Method for producing sugar esters and / or sugar alcohol esters by enzymes

Abstract

The subject of the present invention is a method for the enzymatic production of sugar esters and / or sugar alcohol esters, as well as a mixed composition comprising sugar esters and / or sugar alcohol esters.

Description

Technical Field

[0001] The subject matter of the present invention is a method for producing sugar esters and / or sugar alcohol esters by an enzyme, as well as a mixed composition containing sugar esters and / or sugar alcohol esters.

[0002] Prior Art Fatty acid esters of sugars and sugar alcohols have surfactant properties and are particularly suitable for applications in the food sector and the cosmetics industry due to their natural raw material base and sustainability.

[0003] Fatty acid esters of sugars or sugar alcohols have conventionally been synthesized by reacting sugars or sugar alcohols with fatty acid chlorides in the presence of pyridine (Surfactants, K. Kosswig in Ullmann’s Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2000, https: / / doi.org / 10.1002 / 14356007.a25_747). However, the disadvantages of this process described in the prior art are that the use of such solvents is not permitted for applications in the food or cosmetics sector, and furthermore, additional process steps such as crystallization, filtration or distillation are required for the removal of the corresponding solvents. A further disadvantage of this process described in the prior art is the quantitative liberation of HCl when using fatty acid chlorides, since HCl can cause corrosion of the metal surfaces of the reactor.

[0004] In particular, in alternative processes to the prior art used on an industrial scale, sugars or sugar alcohols are reacted with free fatty acids or fatty acid alkyl esters at a temperature of 200-250°C in the absence of a solvent, for example, in the presence of a basic catalyst such as sodium hydroxide (Roempp, Georg Thieme Verlag KG, 2019, index term “Sorbitans” und Surfactants, K. Kosswig in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2000, https: / / doi.org / 10.1002 / 14356007.a25_747). However, a drawback of this process described in the prior art is that, for example, when reacting sorbitol under the aforementioned conditions, dehydration of sugars or sugar alcohols occurs as a side reaction. This side reaction already occurs at around 140°C in the presence of an acidic catalyst. For example, sorbitol is first dehydrated (by loss of water molecules) to sorbitan, and then further dehydrated (by further loss of water molecules) to isosorbide. The sugar or sugar alcohol used thus loses its hydrophilicity and is therefore increasingly unsuitable as a hydrophilic head group of a surfactant. A further drawback of this process described in the prior art is that the resulting side reactions lead to a dark color in the resulting product, which may require further treatment with bleaching agents such as hydrogen peroxide or activated carbon in order to make the product usable, for example, in cosmetic formulations. A further drawback of this process described in the prior art is that the resulting side reactions produce an unpleasant odor in the resulting product, which may interact unfavorably with fragrances used in cosmetic formulations.

[0005] For example, the enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols in dilute solutions of organic solvents such as 2-methyl-2-butanol, pyridine, dimethylformamide, or 2-pyrrolidone has been described (A. Ducret, A. Giroux, M. Trani, and R. Lortie, Characterization of enzymatically prepared biosurfactants, J. Am. Oil Chem. Soc. 1996, 73, 109-113, doi: 10.1007 / BF02523456; M. Therisod, AM Klibanov, Facile enzymatic preparation of monoacylated sugars in pyridine, J. Am. Chem. Soc., 1986, 108 (18), pp 5638-5640; J. Chem. Soc., Perkin Trans. 1, 1989, 0). 1057-1061,10.1039 / P19890001057; AEM Janssen, C. Klabbers, MCR Franssen, K. van't Riet, Enzymatic synthesis of carbohydrate esters in 2-pyrrolidone, Enzyme and Microbial Technology, 1991, 13 (7), 565-572). However, the drawbacks of these processes described in the prior art are that the use of such solvents is unacceptable for applications in the food or cosmetic fields, and furthermore, the removal of the corresponding solvent requires additional process steps that consume a large amount of energy, such as crystallization, filtration, or distillation.

[0006] Enzymatic synthesis of fatty acid esters of sugars or sugar alcohols using dilute aqueous solutions of enzymes is described in AEM Janssen, AG Lefferts, K. van't Riet, Enzymatic synthesis of carbohydrate esters in aqueous media, Biotechnology Letters 1990, 12 (10), 711-716, DOI https: / / doi.org / 10.1007 / BF01024726; H. Seino, T. Uchibori, T. Nishitani, et al., Enzymatic synthesis of carbohydrate esters of fatty acid (I) esterification of sucrose, glucose, fructose and sorbitol, J. Am. Oil Chem. Soc. 1984, 61 1761-1765, https: / / doi.org / 10.1007 / BF02582144, and International Publication No. 9412651. The drawbacks of this process, as described in the prior art, are the additional energy-intensive process steps required to isolate the product from aqueous systems, such as crystallization, filtration, or distillation, and, in the case of buffered aqueous systems, the removal of further salt loads. A further drawback here is that the presence of water when using fatty acids as acyl donors inhibits the shift of equilibrium to the product side. A further drawback is that enzymes typically exhibit maximum performance at a specific water activity.

[0007] T. Itoh, *Ionic Liquids as Tool to Improve Enzymatic Organic Synthesis*, Chemical Reviews 2017, 117, 10567-10607, discloses the enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols using ionic liquids as solvents. However, a drawback of these processes described in the prior art is that the ionic liquid cannot remain in the product for downstream applications in the food or cosmetics industry, and therefore at least one additional energy-intensive process step, such as crystallization, filtration, or distillation, is required to remove the ionic liquid. A further drawback of these processes described in the prior art is that the ionic liquids are produced from petrochemical raw materials, and therefore their use is undesirable for natural and sustainable applications in the food or cosmetics industry. A further drawback of the processes described in the prior art is the use of fatty acid vinyl esters as acyl donors, because they release acetaldehyde, which is of toxicological concern during the reaction, complicating handling on an industrial scale and further undesirable for applications in the food or cosmetics industry. Furthermore, fatty acid vinyl esters are produced from petrochemical raw materials such as acetylene or ethylene in the presence of toxicologically questionable metal catalysts, such as mercury, cadmium, palladium, or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27_419), which prevents these raw materials from being used in natural and sustainable applications in the food or cosmetics industries.

[0008] The enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols in the presence of choline chloride (or other ammonium or phosphonium salts) to form a deep eutectic mixture has also been described (S. Siebenhaller, C. Muhle-Goll, B. Luy, F. Kirschhoefer, G. Brenner-Weiss, E. Hiller, et al., Sustainable enzymatic synthesis of glycolipids in a deep eutectic solvent system, J. Mol. Catal. B Enzym. 2016, 133, 281-287, doi: 10.1016 / j.molcatb.2017.01.015). However, a drawback of this process described in the prior art is that if choline chloride or other ammonium or phosphonium salts remain in the product, their salt properties may adversely affect the use profile of the fatty acid esters of sugars or sugar alcohols. A further drawback of this process described in the prior art is that, since industrially usable quality choline chloride is a petrochemical raw material, its presence in the product is undesirable for natural and sustainable applications in the food or cosmetics industries. Therefore, a further drawback of this process described in the prior art is that at least one additional process step is required to remove choline chloride or other ammonium or phosphonium salts, such as crystallization, filtration, or distillation.

[0009] The enzymatic esterification of individual sugars contained in honey or agave syrup using fatty acid vinyl esters as acyl donors is described in S. Siebenhaller, J. Gentes, A. Infantes, C. Muhle-Goll, F. Kirschhoefer, G. Brenner-Weiss, K. Ochsenreither, C. Syldatk, Lipase-Catalyzed Synthesis of Sugar Esters in Honey and Agave Syrup, Front. Chem. 2018, 6, Article 24, 1-9, doi: 10.3389 / fchem.2018.00024). The drawback of this process described in the prior art is the use of fatty acid vinyl esters as acyl donors, because they release acetaldehyde, which is of toxicological concern during the reaction, complicating handling on an industrial scale and making it undesirable for use in the food or cosmetic industries. Furthermore, fatty acid vinyl esters are produced from petrochemical raw materials such as acetylene or ethylene, for example, in the presence of toxicologically concerning metal catalysts such as mercury, cadmium, palladium, or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27_419), which prevents these raw materials from being used in natural and sustainable applications in the food or cosmetics industries. A further drawback of this process described in the prior art is that it uses at most 0.066 equivalents of acyl donors relative to the total amount of sugars and sugar alcohols. Another further drawback of this process described in the prior art is that, due to the use of large excesses of sugars and sugar alcohols, at least one additional process step, such as extraction, crystallization, filtration, or distillation, is required for the isolation of fatty acid esters from the sugars and sugar alcohols.Further drawbacks of this process, as described in the prior art, are that the large excess sugars and sugar alcohols used are uneconomical on an industrial scale, and that it requires the cumbersome recycling of the sugars and sugar alcohols used. Another drawback of this process, as described in the prior art, is that when honey is used as the substrate, only glucose esters are detected, and when agave syrup is used as the substrate, only fructose esters are detected; in other words, only one of the sugar components contained in honey or agave syrup is actually esterified.

[0010] Japanese Patent Publication No. 58-116688 discloses the enzyme-catalyzed esterification of polysaccharides and / or mixtures of monosaccharides and oligosaccharides, which therefore always contain oligosaccharides or polysaccharides. The reaction is carried out in water or hexane as the solvent, and comparative examples have shown that little to no conversion can be achieved with no solvent or only a small amount of solvent.

[0011] Korean Patent No. 20180007129 discloses a method for producing a mixture of sucrose esters, fructose esters, and glucose esters by enzymatic esterification of sucrose. This process is carried out in a solution diluted with water to the extent that the lauric acid used is present in a dissolved form. Under aqueous and acidic conditions, sucrose is broken down into the corresponding monosaccharides during the reaction and esterified. Since the acyl group is always used in excess of the resulting esterified sugar, the product always contains unreacted sugar. The majority of the resulting ester is always sucrose ester. A further drawback of this prior art process is that the ratio of the different sugar esters obtained cannot be predicted or controlled.

[0012] The object of the present invention was to provide a method for producing sugar esters and / or sugar alcohol esters that can overcome at least one drawback of prior art processes, wherein the sugar portion or sugar alcohol portion contains 4 to 12, preferably 4 to 6, carbon atoms. In particular, sugar esters and / or sugar alcohol esters can be represented by readily available sugars or sugar alcohols having 4 to 12, preferably 4 to 6, carbon atoms.

[0013] Detailed description of the invention Surprisingly, it was found that the problem of the present invention can be solved by the method described below.

[0014] The subject of the present invention is a method for producing a mixed composition by enzymes comprising at least two selected sugar esters and / or sugar alcohol esters, each containing 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol portion, B) A method comprising a process step of reacting a mixture comprising at least two selected from sugars and sugar alcohols with at least one acyl group donor, preferably a fatty acid acyl group donor, particularly a fatty acid acyl group donor selected from fatty acid esters and fatty acids, particularly preferably a fatty acid, in the presence of a lipase, wherein the sugars and sugar alcohols particularly contain 4 to 12, preferably 4 to 6 carbon atoms.

[0015] A further subject of the present invention is a mixed composition comprising specific sugar esters and / or sugar alcohol esters, particularly those having 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol portion.

[0016] An advantage of the present invention is that the method according to the present invention can be carried out in the absence of a solvent.

[0017] Furthermore, an advantage of the present invention is that the method according to the present invention can be carried out using natural and sustainable synthetic ingredients.

[0018] A further advantage of the present invention is that the sugar ester and / or sugar alcohol ester according to the present invention can be obtained in a homogeneous reaction mixture, and this property can be obtained even with a low degree of esterification.

[0019] A further advantage of the present invention is that the sugar ester and / or sugar alcohol ester according to the present invention has excellent color properties.

[0020] A further advantage of the present invention is that the sugar ester and / or sugar alcohol ester according to the present invention has only a slight odor, and particularly the characteristic odor of caramel is hardly felt.

[0021] An advantage of the present invention is that the substrate can be successfully converted in the mixture, while its single conversion in the absence of a solvent is not successful.

[0022] A further advantage of the present invention is that no undesirable by-products are formed by the removal of water from the sugar / sugar alcohol used, such as sorbitan from sorbitol.

[0023] A further advantage of the present invention is that the obtained sugar ester and / or sugar alcohol ester can be very easily incorporated into formulations, particularly cosmetic formulations.

[0024] A further advantage of the present invention is that a mild formulation can be produced using the obtained sugar ester and / or sugar alcohol ester.

[0025] A further advantage of the present invention is that a formulation having particularly good skin feel can be produced using the obtained sugar ester and / or sugar alcohol ester.

[0026] A further advantage of the present invention is that a sustainable formulation free of petroleum chemical components can be produced using the obtained sugar ester and / or sugar alcohol ester.

[0027] A further advantage of the present invention is that the obtained sugar ester and / or sugar alcohol ester can be produced without quantitative liberation of HCl or acetaldehyde.

[0028] A further advantage of the present invention is that the reaction can be carried out in a bubble column due to the good miscibility of the reaction batch, and as a result, a longer catalyst life can be achieved.

[0029] A further advantage of the present invention is that a large amount of acyl donor can be used relative to the total amount of sugar and / or sugar alcohol.

[0030] A further advantage of the present invention is that additional process steps such as extraction, crystallization, filtration or distillation are not required because the esters of the sugars and sugar alcohols used are obtained in a homogeneous reaction mixture.

[0031] A further advantage of the present invention is that during the reaction, two or more of the sugar components and sugar alcohol components used are esterified.

[0032] A further advantage of the present invention is that a homogeneous melt is obtained when the reaction is carried out at a relatively low degree of esterification.

[0033] The subject of the present invention is a method for producing an enzyme-containing mixed composition comprising at least two selected from sugar esters and / or sugar alcohol esters containing particularly 4 to 12, preferably 4 to 6 carbon atoms in the sugar moiety or sugar alcohol moiety, B) a process step of reacting a mixture containing at least two selected from sugars and sugar alcohols with at least one acyl group donor, preferably a fatty acid acyl group donor, particularly a fatty acid acyl group donor selected from fatty acid esters and fatty acids, particularly preferably a fatty acid, in the presence of lipase.

[0034] In this invention, the term "two selected from sugar esters and / or sugar alcohol esters" should be understood to mean that the two esters differ in terms of their sugar or sugar alcohol content. Therefore, the invention must include esters having two residues that differ in terms of sugar residues and / or sugar alcohol residues.

[0035] Unless otherwise specified, all percentages (%) shown are weight percentages.

[0036] According to the present invention, for example, agarose, amylopectin, amylose, cellulose, chitin, cyclodextrin, dextran, fructan, glycogen, hyaluronic acid, inulin, isomerisitose, maltohexose, maltopentose, maltotetrose, maltotriose, meriditose, pectin, raffinose, stachyose, starch, starch hydrolysate, umbelliferose, cellobiose, isomalt, isomaltulose, lactitol, lactose, lactulose, mal All sugars and sugar alcohols, such as titol, maltose, maltulose, sucrose, trehalose, trehalulose, allitol, allulose, altriitol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, sreitol, xylitol, and xylose, can be used.

[0037] Preferably, according to the present invention, the sugars and sugar alcohols are selected from the group of sugars and sugar alcohols containing 4 to 12, preferably 4 to 6, carbon atoms.

[0038] Preferably, according to the present invention, sugars and sugar alcohols from the group of sugars and sugar alcohols containing 4 to 12 carbon atoms are, Selected from cellobiose, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, saccharose, trehalose, trehalulose, alitol, allulose, althritol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, sreitol, xylitol and xylose, where alitol, allulose, althritol, arabinitol, arabinose, cellobiose, deoxyribose Erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, slayitol, trehalulose, xylitol, and xylose are particularly preferred, and erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose, maltulose, mannitol, sorbitol, sorbose, xylitol, and xylose are very particularly preferred.

[0039] Preferably, according to the present invention, the sugars and sugar alcohols from the group of sugars and sugar alcohols containing 4 to 6 carbon atoms are selected from allitol, allulose, althritol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, sreitol, xylitol, and xylose, where erythritol, fructose, glucose, sorbitol, xylitol, and xylose are particularly preferred.

[0040] Particularly preferably, according to the present invention, sugars and sugar alcohols are selected from the group.

[0041] A preferred method according to the present invention is characterized in that, in process step B), the mixture comprising at least two selected from sugars and sugar alcohols excludes mixtures containing the following: Glucose, fructose, and maltose having a glucose content of 40% to 50% by weight and a fructose content of 47% to 57% by weight, respectively, relative to all sugars and sugar alcohols contained in the mixture, and Glucose, fructose, and saccharose, having a glucose content of 5% to 24% by weight and a fructose content of 75% to 94% by weight, respectively, relative to all sugars and sugar alcohols contained in the mixture.

[0042] According to the present invention, any acyl group donor can be used. These are, for example, carboxylic acid esters or carboxylic acids themselves, and mixtures thereof. Preferably, according to the present invention, the carboxylic acid ester used as the acyl group donor is selected from alkanol and polyol-based esters having up to six carbon atoms, particularly preferably alkanol and polyol-based esters having up to three carbon atoms, and very preferably glycerol esters. Particularly preferably, according to the present invention, the carboxylic acid ester used as the acyl group donor is selected from triglycerides, particularly natural fats and oils, particularly preferably from the group including coconut oil, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algal oil, sesame oil, soybean oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuacu butter, and oils having a high proportion of polyunsaturated fatty acids (PUFAS), and particularly preferably from the group consisting of these. Sorbitan esters, monoglycerides, and diglycerides containing acyl groups, as described later, can also be used in a similarly favorable manner.

[0043] Preferably, according to the present invention, the acyl group donor is selected from fatty acid acyl group donors that provide an acyl group selected from the group of acyl groups of natural fatty acids in particular. Natural fatty acids can be produced based on naturally occurring vegetable or animal oils and preferably have 6 to 30 carbon atoms, particularly 8 to 22 carbon atoms. Natural fatty acids are generally unbranched and usually consist of an even number of carbon atoms. Any double bonds have a cis configuration. Examples include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtained from the ozonolysis of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtained from the thermal decomposition of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroseric acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, and arachidonic acid.

[0044] Preferably, according to the present invention, a carboxylic acid, particularly a fatty acid, is used as the acyl group donor, and particularly preferably, the fatty acids described above are used.

[0045] Preferably, according to the present invention, vinyl esters as acyl group donors are excluded because they release acetaldehyde, which is of toxicological concern during the reaction, complicating industrial-scale handling and making them undesirable for use in the food or cosmetics industries. Furthermore, fatty acid vinyl esters are produced from petrochemical raw materials such as acetylene or ethylene in the presence of metal catalysts of toxicological concern, such as mercury, cadmium, palladium, or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27_419), which prevents these raw materials from being used in natural and sustainable applications in the food or cosmetics industries.

[0046] In particular, according to the present invention, the sugar and sugar alcohol are preferably selected from erythritol, fructose, glucose, sorbitol, xylitol, and xylose, and the acyl group donor is preferably selected from at least one of the group consisting of caproic acid, caprylic acid, pelargonic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroseric acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, and arachidonic acid.

[0047] A preferred method according to the present invention is used in process step B), wherein the mixture comprising at least two selected from sugars and sugar alcohols comprises a substance selected from the group consisting of choline salts, ammonium salts, and phosphonium salts in an amount of less than 2% by weight, preferably less than 1% by weight, and particularly preferably less than 0.1% by weight, and particularly none of these substances, where the weight percentage is relative to all sugars and sugar alcohols in step B) of the mixture comprising at least two selected from sugars and sugar alcohols.

[0048] A preferred method according to the present invention is characterized in that, in process step B), the molar ratio of all sugars and sugar alcohols to the acyl groups contained in all acyl group donors is in the range of 1.00:0.08 to 1.00:10.00, preferably 1.00:0.50 to 1.00:7.00, particularly preferably 1.00:1.25 to 1.00:2.25, or particularly preferably 1.00:2.00 to 1.00:4.50.

[0049] A preferred method according to the present invention is characterized in that, in process step B), the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols to the acyl groups contained in all acyl group donors is in the range of 1.00:0.10 to 1.00:3.00, particularly preferably 1.00:1.25 to 1.00:2.25.

[0050] A preferred method according to the present invention is characterized in that, in process step B), a mixture comprising sugars and / or sugar alcohols having 4 to 6 carbon atoms is used, and the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols having 4 to 6 carbon atoms to the acyl groups contained in all acyl group donors is in the range of 1.00:0.20 to 1.00:1.5.

[0051] The lipase preferably used in this invention is immobilized on a solid carrier. The lipases preferably used in process step B) according to the present invention are: lipase derived from Thermomyces lanuginosus (accession number O59952), lipases A and B derived from Candida antarctica (accession number P41365), lipase derived from Mucor miehei (accession number P19515), lipase derived from Humicola sp. (accession number O59952), lipase derived from Rhizomucor javanicus (accession number S32492), lipase derived from Rhizopus oryzae (accession number P61872), and Candida rugosa. Lipases derived from *Rhizopus rugosa* (accession numbers P20261, P32946, P32947, P3294 and P32949), lipases derived from *Rhizopus niveus* (accession number P61871), lipases derived from *Penicillium camemberti* (accession number P25234), lipases derived from *Aspergillus niger* (ABG73613, ABG73614 and ABG37906), and *Penicillium cyclopium* The lipase is selected from the group including cyclopium-derived lipase (accession number P61869) and those having at least 60%, preferably at least 80%, preferably at least 90%, and particularly preferably at least 95%, 98%, or 99% homology at the amino acid level.

[0052] Enzymes homologous at the amino acid level are propyl laurate units as defined in the present invention, and preferably have at least 50%, and particularly at least 90%, of the enzyme activity compared to the reference sequence.

[0053] Examples of commercially available carboxylic acid ester hydrolases, and those similarly preferred in the method according to the present invention, include the commercially available Lipozyme TL IM, Novozym 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all commercially available from Novozymes A / S, Bausvaer, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercially available from Roche Molecular Biochemicals, Mannheim, Germany), CALB Immo Plus TM from Purolite, and Lipase M "Amano" and Lipase F-AP. 15. "Amano", Lipase AY "Amano", Lipase N "Amano", Lipase R "Amano", Lipase A "Amano", Lipase D "Amano", Lipase G "Amano" (all are commercially available products from Amano Corporation in Japan).

[0054] In this invention, "homology at the amino acid level" is understood to mean "identity of amino acids," which can be determined by known methods. Generally, a specific computer program with an algorithm that takes specific requirements into account is used. A preferred method for determining identity first generates the greatest alignment between the sequences to be compared. Computer programs for determining identity include, but are not limited to, GCG program packages, which include the following: - GAP(Deveroy, J. et al., Nucleic Acid Research 12 (1984), p.387, Genetics Computer Group University of Wisconsin, Medicine (WI), and - BLASTP, BLASTN, and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), p.403-410. The BLAST program is available from the National Center for Biotechnology Information (NCBI) and other sources (BLAST Handbook, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., see above).

[0055] Those skilled in the art will recognize that various computer programs are available for calculating the similarity or identity between two nucleotide or amino acid sequences. For example, the percentage of identity between two amino acid sequences can be determined, for instance, by the algorithm by Needleman and Wunsch (J. Mol. Biol. (48). 444-453 (1970)), which is integrated into the GAP program of the GCG software package (available at http: / / www.gcg.com) and uses a Blossom 62 matrix or PAM250 matrix, gap weights of 16, 14, 12, 10, 8, 6, or 4, and length weights of 1, 2, 3, 4, 5, or 6. Those skilled in the art will recognize that while slightly different results can be obtained by using different parameters, the overall percentage of identity between two amino acid sequences will not differ significantly. The Blossom 62 matrix is ​​typically used with default settings (gap weight: 12, length weight: 1).

[0056] In this invention, an identity of 60% according to the above algorithm means 60% homology. The same applies to higher levels of identity.

[0057] Preferably, according to the present invention, process step B) is carried out at a reaction temperature in the range of 20°C to 160°C, preferably 35°C to 130°C, and particularly 50°C to 110°C.

[0058] Preferably, according to the present invention, process step B) is carried out at a pressure of less than 1 bar, preferably less than 0.5 bar, and particularly preferably less than 0.05 bar.

[0059] Alternatively, according to the present invention, process step B) is carried out in a bubble column reactor through which at least one inert gas is passed through the reaction batch, the gas being preferably selected from the group including nitrogen and argon, and more preferably selected from the group consisting of nitrogen and argon. In this context, according to the present invention, the gas flow is preferably 1 to 60 kg / h, preferably 5 to 25 kg / h, and more preferably 10 to 14 kg / h.

[0060] A preferred method according to the present invention is characterized in that, in process step B), the total of the mixture comprising at least two selected from sugars and sugar alcohols and the acyl group donor accounts for at least 10% by weight, preferably at least 86% by weight, and particularly preferably at least 90% by weight of the entire reaction batch. Accordingly, the above high weight percentage of the starting materials leaves little room for the presence of a solvent such as water or hexane.

[0061] A preferred method according to the present invention is characterized in that a solvent, particularly water or hexane, is added in an amount of up to 5% by weight, preferably up to 2% by weight, and most preferably not added at all, where the weight percentage is relative to the entire reaction batch.

[0062] A preferred method according to the present invention is characterized by the removal of by-products formed in process step B), such as water if the acyl group donor used is an acid, or the corresponding alcohol if the acyl group donor used is an ester. This can be done, for example, by distillation.

[0063] Preferably, according to the present invention, the method according to the present invention includes a process step A), i.e., a process step of mixing at least two selected from sugars and sugar alcohols, provided spatially separately from each other in solid form or in water-soluble form, to obtain a mixture containing at least two selected from sugars and sugar alcohols, which is used in process step B). Here, it may be particularly preferable to concentrate the mixture containing at least two selected from sugars and sugar alcohols and the acyl group donor by removing water, such that the total of the mixture containing at least two selected from sugars and sugar alcohols and the acyl group donor reaches at least 10% by weight, preferably at least 86% by weight, and particularly preferably at least 90% by weight of the entire reaction batch.

[0064] In this context, it is particularly preferable that process step A) includes reducing the water content of the mixture used in process step B) and comprising at least two selected from sugars and sugar alcohols to less than 17% by weight, preferably less than 14% by weight, and especially preferably less than 10% by weight, where the weight percentage is relative to the whole mixture used in process step B) and comprising at least two selected from sugars and sugar alcohols.

[0065] Preferably, according to the present invention, the method according to the present invention includes process step C) of separating lipase.

[0066] Similarly preferably, according to the present invention, the method according to the present invention includes process step D), namely, a process step of filtering a mixed composition comprising at least two selected from sugar esters and / or sugar alcohol esters through a filter having an opening of 0.1 μm to 1250 μm, preferably 0.5 μm to 100 μm, in particular a bag filter.

[0067] Preferably, according to the present invention, process step D) is carried out in a temperature range of 20°C to 150°C, particularly 40°C to 120°C.

[0068] Preferably, according to the present invention, process step D) is carried out in a pressure range of 1 bar to 25 bar, particularly 1.5 bar to 10 bar.

[0069] Preferably, according to the present invention, the method according to the present invention does not optionally include any further purification steps other than process steps C) and D).

[0070] A further subject of the present invention is a mixed composition obtained by the method according to the present invention, comprising at least two selected from sugar esters and sugar alcohol esters, each having 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol portion.

[0071] Furthermore, the subject of the present invention is a mixed composition comprising a sugar ester and / or sugar alcohol ester, wherein the sugar and / or sugar alcohol residues of the sugar ester and / or sugar alcohol ester are allitol, allulose, althritol, arabinitol, arabinose, cellobiose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, isitol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, saccharose, sorbitol, sorbose, slayitol, trehalose, trehalulose, xylitol and xylose, preferably erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose The mixed composition is characterized by being selected from at least two sugar and / or sugar alcohol residues selected from the group of maltulose, mannitol, saccharose, sorbitol, sorbose, xylitol and xylose, particularly preferably erythritol, fructose, glucose, sorbitol, xylitol and xylose residues, and the ester residue being selected from at least one acyl group of fatty acid residues, preferably caproic acid, caprylic acid, pelargonic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroseric acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0072] The preferred mixed composition according to the present invention preferably contains 4 to 6 carbon atoms in the sugar portion or sugar alcohol portion.

[0073] A preferred mixed composition according to the present invention contains sugar esters and / or sugar alcohol esters in an amount of at least 50% by weight, preferably at least 80% by weight, and particularly preferably at least 95% by weight, where the weight percentage is relative to the whole mixed composition.

[0074] A preferred mixed composition according to the present invention is characterized in that the sugar ester and / or sugar alcohol ester contained therein have a degree of esterification of 1.00 or more, particularly 1.00 to 7.00, particularly preferably 1.25 to 2.25, or particularly preferably 2.00 to 4.50.

[0075] The following embodiments are illustrative and illustrate the present invention, and there is no intention to limit the scope of the present invention, which is clear from the entirety of this specification and the claims, to the embodiments described herein.

[0076] Examples: Method for measuring acid value Preferred methods for measuring acid value are those conforming to DGF C-V2, DIN EN ISO 2114, Ph.Eur.2.5.1, ISO 3682, and ASTM D 974.

[0077] Method for measuring the specific activity of the enzyme used in PLU: To investigate the enzyme activity at PLU (propyl laurate unit), 1-propanol and lauric acid are homogeneously mixed in equimolar ratios at 60°C. The enzyme is added to initiate the reaction, and the reaction is allowed to proceed for a specified time. Samples are taken from the reaction mixture at regular intervals, and the amount of reacted lauric acid is measured by titration with potassium hydroxide solution. The enzyme activity at PLU is determined by the rate at which 1 g of the enzyme synthesizes 1 micromolar of propyl laurate per minute at 60°C. For further details, see U.S. Patent Application Publication No. 20070087418, particularly section

[0185] .

[0078] How to determine the number of colors Aliquotes (approximately 10g; enough to fully fill the cuvette) were measured using a Lico690 spectrophotometer in an 11mm round cuvette at 90°C, and the number of colors indicated for each sample was recorded.

[0079] Example 1: Enzymatic esterification of xylitol with 2.00 eq. caprylic acid (not according to the present invention) A mixture of xylitol (60.0 g, 0.394 mol, 1.00 eq.) and caprylic acid (acid value 389 mg KOH / g, >98%, 113.70 g, 0.788 mol, 2.00 eq.) was heated to 80°C with stirring through N2, and after 1 hour, the immobilized enzyme Candida antarctica lipase B (5.21 g; equivalent to Purolite D5619, 45110 PLU) was added. This mixture was stirred at 80°C and 15 mmbar for 24 hours, during which time the generated water was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 80°C through a Buchner funnel with a black ribbon filter. The obtained product was homogeneous in the molten material, colorless, and had an acid value of 1.8 mg KOH / g.

[0080] Example 2: Enzymatic esterification of fructose with 2.00 eq. caprylic acid (not according to the present invention) A mixture of fructose (83.31 g, 0.462 mol, 1.00 eq.) and caprylic acid (acid value 389 mg KOH / g, >98%, 133.36 g, 0.925 mol, 2.00 eq.) was heated to 80°C with N2 while stirring, and after 30 minutes, the immobilized enzyme Candida antarctica lipase B (6.50 g; Fermenta BIOCATALYST CALB) was added. TA10000 NLT (95%, equivalent to 63788 PLU) was added. This mixture was stirred at 80°C and 20 mg bar for 24 hours, during which time the generated water was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 80°C using a Buchner funnel with a black ribbon filter. The resulting product was heterogeneous in the molten material, exhibited a red color, and had an acid value of approximately 140.5 mg KOH / g (unambiguous measurement of the acid value was not possible due to the heterogeneity).

[0081] Example 3: A physical mixture of Example 1 and Example 2 (not according to the present invention) A mixture of the ester obtained as described in Example 1 (42.00 g) and the ester obtained as described in Example 2 (18.00 g) was heated to 80°C over 1 hour with stirring while passing N2 through it. The resulting product was heterogeneous in the molten state, turbid, orange in color, and had an acid value of approximately 40 mg KOH / g (unambiguous measurement of the acid value was impossible due to the heterogeneity).

[0082] Example 4: Enzymatic esterification of a mixture of xylitol, fructose (70:30), and 2.00 eq. caprylic acid (according to the present invention) A mixture of xylitol (42.00 g, 0.276 mol), D-(-)-fructose (18.00 g, 0.100 mol), and caprylic acid (acid value 389 mg KOH / g, >98%, 108.40 g, 0.752 mol, 2.00 eq. relative to the initial total weight of xylitol and fructose) was heated to 80°C with stirring through N2, and after 1 hour, the immobilized enzyme Candida antarctica lipase B (5.05 g; equivalent to Purolite D5619, 43724 PLU) was added. This mixture was stirred at 80°C and 15 mmbar for 27 hours, during which time the generated water was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 80°C through a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, clear and yellowish in color, and had an acid value of 2.4 mg KOH / g.

[0083] Example 5: Enzymatic esterification of xylitol with 1.50 eq. caprylic acid (not according to the present invention) A mixture of xylitol (89.14 g, 0.586 mol, 1.00 eq.) and caprylic acid (acid value 389 mg KOH / g, >98%, 126.7 g, 0.879 mol, 1.50 eq.) was heated to 80°C with N2 while stirring, and after 30 minutes, the immobilized enzyme Candida antarctica lipase B (6.47 g; Fermenta BIOCATALYST CALB) was added. TA 10,000 NLT (95%, equivalent to 63,493 PLU) was added. This mixture was stirred at 80°C and 20 mg bar for 24 hours, during which time the generated water was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 80°C using a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, colorless and clear, and had an acid value of 1.3 mg KOH / g.

[0084] Example 6: Enzymatic esterification of sorbitol with 1.50 eq. caprylic acid (not according to the present invention) A mixture of sorbitol (98.09 g, 0.538 mol, 1.00 eq.) and caprylic acid (acid value 389 mg KOH / g, >98%, 116.47 g, 0.808 mol, 1.50 eq.) was heated to 100°C with N2 while stirring, and after 30 minutes, the immobilized enzyme Candida antarctica lipase B (6.44 g; equivalent to Purolite D5619, 55759 PLU) was added. Subsequently, this mixture was stirred at 90°C and 50 millibars for 24 hours, during which time the generated water was continuously removed by distillation. The resulting product was heterogeneous and pale yellow after 24 hours and had an acid value of approximately 10-11 mg KOH / g (unambiguous measurement of the acid value was not possible due to the heterogeneity).

[0085] Example 7: Physical mixture of Example 5 and Example 6 A mixture of the ester obtained as described in Example 5 (42.00 g) and the ester obtained as described in Example 6 (18.00 g) was heated to 80°C over 1 hour with N2 while stirring. The resulting product was heterogeneous in the molten material and had an acid value of 3.7 mg KOH / g.

[0086] Example 8: Enzymatic esterification of a mixture of xylitol, sorbitol (70:30), and 1.50 eq. caprylic acid (according to the present invention) A mixture of xylitol (64.15 g, 0.421 mol), sorbitol (27.49 g, 0.151 mol), and caprylic acid (acid value 389 mg KOH / g, >98%, 123.81 g, 0.859 mol, 1.50 eq. relative to the initial total weight of xylitol and sorbitol) was heated to 80°C with N2 while stirring, and after 30 minutes, the immobilized enzyme Candida antarctica lipase B (6.02 g; Fermenta BIOCATALYST CALB) was added. TA 10000 NLT (95%, equivalent to 59077 PLU) was added. Subsequently, the mixture was stirred at 80°C and 20 mmbar for 24 hours, during which time the generated water was continuously removed by distillation. Then, to remove the enzyme, the mixture was filtered at 80°C through a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, colorless and clear, and had an acid value of 1.6 mg KOH / g.

[0087] Example 9: Enzymatic esterification of a mixture of xylitol, sorbitol (66:34), and 2.00 eq. industrial-grade oleic acid (according to the present invention) A mixture of xylitol (11.72 g, 0.077 mol), sorbitol (6.01 g, 0.033 mol), and oleic acid (acid value 200 mg KOH / g, iodine value 92.3 g I2 / 100 g, 61.7 g, 0.22 mol, 2.00 eq. relative to the initial total weight of xylitol and sorbitol) was heated to 90°C with N2 while stirring, and after 30 minutes, the immobilized enzyme Candida antarctica lipase B (2.3 g; Fermenta BIOCATALYST CALB) was added. TA 10000 NLT (95%, equivalent to 59077 PLU) was added. Subsequently, the mixture was stirred at 80°C and 10 mmbar for 24 hours, during which time the generated water was continuously removed by distillation. After that, to remove the enzyme, the mixture was filtered at 80°C using a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, slightly turbid and pale yellow in color, with an acid value of 2.0 mg KOH / g.

[0088] Example 10: Enzymatic esterification of a mixture of xylitol, sorbitol (70:30), and 2.00 eq. industrial-grade oleic acid (according to the present invention) A mixture of xylitol (28.0 g, 0.184 mol), sorbitol (12.0 g, 0.066 mol), and oleic acid (acid value 200 mg KOH / g, iodine value 92.3 g I2 / 100 g, 140.2 g, 0.50 mol, 2.00 eq. relative to the initial total weight of xylitol and sorbitol) was heated to 80°C with N2 while stirring, and after 1 hour, the immobilized enzyme Candida antarctica lipase B (5.40 g; equivalent to Purolite D5619, 46754 PLU) was added. Subsequently, this mixture was stirred at 80°C and 25 mmbar for 24 hours, during which time the generated water was continuously removed by distillation. After that, to remove the enzyme, the mixture was filtered at 80°C through a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, slightly cloudy, pale yellow in color, and had an acid value of 1.9 mg KOH / g.

[0089] Example 11: Enzymatic esterification of xylitol with 2.00 eq. stearic acid (not according to the present invention) A mixture of xylitol (40.00 g, 0.263 mol, 1.00 eq.) and stearic acid (acid value 198 mg KOH / g, >92%, 148.18 g, 0.526 mol, 2.00 eq.) was heated to 90°C with stirring through N2, and after 1 hour, the immobilized enzyme Candida antarctica lipase B (5.65 g; equivalent to Purolite D5619, 48919 PLU) was added. Subsequently, this mixture was stirred at 90°C and 15 mmbar for 24 hours, during which time the generated water was continuously removed by distillation. After that, to remove the enzyme, the mixture was filtered at 80°C through a Buchner funnel with a black ribbon filter. The obtained product was homogeneous in the molten material, clear, pale yellow in color, and had an acid value of 1.3 mg KOH / g.

[0090] Example 12: Enzymatic esterification of fructose with 2.00 eq. stearic acid (not according to the present invention) A mixture of fructose (42.00 g, 0.233 mol, 1.00 eq.) and stearic acid (acid value 198 mg KOH / g, >92%, 132.42 g, 0.482 mol, 2.00 eq.) was heated to 90°C with N2 while stirring, and after 1 hour, the immobilized enzyme Candida antarctica lipase B (5.18 g; Fermenta BIOCATALYST CALB) was added. TA 10000 NLT (95%, equivalent to 50834 PLU) was added. Subsequently, the mixture was stirred at 90°C and 15 mmbar for 51 hours, during which time the generated water was continuously removed by distillation. After that, to remove the enzyme, the mixture was filtered at 90°C using a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, clear, orange-red in color, and had an acid value of 14.7 mg KOH / g.

[0091] Example 13: A physical mixture of Example 11 and Example 12 A mixture of the ester obtained as described in Example 11 (42.00 g) and the ester obtained as described in Example 12 (18.00 g) was heated to 80°C over 1 hour with stirring while passing N2 through it. The resulting product was homogeneous in the molten state, clear, orange in color, and had an acid value of 5.1 mg KOH / g.

[0092] Example 14: Enzymatic esterification of a mixture of xylitol, fructose (70:30), and 2.00 eq. stearic acid (according to the present invention) A mixture of xylitol (28.0 g, 0.184 mol) and fructose (12.0 g, 0.067 mol) was heated to 130°C with stirring, and then cooled to 90°C after 2 hours. Subsequently, stearic acid (acid value 198 mg KOH / g, approximately 95%, 142.14 g, 0.501 mol, 2.00 eq.) was added via N2 while stirring. After stirring at 90°C for 30 minutes, the immobilized enzyme Candida antarctica lipase B (Purolite D5619, 5.46 g, equivalent to 47274 PLU) was added. Subsequently, this mixture was stirred at 90°C and 10 millibars for 24 hours, during which time the generated water was continuously removed by distillation. Next, to remove the enzyme, the mixture was filtered through a filter press equipped with a Seitz T-750 depth filter at 80°C and 2 bar N2 pressure. The resulting product was homogeneous and clear in the molten material and had an acid value of 3.2 mg KOH / g.

[0093] Example 15: Enzymatic esterification of a mixture of xylitol, sorbitol, fructose (50:25:25), and 1.91 eq. caprylic acid (according to the present invention) A mixture of xylitol (39.59 g, 0.260 mol), sorbitol (19.80 g, 0.109 mol), fructose (19.80 g, 0.110 mol), and caprylic acid (acid value 389 mg KOH / g, >98%, 138.05 g, 0.957 mol, 1.91 eq. relative to the initial total weight of xylitol, sorbitol, and fructose) was heated to 100°C with N2 while stirring and stirred for 1 hour. Subsequently, the mixture was cooled to 80°C, and the immobilized enzyme Candida antarctica lipase B (5.92 g; equivalent to Purolite D5619, 51257 PLU) was added. The mixture was further stirred at 80°C and 20 millibars for 24 hours, during which time the generated water was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 90°C through a Buchner funnel fitted with a black ribbon filter. The resulting product was homogeneous in the molten material, clear and yellow in color, and had an acid value of 3.1 mg KOH / g.

[0094] Example 16: Enzymatic esterification of a mixture of xylitol, sorbitol, glucose (65:25:10), and 1.91 eq. caprylic acid (according to the present invention) A mixture of xylitol (52.12 g, 0.342 mol), sorbitol (20.05 g, 0.110 mol), glucose (8.02 g, 0.045 mol), and caprylic acid (acid value 389 mg KOH / g, >98%, 136.91 g, 0.949 mol, 1.91 eq. relative to the initial total weight of xylitol, sorbitol, and glucose) was heated to 100°C with N2 while stirring and stirred for 1 hour. The mixture was then cooled to 80°C, and the immobilized enzyme Candida antarctica lipase B (5.91 g; equivalent to Purolite D5619, 51170 PLU) was added. The mixture was further stirred at 80°C and 20 millibars for 24 hours, during which time the water produced was continuously removed by distillation. Subsequently, to remove the enzyme, the mixture was filtered at 90°C using a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, clear and pale yellow in color, and had an acid value of 10.0 mg KOH / g.

[0095] Example 17: Enzymatic esterification of a mixture of xylitol, sorbitol (70:30), and 1.50 eq. lauric acid (according to the present invention) A mixture of xylitol (51.7 g, 0.340 mol), sorbitol (22.16 g, 0.122 mol), and lauric acid (acid value 280 mg KOH / g, >99%, 138.60 g, 0.692 mol, 1.50 eq. relative to the initial total weight of xylitol and sorbitol) was heated to 100°C with stirring through N2, and after 60 minutes, the immobilized enzyme Candida antarctica lipase B (6.02 g; equivalent to Purolite D5619, 52122 PLU) was added. Subsequently, this mixture was stirred at 95°C and 50 mg bar for 24 hours, during which time the generated water was continuously removed by distillation. After that, to remove the enzyme, the mixture was filtered at 90°C through a Buchner funnel with a black ribbon filter. The resulting product was homogeneous in the molten material, slightly turbid, pale yellow to nearly colorless, and had an acid value of 0.8 mg KOH / g.

[0096] Example 18: Distinguishing between the prior art and examples according to the present invention The following examples are intended to illustrate the subject matter of the present invention in detail and are not intended to limit the subject matter to these examples. These examples are intended to demonstrate that the methods according to the present invention have advantages over the prior art. Here, examples that do not conform to the present invention have been selected as representative of the prior art.

[0097] Technical effects: homogeneity and odor Table 1 compares Example 4 according to the present invention with Examples 1, 2, and 3 that do not conform to the present invention, in terms of reaction process, homogeneity, and odor.

[0098] [Table 1]

[0099] As can be seen from Table 1, Example 2, which does not conform to the present invention, is heterogeneous after 24 hours of reaction, still has a high residual acid value of approximately 140.5 mg KOH / g, and still has a noticeable fatty acid odor that can be unpleasant in the case of short-chain fatty acids such as caprylic acid. In contrast, Example 1, which does not conform to the present invention, is homogeneous after 24 hours of reaction, and although the residual acid value is only <1.3 mg KOH / g, a noticeable fatty acid odor can still be detected in this example as well. The same is true for a physical mixture of Example 1 and Example 2 (Example 3). Only in Example 4 according to the present invention is a low residual acid value (i.e., a high conversion rate of fatty acids), a homogeneous product, and a pleasant odor (popcorn-like) achieved after 24 hours of reaction.

[0100] Technical effect: Homogeneous even at relatively low degrees of esterification. Table 2 compares Example 8 according to the present invention with Examples 5 and 6 which do not conform to the present invention, in terms of reaction process and homogeneity.

[0101] [Table 2]

[0102] As can be seen from Table 2, Example 5, which does not conform to the present invention, exhibits phase separation in the form of precipitate in the molten material at 80°C. This phenomenon is even more pronounced in Example 6, which does not conform to the present invention, and also occurs in a physical mixture of Example 5 and Example 6 (Example 7). Only Example 8, which conforms to the present invention, remains homogeneous in the molten material at 80°C and does not exhibit phase separation, despite a relatively low degree of esterification of 1:1.5 (mole ratio of sugar to fatty acid).

[0103] Technical effects: Color and reactivity (i.e., degree of fatty acid conversion) Table 3 compares Example 14 according to the present invention with Example 13 not according to the present invention in terms of reaction process and color.

[0104] [Table 3]

[0105] As can be seen from Table 3, the physical mixture (Example 13) exhibits a much worse color than the method product according to the present invention (Example 14).

[0106] Example formulation The following examples demonstrate that the compositions according to the present invention can be used in a wide range of cosmetic formulations.

[0107] [Table 4-1]

[0108] [Table 4-2]

[0109] [Table 4-3]

[0110] [Table 4-4]

[0111] [Table 4-5]

[0112] [Table 4-6]

[0113] [Table 4-7]

[0114] [Table 4-8]

[0115] [Table 4-9]

[0116] Table 4-10

[0117] Table 4-11

[0118] Table 4-12

[0119] Table 4-13

[0120] Table 4-14

[0121] Table 4-15

[0122] Table 4-16

[0123] Table 4-17

[0124] Table 4-18

[0125] Table 4-19

[0126] Table 4-20

[0127] Table 4-21

[0128] Table 4-22

[0129] Table 4-23

[0130] Table 4-24

[0131] Table 4-25

[0132] Table 4-26

[0133] Table 4-27

[0134] Table 4-28

[0135] Table 4-29

[0136] Table 4-30

[0137] Table 4-31

[0138] Table 4-32

[0139] Table 4-33

[0140] Table 4-34

[0141] Table 4-35

[0142] Table 4-36

[0143] Table 4-37

[0144] Table 4-38

Claims

1. A method for enzymatically producing a mixed composition comprising at least two selected from sugar esters and / or sugar alcohol esters, comprising: B) A process step of reacting a mixture comprising at least two selected from sugars and sugar alcohols with at least one acyl group donor in the presence of lipase comprising wherein the mixture is xylitol and fructose or sorbitol, the acyl group donor is a fatty acid, continuously removing the water produced in the process step B), method.

2. The method according to claim 1, wherein the acyl group donor is selected from the group consisting of caproic acid, caprylic acid, pelargonic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadolenic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

3. The mixture comprising at least two selected from sugars and sugar alcohols used in the process step B) contains a substance selected from the group consisting of choline salts, ammonium salts and phosphonium salts in an amount less than 2% by weight, where the weight percentage is based on all sugars and sugar alcohols in the process step B) in the mixture comprising at least two selected from sugars and sugar alcohols. The method according to claim 1 or 2.

4. The method according to any one of claims 1 to 3, wherein in the process step B), the molar ratio of acyl groups contained in all acyl group donors to all sugars and sugar alcohols is in the range of 1.00:0.08 to 1.00:10.

00.

5. The method according to any one of claims 1 to 4, wherein in the process step B), the molar ratio of primary hydroxyl groups in all sugars and sugar alcohols to acyl groups contained in all acyl group donors is in the range of 1.00:0.10 to 1.00:3.

00.

6. The lipase is selected from the group consisting of a lipase derived from Thermomyces lanuginosus (accession number O59952), lipases A and B derived from Candida antarctica (accession number P41365), a lipase derived from Mucor miehei (accession number P19515), a lipase derived from Humicola sp. (accession number O59952), a lipase derived from Rhizomucor javanicus (accession number S32492), a lipase derived from Rhizopus oryzae (accession number P61872), a lipase derived from Candida rugosa (accession numbers P20261, P32946, P32947, P3294, and P32949), a lipase derived from Rhizopus niveus (accession number P61871), a lipase derived from Penicillium camemberti (accession number P25234), lipases derived from Aspergillus niger (ABG73613, ABG73614, and ABG37906), and a lipase derived from Penicillium cyclopium (accession number P61869), and those having at least 90% homology at the amino acid level thereof, the method according to any one of claims 1 to 5.

7. The method according to any one of claims 1 to 6, wherein process step B) is carried out at a reaction temperature in the range of 20°C to 160°C.

8. The method according to any one of claims 1 to 7, wherein process step B) is carried out at a pressure of less than 1 bar.

9. The method according to any one of claims 1 to 8, wherein in process step B), the total of the at least two selected from the group consisting of the sugar and the sugar alcohol and the acyl group donor occupies at least 10% by weight of the entire reaction batch.

10. A) A process step to obtain a mixture used in process step B) and comprising at least two selected from sugars and sugar alcohols, provided spatially separately from each other in solid form or dissolved in water, and mixed together. The method according to any one of claims 1 to 9, including

11. The method according to claim 10, wherein process step A) comprises reducing the water content of a mixture used in process step B) and comprising at least two selected from sugars and sugar alcohols to less than 17% by weight, wherein the weight percentage is relative to the whole mixture used in process step B) and comprising at least two selected from sugars and sugar alcohols.

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