be detected, because they are also derivatized.

[0138] A further subject of the present invention is the use of the sorbitol carboxylic acid esters according to the invention as viscosity regulator, care active ingredient, foam booster or solubilizer, biocide, antistatic agent, adhesive, corrosion inhibitor, dispersant, emulsifier, film former, humectant, sunscreen, oral care agent, preservative, skin care agent, hydrophilic emollient, foam stabilizer and nonionic surfactant, preferably as viscosity regulator, emulsifier, biocide and hydrophilic emollient, particularly preferably as viscosity regulator, in particular as thickener, in particular in cleaning or care formulations.

[0139] The invention is described by way of example in the following examples, without intending to limit the invention to the embodiments mentioned in the examples, the scope of application of the invention being derived from the entire description and the claims.

[0140] Example:

[0141] Various sorbitol carboxylates were prepared as described below.

[0142] Methods for determining color values

[0143] A 25% solution of the sample to be tested is prepared in a mixture of concentrated acetic acid and toluene (3:1), optionally filtered to clarity. An aliquot (approximately 10 g, so that the cuvette is fully filled) is measured at room temperature in a Lico 690 spectrocolorimeter in an 11 mm round cuvette and the color value indicated is recorded in each case.

[0144] Example 1: Enzymatic esterification of sorbitol with 1.55 equivalents of octanoic acid (according to the present invention)

[0145] A mixture of sorbitol (96.5 g, 0.529 mol, 1.00 equiv) and octanoic acid (acid value = 389 mg KOH / g, > 98%, 118.34 g, 0.821 mol, 1.55 equiv) was heated to 100°C with stirring and N2. After 1 h, the mixture was cooled to 85°C, immobilized Candida antarctica lipase B enzyme (6.44 g; Purolite D5619, corresponding to 55747 PLU) was added, and further stirred at 85°C and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80°C through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid value of 3.0 mg KOH / g.

[0146] Example 1B: Sorbitan ester according to "Example 0" in DE102009001748A (not according to the invention)

[0147] A mixture of sorbitol (70% aqueous solution, 390.45 g, 1.50 mol, 1.00 eq.), phosphoric acid (2.9 g) and sodium hydroxide (5.0 g) was dehydrated for 30 minutes at 140° C. Subsequently, octanoic acid (acid value = 389 mg KOH / g, >98%, 334.8 g, 2.32 mol, 1.55 eq.) was added and the mixture was stirred at 200° C. until an acid value of 8.1 mg KOH / g was reached.

[0148] Example 1C: Enzymatic esterification of sorbitol with 1.55 equivalents of octanoic acid according to Biotechnol Bioeng 1995 48 214-221 (not according to the invention)

[0149] A mixture of sorbitol (96.5 g, 0.529 mol, 1.00 eq.), octanoic acid (acid number = 389 mg KOH / g, > 98%, 118.34 g, 0.821 mol, 1.55 eq.) and Novozym 435 (57.9 g, 405475 PLU) was stirred at 90° C. and < 7 mbar for 24 hours, with continuous distillation of the water formed. The mixture was then filtered at 85° C. through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid number of 2.0 mg KOH / g.

[0150] Example 2: Enzymatic esterification of sorbitol with 2.00 equivalents of technical grade oleic acid (according to the present invention)

[0151] A mixture of sorbitol (51.3 g, 0.282 mol, 1.00 equiv) and oleic acid (acid value = 200 mg KOH / g, iodine value = 92.3 g I2 / 100 g, 157.9 g, 0.563 mol, 2.00 equiv) was heated to 100°C with stirring and N2. After 1 h, the mixture was cooled to 85°C, immobilized Candida antarctica lipase B enzyme (6.28 g; Purolite D5619, corresponding to 54361 PLU) was added, and further stirred at 85°C and 20 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80°C through a Buchner funnel with a black belt filter to remove the enzyme. The obtained product had an acid value of 4.2 mg KOH / g.

[0152] Example 2B: Enzymatic esterification of sorbitol with 1.00 equivalent of oleic acid according to Biotechnol Bioeng 1995 48 214-221 (not according to the invention)

[0153] A mixture of sorbitol (100.1 g, 0.549 mol, 1.00 equiv), oleic acid (> 99%, 155.1 g, 0.549 mol, 1.00 equiv) and Novozym 435 (38.7 g, 271126 PLU) was stirred at 90°C and < 7 mbar for 24 hours, with continuous distillation of the water formed. The mixture was then filtered at 85°C through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid number of 12.8 mg KOH / g.

[0154] Example 3: Enzymatic esterification of sorbitol with 1.50 equivalents of stearic acid (according to the present invention)

[0155] A mixture of sorbitol (62.6 g, 0.344 mol, 1.00 equiv) and stearic acid (acid value = 198 mg KOH / g, ≥ 92%, 146.7 g, 0.516 mol, 1.50 equiv) was heated to 115°C with stirring and N2. After 1 h, the mixture was cooled to 90°C, immobilized Candida antarctica lipase B enzyme (6.28 g; Purolite D5619, corresponding to 54350 PLU) was added, and further stirred at 90°C and <7 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 85°C through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid value of 6.5 mg KOH / g.

[0156] Example 3B: Enzymatic esterification of sorbitol with 1.50 equivalents of stearic acid according to Biotechnol Bioeng 1995 48 214-221 (not according to the invention)

[0157] A mixture of sorbitol (62.6 g, 0.344 mol, 1.00 eq.), stearic acid (acid number = 198 mg KOH / g, ≥92%, 146.7 g, 0.516 mol, 1.50 eq.) and Novozym 435 (7.77 g, 54393 PLU) was stirred at 90° C. and <7 mbar for 24 hours, with continuous distillation of the water formed. The mixture was then filtered at 85° C. through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid number of 10.4 mg KOH / g.

[0158] Example 4: Enzymatic esterification of sorbitol with 1.80 equivalents of lauric acid (according to the present invention)

[0159] A mixture of sorbitol (71.4 g, 0.392 mol, 1.00 equiv) and lauric acid (acid value = 280 mg KOH / g, ≥ 99%, 141.3 g, 0.705 mol, 1.80 equiv) was heated to 100°C with stirring and N2. After 1 h, the mixture was cooled to 95°C, immobilized Candida antarctica lipase B enzyme (6.38 g; Purolite D5619, corresponding to 55227 PLU) was added, and further stirred at 95°C and 20 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80°C through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid value of 3.5 mg KOH / g.

[0160] Example 4B: Sorbitol ester according to "Preparation (ii), (a)" of EP1755545B1 (not according to the invention)

[0161] Sorbitol (70% aqueous solution, 390.0 g, 1.50 mol, 1.00 equiv), lauric acid (acid number = 280 mg KOH / g, ≥ 99%, 330.0 g, 1.65 mol, 1.10 equiv) and K2CO3 (16 g) were heated to 180°C with stirring and N2, and the water formed was continuously distilled off until an acid number of 3.5 mg KOH / g was reached.

[0162] Example 4C: Sorbitol ester according to "Preparation (ii), (b)" of EP1755545B1 (not according to the invention)

[0163] A stirred mixture of sorbitol (99.0 g, 0.54 mol, 1.00 eq.), methyl laurate (140.0 g, 0.65 mol, 1.20 eq.) and K2CO3 (6 g) was heated to 160°C at 50 mbar for 5 h, during which the methanol formed was continuously distilled off.

[0164] Example 4D: Enzymatic esterification of sorbitol with 1.80 equivalents of lauric acid according to Biotechnol Bioeng 1995 48 214-221 (not according to the invention)

[0165] A mixture of sorbitol (71.4 g, 0.392 mol, 1.00 eq.), lauric acid (acid value = 280 mg KOH / g, ≥99%, 141.3 g, 0.705 mol, 1.80 eq.) and Novozym 435 (49.8 g, 348253 PLU) was stirred at 90° C. and <7 mbar for 24 hours, with continuous distillation of the water formed. The mixture was then filtered at 85° C. through a Buchner funnel with a black belt filter to remove the enzyme. The product obtained had an acid value of 2.8 mg KOH / g.

[0166] Example 5: Characterization of sorbitol carboxylate:

[0167] Table 1 compares the parameters determined in the embodiment of the present invention and in the embodiment not of the present invention.

[0168] In particular, it is apparent from Examples 4, 4B and 4C that sorbitol carboxylates prepared by the method according to the present invention have better colors than those of conventional chemical synthesis.

[0169] Table 1: Examples of the present invention are marked with *

[0170] NMR Primary vs Secondary Esters Sorbitol: Degradation Products Iodine color value in solution: Example 1* 49:51 98:2 0.1 Example 1B not applicable 14:86 2.1 Example 1C 43:57 98:2 0.1 Example 2* 48:52 98:2 0.1 Example 2B 48:52 97:3 0.8 Example 3* 46:54 99:1 0.1 Example 3B 45:55 98:2 0.1 Example 4* 47:53 98:2 0.1 Example 4B 47:53 89:11 2.2 Example 4C 34:66 78:22 1.0 Example 4D 47:53 98:2 0.1

[0171] Example 6: Thickening properties in cosmetic formulations

[0172] The thickening effect of the inventive examples was evaluated in two different formulations by comparison with the corresponding non-inventive examples:

[0173] Formulation 1 consists of an aqueous solution of 9% SLES, 3% cocamidopropyl betaine and 0.7% NaCl. The pH of formulation 1 was adjusted to 5.2 with citric acid. 1.1% of the above-mentioned example substances were incorporated into the formulation in each case by stirring at 60° C. for 30 minutes and the viscosity was measured at 22° C. using a Brookfield viscometer (spindle 62, 30 rpm in Examples 1, 1B, 1C, 2, 2B; spindle 2, 60 rpm in Examples 3, 3B, 4, 4B, 4C, 4D).

[0174] Formulation 2 consists of 5.6% AM C, 4.4% lauryl glucoside, 1.2% cocoyl glucoside and 3.6% aqueous glutamic acid solution. The pH of formulation 2 is adjusted to 5.2 with citric acid. In each case 1.0% of the above-mentioned example substances are incorporated into the formulation by stirring at 60° C. for 30 minutes and the viscosity is measured at 22° C. using a Brookfield viscometer (in Examples 1, 1B, 1C, 2, 2B, spindle 62, 30 rpm; in Examples 3, 3B, 4, 4B, 4C, 4D, spindle 2, 60 rpm).

[0175] The viscosity measurement results are shown in Table 2.

[0176] Table 2: Viscosity of Example Formulations Containing 1.1% Thickener

[0177] Example Viscosity of Formulation 1 [mPa*s] Viscosity of Formulation 2 [mPa*s] 1 The present invention 6517 4341 1B Not the present invention 6221 3723 1C Not the present invention 4627 1877 2 The present invention 93 350 2B Not the present invention 42 170 3 The present invention 50 144 3B Not the present invention 26 <![CDATA[98 § ]]> 4 The present invention 74 2027 4B Not the present invention 50 1000 4C Not the present invention 21 981 4D Not the present invention 35 200

[0178] § = Example 3B is not completely soluble in Formulation 2, which is another disadvantage of this non-inventive example.

[0179] The results in Table 2 show that higher viscosities were achieved in both formulations by inventive Example 1 than by non-inventive Examples 1B and 1C. The same was true for inventive Example 2 compared to non-inventive Example 2B, and for 3 compared to 3B and 4 compared to 4B, 4C and 4D.

[0180] Example 7: Accelerated enzymatic reaction

[0181] Document Biotechnol Bioeng 1995 48 214-221 describes the use of extremely high amounts of enzyme, i.e. about 494000 PLU per mole of used fatty acid. Such high enzyme loading is uneconomical. Interesting loading is roughly about 100000 PLU or lower per mole of used fatty acid. In the case of embodiment 3 (the present invention) and 3B (non-the present invention), after the reaction ends and after removing the enzyme, the acid value is measured and an aliquot (about 30 g) is placed in a 100 ml glass graduated cylinder in a heating cabinet at 90 ℃ for 24 hours, then the ratio (v / v) of the upper ester phase and the lower sorbitol phase is determined after phase separation. Table 2 shows the result.

[0182] Table 2: Acid value and ratio of ester phase to sorbitol phase (v / v)

[0183] Enzyme loading per mole of fatty acid Acid value after 24 hours reaction time [mg KOH / g] Ratio of ester phase to sorbitol phase (v / v) Example 3 The present invention Approximately 105,000 6.5 89:11 Example 3B Not the present invention Approximately 105,000 10.4 83:17

[0184] From the data shown in Table 2 it can be clearly seen that the process according to the invention has the advantage over the processes described in the prior art that lower acid numbers are already achieved after a reaction time of 24 hours, which is desirable, and the sorbitol phase separated in the melt likewise exhibits a smaller proportion.

[0185] A further advantage of the process according to the invention is found in the comparison of Examples 1 and 1C: despite the seven-fold higher amount of lipase, after a reaction time of 24 hours the conversion measured by the acid number in the prior art process is in the same range as in the process according to the invention.

[0186] Table 3: Acid value

[0187] Enzyme loading per mole of fatty acid Acid value after 24 hours reaction time [mg KOH / g] Example 1 The present invention Approximately 68,000 3.0 Example 1C Not the present invention About 500,000 2.0

[0188] A similar situation was found in the comparison of Examples 2 and 2B: at the same lipase amount, after a reaction time of 24 hours, the conversion measured by the acid value in the prior art process was even significantly lower than in the process according to the invention.

[0189] Table 4: Acid value

[0190] Enzyme loading per mole of fatty acid Acid value after 24 hours reaction time [mg KOH / g] Example 2 The present invention Approximately 97,000 4.2 Example 2B Not the present invention About 500,000 12.8

[0191] A similar situation was found in a comparison of Examples 4 and 4D. At the same lipase amount, after 24 hours reaction time, the conversion in the prior art process was in the same range as in the process according to the invention.

[0192] Table 5: Acid value

[0193] Enzyme loading per mole of fatty acid Acid value after 24 hours reaction time [mg KOH / g] Example 4 The present invention Approximately 78,000 3.5 Example 4D Not the present invention About 500,000 2.8

[0194] Formulation Examples

[0195] Formulations 1a, 1b and 1c: Antiperspirant / deodorant formulations containing aluminum salts

[0196] formula 1a 1b 1c Composition of Example 3 3.2% 3.2% 3.2% C18-C22 Hydroxyalkyl Hydroxypropyl Guar Gum (ESAFLOR HM 22, Lamberti SpA) 0.2% Hydroxypropyl guar gum (ESAFLOR HDR, Lamberti SpA) 0.2% 0.2% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 5.4% 5.4% 5.4% water Add to 100% Add to 100% Add to 100% Aluminum chlorohydrate (50% aqueous solution; Locron LIC, Clariant AG) 20.0% 20.0% 20.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Undecylenamidopropyltrimethylammonium methylsulfate; water; propylene glycol (dermosoft® UTM, Evonik Dr.Straetmans GmbH) 1.0%

[0197] Formulations 2a, 2b and 2c: Aluminum-free deodorant formulations without antiperspirant active ingredients

[0198] formula 2a 2b 2c Composition of Example 3 3.2% 3.2% 3.2% C18-C22 Hydroxyalkyl Hydroxypropyl Guar Gum (ESAFLOR HM 22, Lamberti SpA) 0.15% Hydroxypropyl guar gum (ESAFLOR HDR, Lamberti SpA) 0.15% 0.15% Polyglyceryl-3 Caprylate (TEGO® Cosmo P 813, Evonik Operations GmbH) 0.5% 0.5% 0.5% Zinc ricinoleate (TEGODEO® PY 88 G, Evonik Operations GmbH) 1.0% 1.0% 1.0% Caprylic / capric triglyceride (TEGOSOFT® CT, Evonik Operations GmbH) 5.65% 5.65% 5.65% water Add to 100% Add to 100% Add to 100% glycerin 3.0% 3.0% 3.0% Benzyl alcohol, benzoic acid, sorbic acid (Rokonsal BSB-N, Ashland Specialty Ingredients) 1.0% 1.0% 1.0% Citric acid (50% aqueous solution) Moderate Moderate Moderate Pentylene glycol (dermosoft® Pentiol eco, Evonik Dr. Straetmans GmbH) 4.0

[0199] Formulations 3a, 3b and 3c: O / W deodorant lotions containing potassium alum

[0200] formula 3a 3b 3c Composition of Example 3 4.8% 4.8% 4.8% C18-C22 Hydroxyalkyl Hydroxypropyl Guar Gum (ESAFLOR HM 22, Lamberti SpA) 0.25% Hydroxypropyl guar gum (ESAFLOR HDR, Lamberti SpA) 0.25% 0.25% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 5.0% 5.0% 5.0% water Add to 100% Add to 100% Add to 100% glycerin 3.0% 3.0% 3.0% Potassium Alum 5.0% 5.0% 5.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Pentylene glycol (dermosoft® Pentiol eco, Evonik Dr. Straetmans GmbH) 3.5%

[0201] Formulas 4a and 4b: Antiperspirant / Deodorant Lotion

[0202] formula 4a 4b Composition of Example 3 3.0% 3.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 3.0% 3.0% PPG-14 butyl ether (TEGOSOFT® PBE, Evonik Operations GmbH) 3.0% 3.0% Polyglyceryl-3 Caprylate (TEGO® Cosmo P813, Evonik Operations GmbH) 0.5% 0.5% Demineralized water Add to 100% Add to 100% Hydroxyethylcellulose (Natrosol 250 HHR, Ashland Specialty Chemicals) 1.0% 1.0% Aluminum chlorohydrate (50%) (Reach 501L, Reheis) 15.0% 15.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 3.0% 1,2-Hexanediol (dermosoft® Hexiol, Evonik Dr. Straetmans GmbH) 2.8%

[0203] Formulas 5a, 5b, and 5c: Antiperspirant / Deodorant Cream

[0204] formula 5a 5b 5c Composition of Example 3 3.0% 2.5% 2.5% Sodium cetearyl sulfate (Lanette E, BASF SE) 0.5% 0.5% Glyceryl Stearate 1.0% 1.0% 1.0% Stearyl Alcohol 1.0% 1.0% 1.0% PPG-15 stearyl ether 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 5.0% 5.0% 5.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 5.0% 5.0% 5.0% 2.0% 2.0% 2.0% Polyglyceryl-3 Caprylate (TEGO® Cosmo P813, Evonik Operations GmbH) 0.5% 0.5% 0.5% Zinc ricinoleate (TEGODEO® PY88 G, Evonik Operations GmbH) 1.0% 1.0% 1.0% Demineralized water Add to 100% Add to 100% Add to 100% Hydroxyethylcellulose (Natrosol 250 HHR (Ashland Specialty Chemicals) 1.0% 1.0% 1.0% Aluminum chlorohydrate (50% aqueous solution; Locron LIC, Clariant AG) 15.0% 15.0% 15.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Methylpropanediol; Caprylyl glycol; Phenylpropanol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 3.5%

[0205] Formulas 6a and 6b: Sunscreen Spray SPF 30

[0206] formula 6a 6b Composition of Example 3 4.0% 4.0% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 3.2% 3.2% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 2.0% 2.0% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 3.0% 3.0% Butyl Methoxydibenzoylmethane 2.0% 2.0% EHC 2.0% 2.0% Ethylhexyl salicylate 4.0% 4.0% Octocrylene 4.0% 4.0% glycerin 3.0% 3.0% water Add to 100% Add to 100% Carbomer Suspension 1 (Acrylates / C10-30 Alkyl Acrylate Crosspolymer, TEGO® Carbomer 341ER, Evonik Operations GmbH, 20% in Phenoxyethyl Caprylate) 1.0% 1.0% Tris(hydroxymethyl)aminomethane (30% aqueous solution) 0.6% 0.6% UV filter solution (20% phenylbenzimidazole sulfonic acid, 8.8% tris(hydroxymethyl)aminomethane, demineralized water to 100%) 10.0% 10.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% Methylpropanediol; Caprylyl glycol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 4.0

[0207] Formulas 7a, 7b and 7c: Sunscreen spray

[0208] formula 7a 7b 7c Composition of Example 3 3.0% 2.5% 2.5% Glyceryl citrate stearate (AXOL® C 62, Evonik Operations GmbH) 0.5% 0.5% Glyceryl Stearate 0.5% 0.5% 0.5% Stearyl Alcohol 0.5% 0.5% 0.5% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 3.0% 3.0% 3.0% Butyl Methoxydibenzoylmethane 2.0% 2.0% 2.0% Ethylhexyl methoxycinnamate 2.0% 2.0% 2.0% Ethylhexyl salicylate 4.0% 4.0% 4.0% Octocrylene 4.0% 4.0% 4.0% Isopropyl Palmitate 2.0% 2.0% 2.0% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 3.2% 3.2% 3.2% glycerin 3.0% 3.0% 3.0% Demineralized water Add to 100% Add to 100% Add to 100% Carbomer suspension (acrylates / C10-30 alkyl acrylate crosspolymer, TEGO® Carbomer 341ER, 20% in phenoxyethyl octanoate) 1.0% 1.0% 1.0% Tromethamine (30%) 0.9% 0.9% 0.9% UV filter solution (20% phenylbenzimidazole sulfonic acid, 8.8% tris(hydroxymethyl)aminomethane, demineralized water to 100%) 10.0% 10.0% 10.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Methylpropanediol; Caprylyl glycol; Phenylpropanol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 3.0%

[0209] Formulas 8a, 8b and 8c: Sunscreen lotion SPF 30

[0210] formula 8a 8b 8c Composition of Example 3 3.00% 2.00% 2.00% Cetearyl Glucoside (TEGO® Care CG 90, Evonik Operations GmbH) 0.50% 0.50% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 8.00% 8.00% 8.00% Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A Plus, BASF SE) 6.00% 6.00% 6.00% Ethylhexyl methoxycinnamate 8.00% 8.00% 8.00% Stearyl Alcohol 1.00% 1.00% 1.00% Glyceryl Stearate 1.00% 1.00% 1.00% Tocopheryl acetate 0.50% 0.50% 0.50% glycerin 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Tromethamine 0.90% 0.90% 0.90% Phenylbenzimidazole sulfonic acid 2.00% 2.00% 2.00% Acrylates / C10-30 Alkyl Acrylate Crosspolymer (TEGO® Carbomer 341 ER, Evonik Operations GmbH) 0.30% 0.30% 0.30% Sodium hydroxide (10% aqueous solution) Moderate Moderate Moderate Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Caprylyl glycol; glycerin; glyceryl caprylate; phenylpropanol; water (dermosoft® LP MB; Evonik Dr. Straetmans GmbH) 1.0

[0211] Formulas 9a, 9b and 9c: Sunscreen lotion SPF 30, high UVA protection

[0212] formula 9a 9b 9c Composition of Example 3 3.00% 2.50% 2.50% Sodium cetearyl sulfate (Lanette E, BASF SE) 0.50% 0.50% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 7.30% 7.30% 7.30% Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Diethylhexyl butyramido triazone (UVAsorb HEB, 3V Sigma) 1.00% 1.00% 1.00% Ethylhexyl salicylate 1.50% 1.50% 1.50% Octocrylene 3.50% 3.50% 3.50% Titanium dioxide; diethylhexyl carbonate; polyglyceryl-6 polyhydroxystearate (TEGO® Sun TDEC 45, Evonik Operations GmbH) 2.20% 2.20% 2.20% Stearyl Alcohol 1.00% 1.00% 1.00% Nylon-10 / 10 (TEGOLON® ECO 10-10, Evonik Operations GmbH) 0.50% 0.50% 0.50% Glyceryl Stearate 1.00% 1.00% 1.00% Tocopheryl acetate 0.50% 0.50% 0.50% glycerin 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Citric acid (50% aqueous solution) 0.10% 0.10% 0.10% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 20.00% 20.00% 20.00% Acrylates / C10-30 Alkyl Acrylate Crosspolymer (TEGO® Carbomer 341 ER, Evonik Operations GmbH) 0.30% 0.30% 0.30% Sodium hydroxide (10% aqueous solution) 0.90% 0.90% 0.90% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Triethyl citrate; Caprylyl glycol; Benzoic acid (Verstatil® TBO; Evonik Dr. Straetmans GmbH) 1.0%

[0213] Formulas 10a, 10b and 10c: Sunscreen lotion SPF 30

[0214] formula 10a 10b 10c Composition of Example 3 3.00% 2.00% 2.00% Methylglucose sesquistearate (TEGO® Care PS, Evonik Operations GmbH) 1.00% 1.00% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 1.50% 1.50% 1.50% Octocrylene 10.00% 10.00% 10.00% Butyl Methoxydibenzoylmethane 3.50% 3.50% 3.50% Titanium dioxide; diethylhexyl carbonate; polyglyceryl-6 polyhydroxystearate (TEGO® Sun TDEC 45, Evonik Operations GmbH) 14.50% 14.50% 14.50% Stearyl Alcohol 0.20% 0.20% 0.20% Glyceryl Stearate 0.20% 0.20% 0.20% Tocopheryl acetate 0.50% 0.50% 0.50% glycerin 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Acrylates / C10-30 Alkyl Acrylate Crosspolymer (TEGO® Carbomer 341 ER, Evonik Operations GmbH) 0.20% 0.20% 0.20% Sodium hydroxide (10% aqueous solution) 0.60% 0.60% 0.60% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Methylpropanediol; Caprylyl glycol; Phenylpropanol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 3.0%

[0215] Formulas 11a, 11b and 11c: Sunscreen lotion SPF 50, high UVA protection

[0216] formula 11a 11b 11c Composition of Example 3 3.00% 2.50% 2.50% Polyglyceryl-3 Methylglucose Distearate (TEGO® Care 450, Evonik Operations GmbH) 0.50% 0.50% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 2.00% 2.00% 2.00% Nylon-10 / 10 (TEGOLON® ECO 10-10, Evonik Operations GmbH) 0.50% 0.50% 0.50% Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Diethylhexyl butyramido triazone (UVAsorb HEB, 3V Sigma) 1.00% 1.00% 1.00% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 3.00% 3.00% 3.00% Ethylhexyl salicylate 1.00% 1.00% 1.00% Octocrylene 8.00% 8.00% 8.00% Stearyl Alcohol 0.45% 0.45% 0.45% Glyceryl Stearate 0.45% 0.45% 0.45% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.30% 0.30% 0.30% Tocopheryl acetate 0.50% 0.50% 0.50% Hydroxyethylcellulose (Natrosol 250 HHR (Ashland Specialty Chemicals) 0.50% 0.50% 0.50% Demineralized water Add to 100% Add to 100% Add to 100% Sodium hydroxide (10% aqueous solution, pH adjusted to 7.5) Moderate Moderate Moderate Disodium phenyldibenzimidazole tetrasulfonate (Neoheliopan AP, Symrise) 5.00% 5.00% 5.00% Methylene bisbenzotriazolyl tetramethylbutylphenol (Tinosorb M, BASF SE) 8.00% 8.00% 8.00% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Methylpropanediol; Caprylyl glycol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 3.8%

[0217] Formulas 12a, 12b and 12c: Sunscreen Lotion SPF 50

[0218] formula 12a 12b 12c Composition of Example 3 3.50% 3.00% 3.00% Glyceryl citrate stearate (AXOL® C 62, Evonik Operations GmbH) 1.00% 1.00% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 2.50% 2.50% 2.50% Diethylamino Hydroxybenzoyl Hexyl Benzoate 10.00% 10.00% 10.00% Ethylhexyl methoxycinnamate 10.00% 10.00% 10.00% Stearyl Alcohol 1.00% 1.00% 1.00% Glyceryl Stearate 1.00% 1.00% 1.00% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.50% 0.50% 0.50% Tocopheryl acetate 0.50% 0.50% 0.50% glycerin 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Phenylbenzimidazole sulfonic acid 4.00% 4.00% 4.00% Tromethamine 1.80% 1.80% 1.80% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Triethyl citrate; Glyceryl caprylate; Benzoic acid (Verstatil® TBG MB, Evonik Dr. Straetmans GmbH) 1.2%

[0219] Formulas 13a, 13b and 13c: Sunscreen lotion SPF 50+

[0220] formula 13a 13b 13c Composition of Example 3 3.00% 2.5% 2.5% Potassium cetyl phosphate 1.0% 1.0% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 3.00% 3.00% 3.00% Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Octocrylene 4.90% 4.90% 4.90% Ethylhexyl methoxycinnamate 0.10% 0.10% 0.10% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 4.70% 4.70% 4.70% Diethylhexyl butyramido triazone (UVAsorb HEB, 3V Sigma) 3.70% 3.70% 3.70% Titanium dioxide; diethylhexyl carbonate; polyglyceryl-6 polyhydroxystearate (TEGO® Sun TDEC 45, Evonik Operations GmbH) 11.00% 11.00% 11.00% Stearyl Alcohol 0.50% 0.50% 0.50% Glyceryl Stearate 0.50% 0.50% 0.50% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.20% 0.20% 0.20% glycerin 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Triethyl citrate; Caprylyl glycol; Benzoic acid (Verstatil® TBO; Evonik Dr. Straetmans GmbH) 0.9%

[0221] Formulas 14a and 14b: Body Lotion

[0222] formula 14a 14b Composition of Example 3 4.0% 4.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 2.5% 2.5% Caprylic / capric triglyceride (TEGOSOFT® CT, Evonik Operations GmbH) 3.5% 3.5% water Add to 100% Add to 100% Creatine (TEGO® Cosmo C 100, Evonik Operations GmbH) 0.5% 0.5% Carbomer suspension 2 (Carbomer, TEGO® Carbomer 141, Evonik Operations GmbH, 20% in ethylhexyl stearate) 1.0% 1.0% Sodium hydroxide (10% aqueous solution) 0.6% 0.6% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% Water; sodium levulinate; sodium benzoate (Verstatil® BL; Evonik Dr. Straetmans GmbH) 1.5% Glyceryl caprylate (dermosoft® GMCY MB; Evonik Dr. Straetmans GmbH) 0.3%

[0223] Recipes 15a and 15b: Natural Care Cream

[0224] formula 15a 15b Composition of Example 3 6.0% 6.0% Caprylic / capric triglyceride (TEGOSOFT® CT, Evonik Operations GmbH) 8.0% 8.0% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 11.0% 11.0% Prunus Amygdalus Dulcis (Sweet Almond) Oil 10.0% 10.0% water Add to 100% Add to 100% glycerin 3.0% 3.0% Sodium hydroxide (10% aqueous solution) 0.2% 0.2% Benzyl alcohol, benzoic acid, sorbic acid (Rokonsal BSB-N, Ashland Specialty Ingredients) 0.8% Glycerin; water; sodium levulinate; sodium anisate (dermosoft® 1388 eco; Evonik Dr. Straetmans GmbH) 3% Glyceryl caprylate (dermosoft® GMCY MB; Evonik Dr. Straetmans GmbH) 0.2%

[0225] Formulas 16a and 16b: Anti-Aging Cream

[0226] formula 16a 16b Composition of Example 3 6.0% 6.0% Caprylic / capric triglyceride (TEGOSOFT® CT, Evonik Operations GmbH) 9.5% 9.5% C12-15 Alkyl Benzoate (TEGOSOFT® TN, Evonik Operations GmbH) 9.5% 9.5% water Add to 100% Add to 100% glycerin 3.0% 3.0% Tetrapeptide-21; Glycerin; Butylene glycol; Water (TEGO® Pep 4-17, Evonik Operations GmbH) 4.0% 4.0% Sodium hyaluronate (HyaCare®, Evonik Operations GmbH) 0.1% 0.1% Hydrolyzed hyaluronic acid (HyaCare® 50, Evonik Operations GmbH) 0.1% 0.1% Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate (HyaCare® Filler CL, Evonik Operations GmbH) 5.0% 5.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% Water; sodium levulinate; potassium sorbate (Versatil SL non GMO; Evonik Dr. Straetmans GmbH) 1.2% Octanediol (dermosoft® Octiol; Evonik Dr. Straetmans GmbH) 0.2%

[0227] Formula 17a and 17b: O / W foundation

[0228] formula 17a 17b Composition of Example 3 6.0% 6.0% Myristyl myristate (TEGOSOFT® MM, Evonik Operations GmbH) 2.0% 2.0% Isopropyl myristate (TEGOSOFT® M, Evonik Operations GmbH) 6.0% 6.0% Decyl Cocoate (TEGOSOFT® DC, Evonik Operations GmbH) 6.0% 6.0% Cetyl ricinoleate (TEGOSOFT® CR, Evonik Operations GmbH) 1.0% 1.0% water Add to 100% Add to 100% glycerin 1.0% 1.0% Titanium dioxide (Hombitan AC 360, Sachtleben) 8.0% 8.0% Iron oxide (Sicovit Yellow 10E 172, Rockwood Pigments) 0.9% 0.9% Iron oxide (Sicovit Red 30E 172, Rockwood Pigments) 0.2% 0.2% Iron oxide (Sicovit Brown 70E 172, Rockwood Pigments) 0.4% 0.4% Iron oxide (Sicovit Black 80 E 172, Rockwood Pigments) 0.1% 0.1% Cellulose (TEGO® Feel Green, Evonik Operations GmbH) 2.0% 2.0% Sodium hydroxide (10% aqueous solution) 0.2% 0.2% Benzyl alcohol, benzoic acid, sorbic acid (Rokonsal BSB-N, Ashland Specialty Ingredients) 1.0% Methylpropanediol; Caprylyl glycol; Phenylpropanol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 3.2%

[0229] Formulations 18a, 18b, 18c and 18d: Body lotion containing cosmetic active ingredients

[0230] formula 18a 18b 18c 18d Composition of Example 3 3.5% 3.5% 3.0% 3.0% Stearic acid 0.5% 0.5% Glyceryl Stearate 0.5% 0.6% 0.6% 0.6% Cetearyl Alcohol 0.5% 0.6% 0.6% 0.6% Caprylic / capric triglyceride 8.5% 8.5% 8.5% 8.5% Ethylhexyl palmitate (TEGOSOFT® OP, Evonik Operations GmbH) 8.5% 8.5% 8.5% 8.5% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.8% 0.8% 0.8% 0.8% Terminalia chebula bark extract; Pentylene glycol (recommended; TEGO® Arjuna S, Evonik Operations GmbH) 2.0% 2.0% 2.0% Betaine; urea; potassium lactate; sodium polyglutamate (recommended); hydrolyzed sclerotium gum (TEGO® Smooth; Evonik Operations GmbH) 5.0% Phenoxyethanol, methylparaben, ethylparaben, propylparaben (Phenonip XB (Clariant International Ltd.) 1.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Caprylyl glycol; Glyceryl caprylate; Dipropylene glycol (dermosoft® MCAV MB; Evonik Dr. Straetmans GmbH) 1.0%

[0231] Formulas 19a, 19b, and 19c: Low-Oil Body Lotions

[0232] formula 19a 19b 19c Composition of Example 3 3.0% 2.0% 2.0% Polyglyceryl-3 dicitrate / stearate (TEGO® Care PSC 3 (Evonik Operations GmbH) 1.0% 1.0% Cetearyl Alcohol 0.5% 0.5% 0.5% Caprylic / capric triglyceride 6.5% 6.5% 6.5% Demineralized water Add to 100% Add to 100% Add to 100% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% Glycerin; Water; Sodium Levulinate; Sodium Anisate (dermosoft® 1388; Evonik Dr. Straetmans GmbH) 3.0%

[0233] Formula 20a, 20b, 20c and 20d: O / W Essence 1

[0234] formula 20a 20b 20c 20d Composition of Example 3 2.5% 2.5% 4.0% 4.0% Sodium stearoyl glutamate (Eumulgin SG, BASF SE) 1.0% Glyceryl Stearate 0.75% 0.75% Stearyl Alcohol 0.75% 0.75% Caprylic / capric triglyceride 2.0% 2.0% 2.0% 2.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 3.0% 3.0% Avocado (Persea gratis) oil 1.0% 1.0% 1.0% 1.0% Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate (HyaCare® Filler CL, Evonik Operations GmbH) 3.0% 3.0% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Butanediol 5.0% 5.0% 5.0% 5.0% Tetrapeptide-21; Glycerin; Butylene glycol; Water (TEGO® Pep 4-17, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% Hydrolyzed hyaluronic acid (HyaCare® 50, Evonik Operations GmbH) 0.1% 0.1% 0.1% 0.1% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% 0.5% Sodium hydroxide (10% aqueous solution) 0.2% 0.2% 0.2% 0.2% Benzyl alcohol, benzoic acid, sorbic acid (Rokonsal BSB-N, Ashland Specialty Ingredients) 0.8% 0.8% 0.8% Polyglutamic acid; sclerotium glucan; betaine; urea; potassium lactate (TEGO® Smooth Complex, Evonik Operations GmbH) 3.0% 3.0% 3.0% 3.0% Triethyl citrate; Glyceryl caprylate; Benzoic acid (Verstatil® TBG; Evonik Dr. Straetmans GmbH) 1.2%

[0235] Formula 20e, 20f, 20g and 20h: O / W Essence 2

[0236] formula 20e 20f 20g 20h Composition of Example 3 3.0% 3.0% 2.0% 2.0% Cetearyl Glucoside (TEGO® Care CG 90, Evonik Operations GmbH) 0.5% Polyglyceryl-3 dicitrate / stearate (TEGO® Care PSC 3, Evonik Operations GmbH) 1.5% 1.5% Glyceryl Stearate 0.75% 0.5% 0.5% 0.5% Stearyl Alcohol 0.75% 0.5% 0.5% 0.5% Caprylic / capric triglyceride 2.0% 2.0% 2.0% 2.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 3.0% Avocado (Persea gratis) oil 1.0% 1.0% 1.0% 1.0% Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate (HyaCare® Filler CL, Evonik Operations GmbH) 3.0% 3.0% 3.0% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Butanediol 5.0% 5.0% 5.0% 5.0% Tetrapeptide-21; Glycerin; Butylene glycol; Water (TEGO® Pep 4-17, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% Hydrolyzed hyaluronic acid (HyaCare® 50, Evonik Operations GmbH) 0.1% 0.1% 0.1% 0.1% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% 0.5% Sodium hydroxide (10% aqueous solution) 0.2% 0.2% 0.2% 0.2% Benzyl alcohol, benzoic acid, sorbic acid (Rokonsal BSB-N, Ashland Specialty Ingredients) 0.8% 0.8% 0.8% Polyglutamic acid; sclerotium glucan; betaine; urea; potassium lactate (TEGO® Smooth Complex, Evonik Operations GmbH) 3.0% 3.0% Triethyl citrate; Caprylyl glycol; Benzoic acid (Verstatil® TBO; Evonik Dr. Straetmans GmbH) 1.0%

[0237] Formulas 21a, 21b and 21c: O / W Concealer

[0238] formula 21a 21b 21c Composition of Example 3 4.00% 3.00% 3.00% Polyglyceryl-3 Methylglucose Distearate (TEGO® Care 450, Evonik Operations GmbH) 1.00% 1.00% Glyceryl Stearate 0.75% 0.75% 0.75% Stearyl Alcohol 0.75% 0.75% 0.75% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 7.40% 7.40% 7.40% Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate (HyaCare® Filler CL, Evonik Operations GmbH) 2.00% 2.00% 2.00% Ethylhexyl methoxycinnamate 5.00% 5.00% 5.00% Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A Plus, BASF SE) 3.00% 3.00% 3.00% Phytosphingosine 0.10% 0.10% 0.10% Hydrolyzed hyaluronic acid (HyaCare® 50, Evonik Operations GmbH) 0.10% 0.10% 0.10% Tetrapeptide-21; Glycerin; Butylene glycol; Water (TEGO® Pep 4-17, Evonik Operations GmbH) 2.00% 2.00% 2.00% Demineralized water Add to 100% Add to 100% Add to 100% Titanium dioxide (Hombitan AC 360, Sachtleben) 3.00% 3.00% 3.00% talc 2.00% 2.00% 2.00% Iron oxide (Unipure Yellow LC 182, Sensient Technologies) 0.36% 0.36% 0.36% Iron oxide (Unipure Red LC 381, Sensient Technologies) 0.12% 0.12% 0.12% Iron oxide (Unipure Black LC 989, Sensient Technologies) 0.08% 0.08% 0.08% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 4.44% 4.44% 4.44% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 4.00% 4.00% 4.00% Nylon-10 / 10 (TEGOLON® ECO 10-10, Evonik Operations GmbH) 3.00% 3.00% 3.00% glycerin 3.00% 3.00% 3.00% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.50% 0.50% 0.50% Ethanol 3.00% 3.00% 3.00% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.80% 0.80% Methylpropanediol; Caprylyl glycol (dermosoft® OMP; Evonik Dr. Straetmans GmbH) 4.0%

[0239] Formulas 22a, 22b, 22c and 22d: Body Lotion for Sensitive Skin

[0240] formula 22a 22b 22c 22d Composition of Example 3 3.0% 3.0% 3.0% 3.0% Glyceryl Stearate 0.5% 1.0% 0.5% 0.5% Cetearyl Alcohol 1.0% 1.0% 1.0% 1.0% Shea (Shea) Butter 3.0% 3.0% 3.0% 3.0% Caprylic / capric triglyceride 5.0% 5.0% 5.0% 5.0% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% glycerin 5.0% 5.0% 5.0% 5.0% Urea 10.0% 15.0% 20.0% 20.0% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% Sodium hydroxide (10% aqueous solution) (pH adjusted to 5.0) Moderate Sodium benzoate, potassium sorbate (Euxyl K 712, Schülke & Mayr GmbH) 1.2% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% Sodium anisate (dermosoft® anisate; Evonik Dr. Straetmans GmbH) 0.12% Levulinic acid; sodium levulinate; glycerin; water (dermosoft® 700B; Evonik Dr. Straetmans GmbH) 1.0% Glyceryl caprylate (dermosoft® GMC MB; Evonik Dr. Straetmans GmbH) 0.3%

[0241] Formulas 23a, 23b, 23c and 23d: Dry Skin Lotion 1

[0242] formula 23a 23b 23c 23d Composition of Example 3 3.0% 2.5% 3.0% 3.0% Sodium stearoyl glutamate (Eumulgin SG, BASF SE) 1.0% Glyceryl Stearate 1.0% 1.0% 1.5% 1.5% Cetearyl Alcohol 1.0% 1.0% 1.5% 1.5% Cetyl ricinoleate 2.0% 2.0% 2.0% 2.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 8.0% 8.0% 8.0% 8.0% Decyl Cocoate (TEGOSOFT® DC, Evonik Operations GmbH) 3.0% 3.0% 3.0% 3.0% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% glycerin 5.0% 5.0% 5.0% 5.0% Urea 10.0% 10.0% 15.0% 15.0% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% 0.8% Phenylethyl alcohol (dermosoft® PEA; Evonik Dr. Straetmans GmbH) 1.0%

[0243] Formulas 23e, 23f, 23g and 23h: Dry Skin Lotion 2

[0244] formula 23e 23f 23g 23h Composition of Example 3 2.5% 3.0% 3.0% 3.0% Polyglyceryl-6 Distearate 0.5% Stearic acid 0.5% 0.5% Glyceryl Stearate 1.5% 1.5% 1.5% 1.5% Cetearyl Alcohol 1.5% 1.5% 1.5% 1.5% Cetyl ricinoleate 2.0% 2.0% 2.0% 2.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 8.0% 8.0% 8.0% 8.0% Decyl Cocoate (TEGOSOFT® DC, Evonik Operations GmbH) 3.0% 3.0% 3.0% 3.0% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% glycerin 5.0% 5.0% 5.0% 5.0% Urea 15.0% 20.0% 20.0% 20.0% Demineralized water Add to 100% Add to 100% Add to 100% Add to 100% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% 0.8% 0.8% Phenylpropanol (dermosoft® 250 eco; Evonik Dr. Straetmans GmbH) 0.4% 1,2-Hexanediol (dermosoft® Hexiol; Evonik Dr. Straetmans GmbH) 3.0%

[0245] Formulas 24a, 24b and 24c: Paraben-free Body Lotion 1

[0246] formula 24a 24b 24c Composition of Example 3 3.0% 2.0% 3.0% (AXOL® C 62, Evonik Operations GmbH) 1.0% Glyceryl Stearate 0.2% 0.2% 0.5% Stearyl Alcohol 0.2% 0.2% 0.5% Prunus Amygdalus Dulcis (Sweet Almond) Oil 10.0% 10.0% 10.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 6.6% 6.6% 6.0% glycerin 4.0% 4.0% 4.0% Demineralized water Add to 100.0% Add to 100.0% Add to 100.0% Caprylyl glycol, glycerin, glyceryl caprylate, phenylpropanol (Dermosoft® LP; Evonik Dr. Straetmans GmbH) 1.0% 1.0% Methylpropanediol, Caprylyl Glycol, Phenylpropanol (Dermosoft® OMP, Evonik Dr. Straetmans GmbH) 4.0% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5%

[0247] Formulas 24d, 24e and 24f: Paraben-free Body Lotion 2

[0248] formula 24d 24e 24f Composition of Example 3 3.0% 3.0% 1.5% Glyceryl Stearate SE 0.5% Polyglyceryl-3 dicitrate / stearate (TEGO® Care PSC 3, Evonik Operations GmbH) 1.5% Glyceryl Stearate 0.5% 0.5% 0.5% Stearyl Alcohol 0.5% 0.5% 0.5% Prunus Amygdalus Dulcis (Sweet Almond) Oil 10.0% 10.0% 10.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 6.0% 6.0% 6.0% glycerin 4.0% 4.0% 4.0% Demineralized water Add to 100.0% Add to 100.0% Add to 100.0% Methylpropanediol, Caprylyl Glycol, Phenylpropanol (Dermosoft® OMP, Evonik Dr. Straetmans GmbH) 4.0% Octanediol (Dermosoft® Octiol; Evonik Dr. Straetmans GmbH) 0.4% 0.4% 10% p-anisic acid solution (dissolve 3.0 g sodium hydroxide in 56.5 g demineralized water, add 30.0 g glycerol and 10.0 g dermosoft® Octiol (Evonik Dr. Straetmans GmbH) and stir until the solution is clear) 2.0% 2.0% Citric acid (10% aqueous solution) (pH adjusted to 6.0) Moderate Moderate Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5%

[0249] Formula 25a and 25b: W / O Body Lotion

[0250] formula 25a 25b Composition of Example 2 2.0% 2.0% beeswax 0.5% 0.5% Castor wax 0.5% 0.5% Full liquid paraffin 10.5% 10.5% Decyl Cocoate (TEGOSOFT® DC, Evonik Operations GmbH) 8.0% 8.0% Tocopheryl acetate 0.5% 0.5% Cyclopentasiloxane 6.0% 6.0% Sodium chloride 0.5% 0.5% water Add to 100% Add to 100% glycerin 3.0% 3.0% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% Ethanol 5.0% 5.0% Glyceryl caprylate (dermosoft® GMC; Evonik Dr. Straetmans GmbH) 0.4% Zinc sulfate 1.0%

[0251] Formula 26a and 26b: W / O Cream

[0252] formula 26a 26b Composition of Example 2 2.0% 2.0% Mineral oil 17.0% 17.0% Castor wax 0.4% 0.4% Microcrystalline wax 0.6% 0.6% water Add to 100% Add to 100% Sodium chloride 0.5% 0.5% Urea 10.0% 10.0% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% Glyceryl caprylate (dermosoft® GMC; Evonik Dr. Straetmans GmbH) 0.35% Pentylene glycol (dermosoft® Pentiol eco; Evonik Dr. Straetmans GmbH) 2.0%

[0253] Recipes 27a and 27b: Instant Cream

[0254] formula 27a 27b Composition of Example 2 0.8% 0.8% Cetyl dimethicone (ABIL® Wax 9801, Evonik Operations GmbH) 1.6% 1.6% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 4.0% 4.0% Polydimethylsiloxane (ABIL® 350, Evonik Operations GmbH) 1.0% 1.0% Cyclopentasiloxane 4.0% 4.0% Magnesium Stearate 0.3% 0.3% water Add to 100% Add to 100% Propylene glycol 5.0% 5.0% Sodium chloride 1.0% 1.0% Methylisothiazolinone, methylparaben, ethylparaben; dipropylene glycol (Microcare MEM, Thor) 0.8% Glyceryl caprylate (dermosoft® GMC; Evonik Dr. Straetmans GmbH) 0.25% Phenylpropanol (dermosoft® 250 eco; Evonik Dr. Straetmans GmbH) 0.35%

[0255] Formulas 28a, 28b and 28c: Cooling Body Lotion

[0256] formula 28a 28b 28c Composition of Example 2 2.0% 1.5% 1.5% Polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate (ISOLAN® GPS, Evonik Operations GmbH) - 0.5% 0.5% Castor wax 0.5% 0.5% 0.5% beeswax 0.5% 0.5% 0.5% Ethylhexyl stearate (Tegosoft® OS, Evonik Operations GmbH) 10.0% 10.0% 10.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 8.5% 8.5% 8.5% Polydimethylsiloxane (Belsil DM 5, Wacker Chemical Corp.) 6.0% 6.0% 6.0% Tocopheryl acetate 0.5% 0.5% 0.5% glycerin 3.0% 3.0% 3.0% water Add to 100% Add to 100% Add to 100% Sodium chloride 1.0% 1.0% 1.0% Ethanol 20.0% 20.0% 20.0% Ethylhexylglycerin (dermosoft® EHG; Evonik Dr. Straetmans GmbH) 0.5%

[0257] Formulas 29a, 29b and 29c: W / O creams based on natural ingredients

[0258] formula 29a 29b 29c Composition of Example 2 3.0% 2.5% 2.5% Diisostearoyl polyglyceryl-3 dimer dilinoleate (ISOLAN® PDI, Evonik Operations GmbH) - 0.5% 0.5% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 7.0% 7.0% 7.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 3.0% 3.0% 3.0% Almond Oil 7.0% 7.0% 7.0% Shea Butter 2.0% 2.0% 2.0% Cetyl ricinoleate (TEGOSOFT® CR, Evonik Operations GmbH) 1.0% 1.0% 1.0% beeswax 0.6% 0.6% 0.6% Castor wax 0.4% 0.4% 0.4% glycerin 5.0% 5.0% 5.0% water Add to 100% Add to 100% Add to 100% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% Sodium benzoate, potassium sorbate (Euxyl K 712, Schülke & Mayr GmbH) 0.5% 0.5% Pentylene glycol (dermosoft® Pentiol eco; Evonik Dr. Straetmans GmbH) 3.0%

[0259] Formulas 30a, 30b and 30c: Cool Toning Body Lotion

[0260] formula 30a 30b 30c Composition of Example 2 3.0% 2.5% 2.5% Polyglyceryl-3 oleate (ISOLAN® GO 33, Evonik Operations GmbH) - 0.5% 0.5% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 5.0% 5.0% 5.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 12.0% 12.0% 12.0% Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) 4.0% 4.0% 4.0% Zinc stearate 0.5% 0.5% 0.5% water Add to 100% Add to 100% Add to 100% glycerin 3.0% 3.0% 3.0% Sodium chloride 1.5% 1.5% 1.5% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% 0.7% Benzyl alcohol; Caprylyl glycol; Benzoic acid (Verstatil® BOB; Evonik Dr. Straetmans GmbH) 1.5%

[0261] Formulas 31a, 31b and 31c: Moisturizing lotion containing urea

[0262] formula 31a 31b 31c Composition of Example 2 2.0% 1.5% 1.5% Cetyl PEG / PPG-10 / 1 Dimethicone (ABIL® EM 180, Evonik Operations GmbH) - 0.5% 0.5% Microcrystalline wax 0.5% 0.5% 0.5% Castor wax 0.5% 0.5% 0.5% C12-15 Alkyl Benzoate 7.5% 7.5% 7.5% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 5.0% 5.0% 5.0% Ethylhexyl palmitate (TEGOSOFT® OP, Evonik Operations GmbH) 5.0% 5.0% 5.0% Caprylic / capric triglyceride 5.0% 5.0% 5.0% glycerin 3.0% 3.0% 3.0% Urea 20.0% 20.0% 20.0% Magnesium sulfate heptahydrate 1.0% 1.0% 1.0% water Add to 100% Add to 100% Add to 100% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.70% 0.70% perfume 0.10% 0.10% 0.10% Methylpropanediol; Phenoxyethanol; Caprylyl glycol (Verstatil® MPC; Evonik Dr. Straetmans GmbH) 1.5%

[0263] Formulas 32a, 32b, 32c and 32d: W / O body lotion with a silky light feel

[0264] formula 32a 32b 32c 33d Composition of Example 2 2.5% 2.0% 2.0% 2.0% Cetyl PEG / PPG-10 / 1 Dimethicone (ABIL® EM 90, Evonik Operations GmbH) - 0.5% - - Bis-PEG / PPG-14 / 14 Dimethicone; Dimethicone (ABIL® EM 97 S, Evonik Operations GmbH) - - 1.0% 1.0% Microcrystalline wax 0.1% 0.1% 0.1% 0.1% Castor wax 0.1% 0.1% 0.1% 0.1% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 11.8% 11.8% 11.8% 11.8% Myristyl myristate (TEGOSOFT® MM, Evonik Operations GmbH) 1.0% 1.0v 1.0% 1.0% Polydimethylsiloxane (Belsil DM 5, Wacker Chemical Corp.) 8.0% 8.0% 8.0% 8.0% Polydimethylsiloxane (ABIL® 350, Evonik Operations GmbH) 0.5% 0.5% 0.5% 0.5% glycerin 3.0% 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% 1.5% water Add to 100% Add to 100% Add to 100% Add to 100% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% 0.7% Phenoxyethanol; Ethylhexylglycerin (Verstatil® PE; Evonik Dr. Straetmans GmbH) 1.0%

[0265] Formulas 33a, 33b and 33c: Baby care products

[0266] formula 33a 33b 33c Composition of Example 2 3.0% 2.0% 2.0% Liquid paraffin; petrolatum; ozokerite; glyceryl oleate; lanolin alcohol (PROTEGIN ® XN, Evonik Operations GmbH) - 1.0% 1.0% Castor wax 0.1% 0.1% 0.1% Microcrystalline wax 0.1% 0.1% 0.1% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 1.0% 1.0% 1.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 3.8% 3.8% 3.8% Ethylhexyl palmitate (TEGOSOFT® OP, Evonik Operations GmbH) 1.0% 1.0% 1.0% Almond Oil 1.0% 1.0% 1.0% Zinc Oxide 20.0% 20.0% 20.0% glycerin 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.0% 1.0% 1.0% Sodium lactate; sodium PCA; glycine; fructose; urea; niacinamide; inositol; sodium benzoate; lactic acid (LACTIL, Evonik Operations GmbH) 5.0% 5.0% 5.0% Betaine (TEGO® Natural Betaine, Evonik Operations GmbH) 3.0% 3.0% 3.0% water Add to 100% Add to 100% Add to 100% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% p-Anisic acid (dermosoft® 688; Evonik Dr. Straetmans GmbH) 0.12% Pentylene glycol (dermosoft® Pentiol eco; Evonik Dr. Straetmans GmbH) 2.5%

[0267] Formulations 34a, 34b and 34c: Foot Care Products

[0268] formula 34a 34b 34c Composition of Example 2 3.0% 2.5% 2.5% Petrolatum; Ozokerite; Hydrogenated castor oil; Glyceryl isostearate; Polyglyceryl-3 oleate (PROTEGIN ® W, Evonik Operations GmbH) - 0.5% 0.5% Castor wax 0.1% 0.1% 0.1% Microcrystalline wax 0.1% 0.1% 0.1% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 9.0% 9.0% 9.0% Ethylhexyl palmitate (TEGOSOFT® OP, Evonik Operations GmbH) 9.0% 9.0% 9.0% Stearyl heptanoate (Tegosoft® SH, Evonik Operations GmbH) 8.8% 8.8% 8.8% glycerin 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.0% 1.0% 1.0% Ceramide NP; Ceramide AP; Ceramide EOP; Phytosphingosine; Cholesterol; Sodium lauroyl lactylate; Carbomer; Xanthan gum (SK-INFLUX V, Evonik Operations GmbH) 5.0% 5.0% 5.0% Betaine (TEGO® Natural Betaine, Evonik Operations GmbH) 3.0% 3.0% 3.0% water Add to 100% Add to 100% Add to 100% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% Phenoxyethanol; Benzoic acid (Verstatil® BP; Evonik Dr. Straetmans GmbH) 1.0%

[0269] Formulas 35a and 35b: Sunscreen lotion SPF 30 UVA with insect repellent protection

[0270] formula 35a 35b Composition of Example 2 3.0% 2.0% Polyglyceryl-2 dipolyhydroxystearate (Dehymuls PGPH, BASF SE) - 1.0% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 1.5% 1.5% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 1.5% 1.5% Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A Plus, BASF SE) 5.4% 5.4% Ethylhexyl methoxycinnamate 10.0% 10.0% Octocrylene 2.0% 2.0% Polyacrylamide; C13-14 Isoparaffin; Laureth-7 (Sepigel 305, Seppic) 2.1% 2.1% Butylacetylaminopropionic acid ethyl ester (R3535, Merck KGaA) 4.0% 4.0% Tocopheryl acetate 0.5% 0.5% glycerin 3.0% 3.0% Ethanol 0.5% 0.5% Magnesium sulfate heptahydrate 1.0% 1.0% water Add to 100% Add to 100% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% perfume 0.1% 0.1%

[0271] Formulas 36a and 36b: Sunscreen lotion SPF 30 UVA according to Ecocert standards

[0272] formula 36a 36b Composition of Example 2 3.0% 2.0% Cithrol PG3PR, (Croda Int. Plc) - 1.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 2.0% 2.0% Decyl Cocoate (TEGOSOFT® DC, Evonik Operations GmbH) 10.0% 10.0% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 10.0% 10.0% Zinc oxide (zinc oxide PI, Symrise) 16.0% 16.0% Titanium dioxide (nano); aluminum oxide; stearic acid (Eusolex TS, Merck KGaA) 9.0% 9.0% water Add to 100% Add to 100% glycerin 3.0% 3.0% Magnesium sulfate heptahydrate 1.0% 1.0% Sodium benzoate, potassium sorbate (Euxyl K 712, Schülke & Mayr GmbH) 0.5% 0.5%

[0273] Formulas 37a, 37b, 37c and 37d: Sunscreen Spray SPF 30 UVA

[0274] formula 37a 37b 37c 37d Composition of Example 2 3.0% 2.0% 3.0% 2.0% Cetyl PEG / PPG-10 / 1 Dimethicone (ABIL® EM 90, Evonik Operations GmbH) - 1.0% - - Polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate (ISOLAN® GPS, Evonik Operations GmbH) - - - 1.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 13.0% 13.0% 11.3% 11.3% C12-15 Alkyl Benzoate 13.0% 13.0% 11.3% 11.3% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 1.0% 1.0% 1.5% 1.5% Butyl Methoxydibenzoylmethane - - 3.0% 3.0% Ethylhexyl methoxycinnamate 5.0% 5.0% - - Octocrylene - - 6.0% 6.0% Homosalate - - 4.0% 4.0% Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A Plus, BASF SE) 5.0% 5.0% - - water Add to 100% Add to 100% Add to 100% Add to 100% glycerin 3.0% 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.0% 1.0% 1.0% 1.0% UV filter (20% phenylbenzimidazole sulfonic acid (Eusolex 232, Merck KGaA, 8.8% tris(hydroxymethyl)aminomethane, water to 100%) 15.0% 15.0% 15.0% 15.0% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% 0.7% 0.7%

[0275] Formulas 38a, 38b, 38c and 38d: Sunscreen lotion SPF 50 UVA

[0276] formula 38a 38b 38c 38d Composition of Example 2 3.0% 2.5% 3.0% 2.5% Cetyl PEG / PPG-10 / 1 Dimethicone (ABIL® EM 90, Evonik Operations GmbH) - 1.0% - 1.0% Microcrystalline wax 0.3% 0.3% 0.3% 0.3% Castor wax 0.3% 0.3% 0.3% 0.3% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 2.4% 2.4% - - Phenoxyethyl octanoate (TEGOSOFT® XC, Evonik Operations GmbH) - - 3.9% 3.9% Bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S, BASF SE) 6.0% 6.0% - - Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A Plus, BASF SE) 7.0% 7.0% 5.0% 5.0% Butyl Methoxydibenzoylmethane - - 4.5% 4.5% Ethylhexyl salicylate 3.0% 3.0% 5.0% 5.0% Ethylhexyl methoxycinnamate 7.0% 7.0% - - Octocrylene - - 9.0% 9.0% Homosalate 3.0% 3.0% 5.0% 5.0% Ethylhexyl triazone (Uvinul T 150, BASF SE) 1.0% 1.0% 2.0% 2.0% Titanium dioxide; Silicon dioxide; Dimethicone (Parsol TX (DSM Nutritional Products Llc.) 2.0% 2.0% 2.0% 2.0% water Add to 100% Add to 100% Add to 100% Add to 100% glycerin 3.0% 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% 1.5% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% 0.7% Natural phenylethyl alcohol 0.7%

[0277] Formulas 39a, 39b and 39c: Sunscreen SPF 50 according to FDA standards

[0278] formula 39a 39b 39c Composition of Example 2 2.0% 1.5% 1.5% Lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone (ES-5300 formulation aid, Dow Corning Corp.) - 0.5% 0.5% Ethylhexyl methoxycinnamate; Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A+B, BASF SE) 7.5% 7.5% 7.5% Ethylhexyl salicylate 5.0% 5.0% 5.0% Homosalate 15.0% 15.0% 15.0% Butyl Methoxydibenzoylmethane 3.0% 3.0% 3.0% Benzophenone-3 6.0% 6.0% 6.0% Octocrylene 10.0% 10.0% 10.0% Triisostearate 2.0% 2.0% 2.0% Microcrystalline wax 1.2% 1.2% 1.2% Castor wax 0.8% 0.8% 0.8% Cetyl dimethicone (ABIL® Wax 9801, Evonik Operations GmbH) 2.0% 2.0% 2.0% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 2.0% 2.0% 2.0% water Add to 100% Add to 100% Add to 100% Sodium chloride 1.0% 1.0% 1.0% EDTA 0.1% 0.1% 0.1% Propylene glycol 3.0% 3.0% 3.0% Phenoxyethanol, ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH) 0.7% 0.7% Verstatil PC 1.0%

[0279] Formulations 40a, 40b, 40c, 40d, 40e and 40f: Foundation

[0280] formula 40a 40b 40c 40d 40e 40f Composition of Example 2 4.5% 2.5% 3.0% 2.5% 2.0% 2.0% Bis-(Glyceryl / Lauryl) Glyceryl Lauryl Dimethicone; Caprylic / Capric Triglyceride (ABIL® EM 120, Evonik Operations GmbH) - 2.0% - - - - Polyglyceryl-4 Isostearate (ISOLAN® GI 34, Evonik Operations GmbH) - - 1.0% - - - Hexadecyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone (DC-5600, DowCorning Corp.) - - - 1.0% - - Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (KF-6105, Shin-Etsu Chemical Co.) - - - - 1.0% - <![CDATA[Polyglyceryl-4 isostearate; Cetyl PEG / PPG-10 / 1 dimethicone; Hexyl laurate (ABIL® ® WE 09, Evonik Operations GmbH)]]> - - - - - 2.0% Isoamyl Cocoate (TEGOSOFT® AC, Evonik Operations GmbH) 10.8% 10.8% 10.8% 10.8% 10.8% 10.8% Oleyl erucate (TEGOSOFT® OER, Evonik Operations GmbH) 8.0% 8.0% 8.0% 8.0% 8.0% 8.0% Titanium dioxide, aluminum oxide, triethoxyoctylsilane (Hombitan AC360, Sachtleben) 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% Iron oxide (Sicovit Brown 70 E 172, Rockwood) 2.1% 2.1% 2.1% 2.1% 2.1% 2.1% Nylon-12 (TEGOLON® 12-20, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% Cyclopentasiloxane 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% Disteardimonium hectorite (Bentone 38 V CG, Elementis) 1.0% 1.0% 1.0% 1.0% 1.0% 1.0% Propylene carbonate 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% water Add to 100% Add to 100% Add to 100% Add to 100% Add to 100% Add to 100% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% glycerin 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% <![CDATA[Creatine (TEGO ® Cosmo C 100, Evonik Operations GmbH)]]> 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% Ceteareth-25; Glycerin; Cetyl Alcohol; Behenic Acid; Cholesterol; Ceramide EOP; Ceramide EOS; Ceramide NP; Ceramide NS; Ceramide AP; Hexanoyl Phytosphingosine; Hexanoyl Sphingosine (SKINMIMICS, Evonik Operations GmbH) 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% Benzyl alcohol; Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) 0.7% 0.7% 0.7% 0.7% 0.7% 0.7%

[0281] Formulations 41a, 41b, 41c, 41d, 41e, 41f and 41g: CC (color control) fluids

[0282] formula 41a 41b 41c 41d 41e 41f 41g Composition of Example 2 3.0% 2.0% 2.5% 3.0% 2.5% 2.0% 1.0% Polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate (ISOLAN® GPS, Evonik Operations GmbH) - 1.0% - - - - - Sorbitol oleate (TEGO® SMO V, Evonik Operations GmbH) - - 0.5% - - - - PEG-30 dipolyhydroxystearate (Arlacel P135, Croda) - - - 1.0% - - - Polyglyceryl-3 diisostearate (Lameform TGI, BASF SE) - - - - 1.5% - - Glyceryl Oleate, Polyglyceryl-3 Polyricinoleate, Olea Europaea (Olive) Oil Unsaponifiables (Plantasens Natural Emulsifier CP5, Clariant) - - - - - 1.0% - Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone (KF-6038, Shin-Etsu Chemical Co.) - - - - - - 1.0% Ethylhexyl methoxycinnamate; Diethylaminohydroxybenzoyl hexyl benzoate (Uvinul A+B, BASF SE) 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% Cyclopentasiloxane 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% Disteardimonium hectorite (Bentone 38 V CG, Elementis) 1.0% 1.0% 1.0% 1.0% 1.0% 1.0% 1.0% Propylene carbonate 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% Titanium dioxide, aluminum oxide, triethoxyoctylsilane (Hombitan AC360, Sachtleben) 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% talc 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% Iron oxide; triethoxyoctylsilane (Unipure Yellow LC 182 AS-EM, Sensient) 0.4% 0.4% 0.4% 0.4% 0.4% 0.4% 0.4% Iron oxide; triethoxycaprylylsilane (Unipure Red LC 381 AS-EM, Sensient) 0.12% 0.12% 0.12% 0.12% 0.12% 0.12% 0.12% Iron oxide; triethoxyoctylsilane (Unipure Black LC 989 AS-EM, Sensient) 0.08% 0.08% 0.08% 0.08% 0.08% 0.08% 0.08% Diethylhexyl carbonate (TEGOSOFT® DEC, Evonik Operations GmbH) 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% C12-15 Alkyl Benzoate 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% Isopropyl palmitate (TEGOSOFT® P, Evonik Operations GmbH) 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% 4.0% Nylon-12 (TEGOLON® 12-20, Evonik Operations GmbH) 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% water Add to 100% Add to 100% Add to 100% Add to 100% Add to 100% Add to 100% Add to 100% glycerin 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% Sodium chloride 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% 1.5% Tetrapeptide-30; Glycerin (TEGO® Pep 4-Even, Evonik Operations GmbH) 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% Phenoxyethanol; Methylparaben; Ethylparaben; Propylparaben (Phenonip XB, Clariant) 0.7% 0.7% 0.7% 0.7% 0.7% 0.7% 0.7%

[0283] Formulations 42a, 42b, 42c, 42d and 42e: Antiperspirant / deodorant spray or aerosol spray

[0284]

[0285] Formulas 43a, 43b, 43c and 43d: Sunscreen Aerosol SPF 50 UVA

[0286]

[0287] Formulation 44: Shower Gel

[0288] water Add to 100.0% Composition of Example 1 1.5% Sodium laureth sulfate (Texapon NSO, BASF, 28%) 25.0% Coco-glucoside (Plantacare 818 UP, BASF, 51%) 8.0% Cocamidopropyl betaine (TEGO® Betain F 50, Evonik, 38%) 8.0% PEG-18 Glyceryl Oleate / Cocoate (ANTIL® 171, Evonik) 1.5% Sorbitan sesquioctanoate (ANTIL® Soft SC, Evonik) 0.8% Olein (TEGIN® OV, Evonik) 0.8% Spicy Herb(IFF) 0.2% Polyglyceryl-4 caprate (TEGOSOFT® PC 41, Evonik) 0.6% Helianthus annuus seed oil (AEC Sunflower Seed Oil, A & E Connock, Perfumery & Cosmetics Ltd.) 0.2% Linalool (Lipofresh, Lipo Chemicals, Inc.) 0.1% Coumarin (Rhodiascent extra pure, Solvay Rhodia) 0.1% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 0.4% Hydroxypropyl methylcellulose (TEGOCEL ® HPM 50, Evonik) 0.2% Ethylene glycol distearate (TEGIN ® G 1100 Pellets, Evonik) 0.4% Sodium chloride 0.5% Hydroxypropyl guar hydroxypropyltrimonium chloride (Jaguar C-162, Solvay Rhodia) 0.2% dermofeel TOCO 70 non GMO 0.1% Disodium EDTA (Dissolvine NA-2-P, AkzoNobel) 0.1% preservative Moderate Citric acid Add to pH 5.2

[0289] Formulation 45: Shower Gel

[0290]

[0291] Formulation 46: Shampoo

[0292]

[0293] Formulas 47a and 47b: Shampoo

[0294] formula 47a 47b water Add to 100.0% Add to 100.0% Composition of Example 1 2.5% 2.5% Composition of Example 3 1.5% 1.5% Cocamidopropyl betaine (TEGO® Betain F 50, Evonik, 38%) 22.0% 22.0% Lauryl glucoside (Plantacare 1200 UP, BASF, 50%) 6.0% 6.0% Sodium Cocoyl Glutamate (Plantapon ACG HC, BASF) 1.5% 1.5% Sodium Cocoyl Glycinate (Hostapon SG, Clariant) 0.8% 0.8% Zinc pyrithione (Microcare ZP, Thor) 0.1% 0.1% PEG-120 Methyl Glucose Dioleate (ANTIL® 120 Plus, Evonik) 0.4% 0.4% Sodium chloride 0.5% 0.5% Isostearamide MIPA; Glyceryl laurate (ANTIL® SPA 80, Evonik) 0.5% 0.5% Xanthan gum (Keltrol CG-SFT, CP Kelco) 0.3% 0.3% Hydroxypropyl guar hydroxypropyltrimonium chloride (Jaguar C-162, Solvay Rhodia) 0.3% 0.3% Quaternary ammonium salt-80 (ABIL® Quat 3272, Evonik) 0.4% 0.4% Palmitamidopropyltrimethylammonium chloride (VARISOFT® PATC, Evonik) 0.4% 0.4% Argan Oil (Argan Oil, DSM Nutritional Products Ltd.) 0.1% 0.1% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 0.6% 0.6% Tetrasodium EDTA (Versene 100, The Dow Chemical Company) 0.1% 0.1% Caffeine (Merck KGaA / EMD Chemicals, Inc.) 0.1% 0.1% Hydrolyzed wheat protein (Gluadin WLM, BASF) 0.1% 0.1% Limonene (Dipentene No. 122, Hercules Inc.) 0.1% 0.1% Citric acid Add to pH 5.5 Add to pH 5.5 Sodium phytate; water; alcohol (dermofeel® PA-3; Evonik Dr. Straetmans GmbH (PA-3) 0.1% perfume 0.2% preservative Moderate Water; sodium levulinate; sodium benzoate (Verstatil® BL non-GMO; Evonik Dr. Straetmans GmbH) 1.2%

[0295] Preparation 48: Hand sanitizer

[0296] water Add to 100% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 4.0% alcohol 4.0% Sodium cocoyl sulfate (Texapon HC G, BASF) 3.0% Lauryl glucoside (Plantacare 1200 UP, BASF, 50%) 6.0% Composition of Example 1 3.0% Xanthan gum (Keltrol CG-SFT, CP Kelco) 1.5% Mangifera indica (Mango) fruit extract (Mango Extract, Draco Natural Products) 0.5% Limonene (Dipentene 122, Hercules Inc.) 0.1% Linalool (Lipofresh, Lipo Chemicals, Inc.) 0.1% Citric acid Add to pH 4.9 preservative Moderate dye Moderate

[0297] Formulation 49: Soap paste

[0298] water Add to 100% Propylene glycol (Euxyl K 320, Schülke & Mayr GmbH) 2.0% Coco-glucoside (Plantacare 818 UP, BASF, 51%) 10.0% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 5.0% Composition of Example 1 2.5% Disodium cocoyl glutamate (Planatpon ACG LC, BASF) 2.5% Xanthan gum (Keltrol CG-SFT, CP Kelco) 1.2% Stearic acid (Pristerene 4922, Croda Europe, Ltd.) 1.2% Citric acid Add to pH 5.5 Olive oil (Cropure Olive, Croda Europe, Ltd.) 0.2% Olein (TEGIN® OV, Evonik) 1.0% Sodium Cocoyl Glutamate (Plantapon ACG HC, BASF) 0.8% Tetrasodium EDTA (Versene 100, The Dow Chemical Company) 0.2% perfume 0.1% preservative Moderate dye Moderate

[0299] Formulation 50: Oil bath

[0300] water to 100.0% Glycine soybean oil (Cropure Soybean, Croda Europe, Ltd.) 20.0% Composition of Example 1 12.0% Polyglyceryl-3 palmitate (Dermofeel® PP, Evonik Dr. Straetmans) 4.5% Glyceryl Caprylate (Dermosoft® GMCY, Evonik Dr. Straetmans) 3.0% Jojoba oil (AEC Refined Jojoba Oil, A & E Connock, Perfumery & Cosmetics Ltd.) 1.2% Prunus amygdalus dulcis (sweet almond) oil (Cropure Almond, Croda Europe, Ltd.) 1.0% Wheat germ oil (Cropure Wheatgerm, Croda Europe, Ltd.) 0.5% Tocopherol (Euxyl K 700, Schülke & Mayr GmbH) 0.2% Limonene (Dipentene 122, Hercules Inc.) 0.1% Citral 0.1% preservative Moderate dye Moderate

[0301] Formulation 51: Micellar water for makeup removal

[0302] water Add to 100.0% perfume 0.1% Composition of Example 1 2.0% Octyl / decylamidopropyl betaine (TEGO® Betain 810, Evonik, 38%) 1.3% Polyglyceryl-6 caprylate; Polyglyceryl-3 cocoate; Polyglyceryl-4 caprate; Polyglyceryl-6 ricinoleate (TEGO® Solve 61, Evonik) 1.0% Betaine (TEGO® Natural Betaine, Evonik) 2.0% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 1.0% preservative Moderate

[0303] Formulations 52a and 52b: Solution for Wet Wipes

[0304] formula 52a 52b Composition of Example 1 3.5% 3.5% Aloe barbadensis leaf extract (Aloe-Con UP 40, Florida Food Products Inc.) 0.2% 0.2% Isopropyl myristate (TEGOSOFT® M, Evonik) 0.2% 0.2% Disodium cocoamphodiacetate (REWOTERIC® AM 2 C NM, Evonik, 39%) 1.5% 1.5% perfume 0.2% 0.2% Propylene glycol (Euxyl K 320, Schülke & Mayr GmbH) 2.5% 2.5% Hydrolyzed silk (Crosilk 10000, Croda Inc.) 0.2% 0.2% Caprylyl / decyl glucoside (Plantacare 810 UP, BASF) 1.0% 1.0% water Add to 100.0% Add to 100.0% Citric Acid Add to pH 5.0 Add to pH 5.0 Phenoxyethanol (S&M Phenoxyethanol, Schülke & Mayr GmbH) 0.5% 0.5% Dehydroacetic acid (Unisept DHA (Universal Preserv-A-Chem, Inc.) 0.1% 0.1% Sodium benzoate (Euxyl K 712, Schülke & Mayr GmbH) 0.4% 0.4% Salicylic acid (natural salicylic acid; Evonik Dr. Straetmans GmbH) 0.5%

[0305] Formulation 53: Antiperspirant deodorant

[0306]

[0307] Formulation 54: Mouthwash

[0308] Composition of Example 1 0.4% Glycolipids (Rheance One, Evonik) 0.2% Flavoring 0.2% water Add to 100.0% Sorbitol (Karion FP Liquid, Merck) 3.0% preservative Moderate dye Moderate

[0309] Preparation 55: Toothpaste

[0310]

Claims

1. A method for enzymatically preparing sorbitol carboxylate, comprising the following steps: A) providing sorbitol and at least one acyl donor selected from fatty acid esters and fatty acids, B) reacting sorbitol with the at least one acyl donor in the presence of a lipase at a temperature of 75° C. to 110° C. to obtain sorbitol carboxylate, wherein the lipase is lipase B from Candida antarctica, and optionally C) purifying the sorbitol carboxylate, Features: Process step A) comprises blending sorbitol and the at least one acyl donor at a temperature in the range of 80°C to 120°C for at least 10 minutes.

2. The method according to claim 1, characterized in that: Process step B) reacting sorbitol with the at least one acyl donor in the presence of a lipase at a temperature of 80° C. to 95° C. to obtain sorbitol carboxylate.

3. The method according to claim 1, characterized in that: Process step A) comprises blending sorbitol and the at least one acyl donor at a temperature in the range of 100° C. to 120° C. for at least 10 minutes.

4. The method according to claim 1, characterized in that: Process step A) comprises blending sorbitol and the at least one acyl donor at a temperature in the range of 80°C to 120°C for at least 60 minutes.

5. The method according to claim 1, characterized in that: The acyl donor provided in process step A) provides an acyl group which is derived from a carboxylic acid containing 2 to 34 carbon atoms.

6. The method according to claim 5, characterized in that: The acyl donor provided in process step A) provides an acyl group which is derived from a carboxylic acid containing 6 to 22 carbon atoms.

7. The method according to claim 5, characterized in that: The acyl donor provided in process step A) provides an acyl group which is derived from a natural fatty acid or a mixture thereof.

8. The method according to any one of claims 1 to 7, characterized in that: The sorbitol and the at least one acyl donor constitute at least 80% by weight, based on the entire reaction mixture at the start of process step B).

9. The method according to claim 8, characterized in that: The sorbitol and the at least one acyl donor constitute at least 95% by weight, based on the entire reaction mixture at the start of process step B).

10. The method according to any one of claims 1 to 7, characterized in that: The water content in process step B) is less than 15% by weight, based on the entire reaction mixture.

11. The method according to claim 10, characterized in that: The water content in process step B) is less than 1.0% by weight, based on the entire reaction mixture.

12. The method according to any one of claims 1 to 7, characterized in that: The process step B) is carried out at a pressure of less than 1 bar.

13. The method according to claim 12, characterized in that: The process step B) is carried out at a pressure of less than 0.1 bar.

14. The method according to any one of claims 1 to 7, characterized in that: Process step B) is completed at the latest 180 hours after the addition of the lipase.

15. The method according to claim 14, characterized in that: Process step B) is ended at the latest 100 hours after the addition of the lipase.

16. The method according to any one of claims 1 to 7, characterized in that: The molar ratio of the provided sorbitol to the acyl groups contained in all the provided acyl donors is 1.00:0.50 to 1.00:5.

00.

17. The method according to claim 16, characterized in that: The molar ratio of the provided sorbitol to the acyl groups contained in all the provided acyl donors is 1.00:0.70 to 1.00:3.

00.

18. Sorbitol carboxylate obtainable by the process according to any one of claims 1 to 17, comprising carboxylate of sorbitol, carboxylate of 1,4-sorbitan, carboxylate of 2,5-sorbitan, carboxylate of 1,5-sorbitan and carboxylate of isosorbide, wherein the weight ratio of the sorbitol residue contained in the sorbitol carboxylate to the sum of all the 1,4-sorbitan residues, 2,5-sorbitan residues, 1,5-sorbitan residues and isosorbide residues contained in the sorbitol carboxylate is greater than 90:10, Features: The molar ratio of the esterified primary hydroxyl group to the esterified secondary hydroxyl group in the carboxylic acid ester of sorbitol is 80:20 to 20:

80.

19. The sorbitol carboxylate according to claim 18, characterized in that: The weight ratio of the sorbitol residue contained in the sorbitol carboxylate to the sum of all 1,4-sorbitan residues, 2,5-sorbitan residues, 1,5-sorbitan residues and isosorbide residues contained in the sorbitol carboxylate is greater than 96:

4.

20. The sorbitol carboxylate according to claim 18, characterized in that: The molar ratio of the esterified primary hydroxyl group to the esterified secondary hydroxyl group in the carboxylic acid ester of sorbitol is 55:45 to 45:

55.

21. The sorbitol carboxylate according to any one of claims 18 to 20, characterized in that: The average degree of esterification of the contained carboxylic acid ester of sorbitol is from 0.3 to 4.

0.

22. The sorbitol carboxylate according to claim 21, characterized in that: The average degree of esterification of the contained carboxylic acid esters of sorbitol is from 1.3 to 2.

6.

23. The sorbitol carboxylate according to any one of claims 18 to 20, characterized in that: It contains from 0.05% to 40% by weight of free sorbitol.

24. The sorbitol carboxylate according to claim 23, characterized in that: It contains 0.5 to 10 wt. % free sorbitol.

25. The sorbitol carboxylate according to any one of claims 18 to 20, characterized in that: It contains less than 25% by weight of at least one free carboxylic acid.

26. The sorbitol carboxylate according to claim 25, characterized in that: It contains 0.05 to 10 wt. % of at least one free carboxylic acid.

27. The sorbitol carboxylate according to any one of claims 18 to 20, characterized in that: The carboxylic acid ester of sorbitol contains 5 to 25 wt % of secondary ester regioisomers in the entire monoester portion.

28. The sorbitol carboxylate according to claim 27, characterized in that: The carboxylic acid ester of sorbitol contains 9 to 13 wt % of secondary ester regioisomers in the entire monoester portion.

29. Use of a sorbitan carboxylate according to any one of claims 18 to 28 as a viscosity regulator, care active ingredient, foam booster or solubilizer, antimicrobial agent, antistatic agent, adhesive, corrosion inhibitor, dispersant, emulsifier, film former, humectant, sunscreen, oral care agent, preservative, skin care agent, hydrophilic emollient, foam stabilizer and nonionic surfactant.

30. Use of sorbitan carboxylate according to claim 29 as a thickener.

31. Use of sorbitan carboxylate according to claim 29 in cleaning or care formulations.

Images