Ester Composition

Abstract

The present invention relates to methods for preparing blend compositions, ester compositions, and uses of the blend compositions and ester compositions, especially in cosmetic applications, that include selected alkyl carboxylates.

Description

[Technical field]

[0001] The present invention relates to a method for preparing mixture compositions, ester compositions, especially those containing selected alkyl carboxylates, and to the use of the mixture compositions and ester compositions, especially in cosmetic applications.

[0002] Prior Art Petrochemical-based mineral oils are traditionally often used in the oil phase of emulsions as cheap fillers. However, modern formulation projects require that petrochemical sources of formulation ingredients be avoided as much as possible for sustainability reasons. For such applications, suitable oils are rather moderately heavy oils with average application properties, e.g., viscosities in the range of 10-50 mPa·s at ambient temperature and surface tensions in the range of 26-32 mN / m, with associated medium to good spreading behavior and medium to low polarity. A commercially available alternative made from at least partially sustainable raw materials is cetyl ethylhexanoate.

[0003] Sensorine Care DD (INCI: Lauryl Olivate; CAS number: 92113-71-8; EINECS number: 295-679-5), for example, which is marketed for cosmetics as being entirely based on sustainable raw materials, is a yellow wax, soft at 20°C, has a characteristic odor and a content of the active ingredient Lauryl Olivate of 99.0-99.9%. Sensorine Care DD is promoted as a raw material with a protective effect on the skin and organoleptic benefits such as a light and silky feel. However, its melting point is in the range of 25-27°C and can even go up to 32°C, which may be considered a fatal drawback. Because, by definition, oils for cosmetics must typically be liquid, the applicability of waxy raw materials as such oils is limited.

[0004] Similarly, Dermol CV (INCI: Lauryl Oleate; CAS number: 36078-10-1), which is entirely made from sustainable raw materials, is commercially available for use in cosmetics. Dermol CV is recommended as a weakly occlusive mineral oil to replace occlusive mineral oils and can also be used as a pigment dispersant.

[0005] Although the above-mentioned olivary lauryl fatty acid, or lauryl oleate, has the drawbacks as explained, it can in principle be used as a natural-based alternative to conventional petrochemical-based mineral oils.

[0006] US Patent 4826767 describes the enzymatic reaction of different fatty acids with different fatty alcohols in a ratio of fatty acid to fatty alcohol of 1.1:1.0 to 0.9:1.0, using at least 0.45% Lipozyme at 60-80°C and 0.005-1.0 bar for 1-7 hours. A disadvantage of the methods described in the prior art is that only pure chain scission fragments are always reacted with each other. A further disadvantage is that the enzyme charge during the reaction can be very high. A further disadvantage is that wax is obtained as product, which the skilled person will understand to mean a substance that is solid at 20°C.

[0007] US Patent No. 8,505,736 describes the catalytic synthesis of esters by reaction of linear or branched alcohols with a chain length of C8-C20 with linear fatty acids with a chain length of C12-C22 to produce more biodegradable flotation aids for froth flotation. The temperature of the reaction can be between 100°C and 200°C.

[0008] CN101076509 describes the synthesis of esters from fatty alcohols and fatty acids having more than 10 carbon atoms, respectively, using metal hydrates as catalysts.

[0009] Japanese Patent No. 62104589 describes the reaction of individual alcohols with individual fatty acids in the presence of an organic solvent and alkaline lipase to prepare fatty acid esters.

[0010] The aim of the present invention is to make available oil bodies which exhibit excellent properties with regard to their use in cosmetic products.

[0011] Detailed Description of the Invention Surprisingly, it has been found that the problems of the present invention can be solved by the mixture and ester compositions described below.

[0012] The present invention therefore provides a mixed composition comprising an alkyl carboxylate as claimed in claim 1.

[0013] The present invention also relates to a method for preparing an ester composition according to claim 8.

[0014] An advantage of the present invention is that the mixed composition according to the present invention exhibits excellent odor.

[0015] Another advantage of the present invention is that the mixed composition according to the present invention exhibits excellent wetting properties.

[0016] A further advantage of the present invention is that the mixed composition according to the present invention can be widely used in color cosmetics.

[0017] Another advantage of the present invention is that the mixed composition according to the present invention is liquid at ambient temperature and can be used as a typical cosmetic oil in emulsions.

[0018] A further advantage of the present invention is that the mixed composition according to the invention is based on a very high proportion of renewable raw materials or is based exclusively on renewable raw materials.

[0019] Another advantage of the present invention is that the mixed composition according to the present invention confers very good stability to cosmetic formulations, especially with regard to stability under high temperature conditions.

[0020] A further advantage of the present invention is that the organic UV screening agent is only relatively poorly dissolved by the mixed composition according to the present invention, and therefore does not contribute to the penetration of the organic UV screening agent through the skin barrier.

[0021] Another advantage of the present invention is that the mixed composition according to the present invention provides a very good skin feel to cosmetic formulations.

[0022] A further advantage of the present invention is that the mixed compositions according to the invention exhibit particularly good color.

[0023] Another advantage of the present invention is that the mixed composition according to the present invention exhibits excellent viscosity characteristics.

[0024] A further advantage of the present invention is that the mixed composition according to the present invention exhibits very low surface tension.

[0025] Another advantage of the present invention is that the mixed composition according to the present invention exhibits excellent diffusion behavior.

[0026] A further advantage of the present invention is that the mixed composition according to the present invention exhibits very low interfacial tension.

[0027] A further advantage of the present invention is that the mixed compositions according to the present invention exhibit very low polarity.

[0028] A further advantage of the present invention is that the mixed composition according to the present invention may be advantageously used in skin and hair conditioning applications and as a sensory additive.

[0029] Another advantage of the present invention is that the mixed composition according to the present invention exhibits a protective function and can therefore be advantageously used to improve skin hydration and strengthen the skin barrier.

[0030] Another advantage of the present invention is that the mixed composition according to the present invention exhibits low occlusiveness, thereby reducing water loss upon application to the skin.

[0031] Another advantage of the present invention is that the mixed composition according to the present invention has very standard application properties and therefore can be used very widely in cosmetics, such as color cosmetics, deodorants, fragrances, hair products, shaving preparations, depilatories, skin care (body care, eye care, face care, foot care, hand care, lip care, sun care, etc.), soap products, and bath cosmetics.

[0032] Thus, the present invention provides A mixed composition comprising: General formula (Ia) [ka] a first alkyl carboxylate group of General formula (Ib) [ka] a second alkyl carboxylate group [In the ceremony R 1a and R 1b is selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbyl acyl groups having 6 to 30, preferably 8 to 22, particularly preferably 10 to 18, carbon atoms, R 2a and R 2b are each selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon radicals having 4 to 22, preferably 8 to 18, particularly preferably 12 to 14, carbon atoms, however, R 2a is R 2b Unlike, The alkyl carboxylates of the first and second groups are present in a total amount of at least 55% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, based on all alkyl carboxylates present in the mixed composition. In a mixed composition comprising: The mixed composition is characterized in that the weight ratio of all the alkyl carboxylates of the first group to all the alkyl carboxylates of the second group is 10.0:1.0 to 1.0:1.0, preferably 4.0:1.0 to 1.5:1.0, and particularly preferably 3.5:1.0 to 2.0:1.0.

[0033] In the context of the present invention, the term "alkyl carboxylate" is understood to mean an alkyl carboxylate of general formula (Ia) in which R 1a is selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted, hydrocarbon acyl groups having 1 to 40 carbon atoms; R 2a is selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted, hydrocarbon groups having 1 to 40 carbon atoms.

[0034] Unless otherwise stated, all percentages (%) listed are by weight.

[0035] In the mixed composition according to the present invention, R 1a and R 1b may be identical or different and may represent a mixture selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbyl acyl groups having 6 to 30, preferably 8 to 22, particularly preferably 10 to 18 carbon atoms.

[0036] On the other hand, in the mixed composition according to the present invention, R 2a and R 2bare each selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon radicals having 4 to 22, preferably 8 to 18, particularly preferably 12 to 14, carbon atoms.

[0037] In a preferred mixed composition according to the invention, the sum of the alkyl carboxylates of the first and second groups is present in an amount of 55% to 99% by weight, preferably 70% to 98% by weight, particularly preferably 80% to 97% by weight, based on all alkyl carboxylates present in the mixed composition.

[0038] In a preferred mixed composition according to the present invention, R 1a , R 1b , R 2a , and R 2b The amount of R groups in the mixture composition is 1a , R 1b , R 2a , and R 2b Based on the group, the weight percentage is a total of 40% by weight or less, preferably less than 20% by weight, more preferably less than 10% by weight, and particularly preferably less than 3.0% by weight.

[0039] Alternatively, in a preferred mixed composition according to the present invention, R 1a , R 1b , R 2a , and R 2b The amount of R groups is determined based on the total amount of R groups present in the mixed composition. 1a , R 1b , R 2a , and R 2b Based on the group, the weight percentage is a total of more than 40% by weight, preferably 50% by weight or more, more preferably more than 60% by weight, and particularly preferably more than 80% by weight.

[0040] In this regard, R 1a , R 1b , R 2a , and R 2b The group is a group having 11 carbon atoms.

[0041] In a preferred mixed composition according to the present invention, R 2a and R 2b are each selected from saturated, straight chain, optionally hydroxy-substituted hydrocarbon groups having 12 and 14 carbon atoms.

[0042] A preferred mixed composition according to the present invention is 2a is a lauryl group, and R 2b is a myristyl group.

[0043] In a preferred mixed composition according to the present invention, R 1a and R 1b is selected from saturated or unsaturated, preferably unsaturated, particularly preferably mono- and di-unsaturated, linear, hydrocarbon acyl groups having 18 carbon atoms.

[0044] Particularly preferred mixed compositions according to the invention are 2a is a lauryl group, and R 2b is a myristyl group, and R 1a and R 1b is selected from mono- and di-unsaturated, linear, hydrocarbyl acyl groups having 18 carbon atoms.

[0045] In this connection, it is preferred according to the invention that the alkyl carboxylates of the first and second groups are present in a total weight percentage of 70% to 99% by weight, preferably 85% to 95% by weight, based on all alkyl carboxylates present in the mixed composition.

[0046] In this connection, it is furthermore particularly preferred according to the invention that the alkyl carboxylates of the second group are present in an amount by weight of 15% to 35% by weight, preferably 20% to 30% by weight, based on all the alkyl carboxylates present in the mixed composition.

[0047] In this connection, it is even more particularly preferred according to the invention that the mixed composition according to the invention comprises lauryl palmitate and / or myristyl myristate in a total weight percentage amount of 0.5% to 7.0% by weight, in particular 1.0% to 5.0% by weight, based on all alkyl carboxylates present in the mixed composition.

[0048] Particularly preferred mixed compositions according to the invention are characterized in that they exhibit a melting point below 25°C, preferably below 23°C.

[0049] A preferred mixed composition according to the invention is characterized in that it contains an antioxidant.

[0050] Preferred antioxidants, which are preferably present in the mixed composition according to the invention, are 3,5-di-tert-butyl-4-hydroxytoluene (BHT), 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole, tert-butylhydroquinone (TBHQ), digalloyl trioleate, propyl gallate, octyl gallate, dodecyl gallate, mercaptoacetic acid, sodium thioglycolate, rosmarinic acid, carnosine, methyl methacrylate ... siderophores including catechol type, hydroxamate type, e.g., deferoxamine B, D1, D2, E, and H, citrate, cysteine ​​and its derivatives, e.g., cysteine ​​hydrochloride and acetylcysteine, ascorbic acid and its derivatives, e.g., ascorbyl glucoside, ascorbyl palmitate, ascorbyl dipalmitate, ascorbyl tetraisopalmitate, ascorbyl mag. nesium, magnesium ascorbate phosphate, etc.), vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and α-tocotrienol, β-tocotrienol, γ-tocotrienol, and δ-tocotrienol) and its derivatives (e.g. vitamin E acetate, vitamin E linoleate, vitamin E nicotinate, vitamin E succinate), hesperetin, naringenin, flavonoids, taxifolin , catechin, epicatechin, resveratrol and its derivatives (especially its oligomers), carotenoids (e.g. lycopene, β-carotene, lutein), isosakuranetin, quercetin, eriodictyol, aromadendrin, acacetin, luteolin, kaempferol, apigenin, diosmetin, chrysoeriol, chrysin, galangin, limocitrin, phytic acid, and its derivatives, particularly its salts, are preferably selected from the group consisting of them.

[0051] Mixtures of the abovementioned antioxidants may also be preferably used. Particularly preferred are phytic acid and its derivatives, especially its salts, and vitamin E (e.g. in the form of α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol and / or δ-tocotrienol) and its derivatives, especially vitamin E acetate, vitamin E linoleate, vitamin E nicotinate or vitamin E succinate, and mixtures thereof.

[0052] In the preferred mixed compositions according to the invention, the antioxidant is preferably present in an amount of 0.001% to 5.0% by weight, preferably 0.01% to 1.0% by weight, in particular 0.02% to 0.35% by weight, based on the total composition.

[0053] The blended composition according to the present invention can be prepared by any method known to those skilled in the art for preparing esterified products.

[0054] The present invention further comprises: A) a process step of providing a first alcohol and a second alcohol which differs from the first alcohol and is selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon alcohols having 4 to 22, preferably 8 to 18, particularly preferably 12 to 14, carbon atoms, B) a process step of providing at least one acid selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted carboxylic acids having 6 to 30, preferably 8 to 22, particularly preferably 10 to 18 carbon atoms, C) a process step of esterifying the first and second alcohols with an acid to obtain an ester composition, and optionally D) process steps for purifying the ester composition; A method comprising: It relates to a method for the preparation of a mixed composition preferably according to the present invention, characterized in that the weight ratio of the amount of the first alcohol and the amount of the second alcohol is from 85.0:15.0 to 1.0:1.0, preferably from 80.0:20.0 to 65.0:35.0.

[0055] A preferred process according to the invention is characterized in that the sum of the amount of the first alcohol and the amount of the second alcohol amounts to at least 55% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, based on all alcohols used in the process.

[0056] A preferred process according to the invention is characterized in that the first alcohol is selected from lauryl alcohol and the second alcohol is selected from myristyl alcohol.

[0057] A preferred process according to the invention is characterized in that the acid is selected from oleic acid and linoleic acid.

[0058] According to the invention, it is preferred that process step C) of the process according to the invention is carried out by enzyme-catalyzed reaction.

[0059] The present invention further relates to an ester composition obtainable by the process according to the invention.

[0060] The present invention further relates to the use of the mixture composition according to the invention and / or the ester composition according to the invention for preparing a cosmetic formulation, in particular a cosmetic sunscreen formulation.

[0061] The present invention further relates to the use of the mixture composition according to the invention and / or the ester composition according to the invention for dispersing solid pigments, in particular hydrophobized solid pigments.

[0062] The present invention further relates to the use of the mixture composition according to the invention and / or the ester composition according to the invention for dissolving organic UV filters.

[0063] In the use according to the invention, the mixture composition according to the invention and / or the ester composition according to the invention are preferably used according to the invention as well, depending on their preferences.

[0064] The present invention is illustrated by way of example in the following examples, but the scope of the invention as understood from the invention, the full specification and the claims is not limited to the embodiments mentioned in the examples.

[0065] The following drawings form part of the examples: [Brief description of the drawings]

[0066] [Figure 1] FIG. 1 shows phase separation of an emulsion after two months of storage at ambient temperature. [Diagram 2] FIG. 1 is a graph showing sensory evaluations regarding oily feel and absorbency. [Diagram 3] FIG. 1 shows sensory evaluation results for oiliness, absorbency, and stickiness. [Figure 4] FIG. 1 shows sensory evaluations of oiliness, absorbency, and stickiness after 5 minutes.

[0067] Working Example How to measure acid value Suitable methods for determining the acid number are, in particular, the methods according to DGF CV 2, DIN EN ISO 2114, Ph.Eur.2.5.1, ISO 3682, and ASTM D 974.

[0068] Methods for measuring the specific activity of enzymes used in PLU: To measure the enzyme activity in PLU (propyl laurate units), 1-propanol and lauric acid are mixed homogeneously at 60° C. in an equimolar ratio. The reaction is started by adding the enzyme and the reaction time is measured. Samples are taken from the reaction mixture at intervals and the content of converted lauric acid is measured by titration with potassium hydroxide solution. The enzyme activity in PLU is determined from the rate at which 1 g of the enzyme synthesizes 1 μmol of propyl laurate per minute at 60° C. See also US Patent Application Publication No. 2007 / 0087418, in particular paragraph

[0185] , in this regard.

[0069] How to measure Hazen color scale Suitable methods for determining the Hazen colour number are, in particular, the methods according to DIN-ISO 627, DIN EN 1557, ASTM D 1209-84 and DGK F 040.

[0070] Method for determining chain distribution of alkyl carboxylates by GC-FID and GC-MS A 10 mg sample of the corresponding alkyl carboxylate mixture is first dissolved in 1.5 ml trichloromethane and then 0.15 ml N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) is added. Derivatization is carried out at 80° C. for 30 min. A sample of the clear solution thus obtained is analyzed by GC-FID and GC-MS. The parameters of the measurement method are: Gas chromatograph: Agilent 7890 Column: Agilent HP-5 (50m, 0.32mm, 0.5μm), Flow rate: maintained at 2 mL / min, carrier gas: hydrogen (GC-MS: helium) Preheat 80℃, 8℃ / min, 300℃, 30min, injector 1μL, split 1:20, detector temperature 310℃ Detector: FID, 310℃ / GC-MS scan 35-650d It is.

[0071] In GC-FID analysis, the esters present in a sample are separated according to their total chain length. The ratio of the individual esters to each other is determined by their respective area % of the GC-FID peak. Identification / assignment of the peaks to the individual ester forms is performed by GC-MS.

[0072] The chain distribution of the fatty acids and fatty alcohols used as raw materials, their hydroxyl and iodine values ​​were obtained from available certificates of analysis.

[0073] Example ##001#: Preparation of a mixed composition according to the present invention A mixture of technical C12 / C14 fatty alcohols (hydroxyl value = 289 mg KOH / g, C12 = 72%, C14 = 26%, 620 g) and oleic acid (acid value = 200 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1 78%, 881 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica lipase B (142950 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h, while the water formed was continuously distilled off. The enzyme was subsequently filtered off by a black ribbon filter. The obtained product showed an acid value of less than 0.5 mg KOH / g and a Hazen color number of less than 100.

[0074] Example ##002a#: Preparation of a mixed composition according to the present invention The bubble column was then cooled to room temperature with C8 fatty alcohol (molar mass = 144.21 g / mol, C8 > 99%, 311 g), C10 fatty alcohol (molar mass = 172.26 g / mol, C10 > The flask was filled with 100 ml of ethanol (C18:1 78%, 1000 g), 100 ml of ethanol (C18:1 78%, 1000 g), and oleic acid (acid value = 202 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1 78%, 1000 g) and heated to 60 °C while continuing the nitrogen gas supply. After adding the immobilized enzyme Candida Antarctica lipase B (82522 PLU), the mixture was reacted under these conditions for 22 h. The enzyme was then filtered off by a black ribbon filter. The obtained product showed an acid value of less than 0.5 mg KOH / g and a Hazen color number of less than 120.

[0075] Example ##002b#: Preparation of a mixed composition according to the present invention A bubble column was filled with a mixture of technical C16 / C18 fatty alcohols (hydroxyl value = 216.5 mg KOH / g, C16 = 31%, C18 = 67%, 949 g) and oleic acid (acid value = 202 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1 78%, 1000 g) and heated to 80 °C with a continuous nitrogen gas supply. After adding the immobilized enzyme Candida Antarctica lipase B (81481 PLU), the mixture was reacted under these conditions for 22 h. The enzyme was subsequently filtered off by a black ribbon filter. The resulting product showed an acid value of less than 0.5 mg KOH / g and a Hazen color number of less than 200.

[0076] Example ##003#: Preparation of a mixed composition according to the present invention Technical C12 / C14 fatty alcohol (hydroxyl value = 289 mg KOH / g, C12 = 72%, C14 = 26%, 152 g) and oleic acid (acid value = 198 mg KOH / g, iodine value = 91 g I2 / 100 g, C18:1 > A mixture of 100% ethanol (90%, 220 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica lipase B (10201 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h, while the water formed was continuously distilled off. The enzyme was subsequently filtered off through a black ribbon filter. The obtained product showed an acid value of less than 0.6 mg KOH / g and a Hazen color number of less than 50.

[0077] Example ##004#: Preparation of a product not according to the invention from a mixture of pure lauryl alcohol and fatty acids Lauryl alcohol (C12>99%, 175g), oleic acid (acid value = 200mg KOH / g, iodine value = 93g I2 / 100g, C18:1<80%, 125g), palmitic acid (C16 > 99%, 73g), and stearic acid (C18:0 >A mixture of 100% ethanol (92%, 48 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica lipase B (21420 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h while the water formed was continuously distilled off. The enzyme was then filtered off through a black ribbon filter. The obtained product showed an acid value of less than 0.3 mg KOH / g and a Hazen color number of less than 60.

[0078] Example ##005#: Preparation of a product not according to the invention from pure lauryl alcohol and pure oleic acid Lauryl alcohol (C12>99%, 70.0 g) and oleic acid (acid value = 198 mg KOH / g, iodine value = 91 g I2 / 100 g, C18:1 > A mixture of 100% ethanol (89.5%, 96.5 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica Lipase B (8466PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h, while the water produced was continuously distilled off. The enzyme was then filtered off by a black ribbon filter. The obtained product showed an acid value of less than 0.5 mg KOH / g and a Hazen color number of less than 50.

[0079] Example ##006#: Preparation of a product not according to the invention from technical oleic acid and pure lauryl alcohol A mixture of lauryl alcohol (C12>99%, 120 g) and oleic acid (acid value = 200 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1<80%, 179 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica lipase B (15198 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h, while the water formed was continuously distilled off. The enzyme was then filtered off by a black ribbon filter. The obtained product showed an acid value of less than 0.5 mg KOH / g and a Hazen color number of less than 200.

[0080] Example ##007#: Preparation of a product not according to the invention from technical oleic acid and myristyl alcohol Myristyl alcohol (C14 > A mixture of oleic acid (acid value = 200 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1 < 80%, 419 g) and oleic acid (acid value = 200 mg KOH / g, iodine value = 93 g I2 / 100 g, C18:1 < 80%, 419 g) was heated to 60 °C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica Lipase B (37944 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h, while the water formed was continuously distilled off. The enzyme was then filtered off with a black ribbon filter. The obtained product showed an acid value of less than 0.5 mg KOH / g. As the product was solid at ambient temperature, the Hazen color number had a value of less than 100 at 40 °C.

[0081] Example ##008#: Preparation of a product not according to the invention from pure oleic acid and myristyl alcohol Myristyl alcohol (C14 > 96%, 307g) and oleic acid (acid value = 198mg KOH / g, iodine value = 91g I2 / 100g, C18:1 > A mixture of 100% ethanol (89.5%, 401 g) was heated to 60°C under stirring in a stirred reactor. After addition of the immobilized enzyme Candida Antarctica Lipase B (36108 PLU), the pressure was reduced to 25 mbar and the mixture was stirred for 24 h while the water formed was continuously distilled off. The enzyme was then filtered off with a black ribbon filter. The product obtained showed an acid value of less than 2 mg KOH / g. As the product was solid at ambient temperature, the Hazen colour number was less than 50 at 40°C.

[0082] Application example: Storage stability of W / O emulsions The alkyl carboxylates according to the invention are representative cosmetic oils in emulsions that can be used, especially when the emulsion contains a very high proportion of natural raw materials or only natural raw materials.The formulations obtained with alkyl carboxylates are characterized by good stability, especially in terms of stability under high temperature conditions, and are therefore preferred compared to emulsions using other natural-based or petrochemical-based oils, which may be considered as first choice.The water-in-oil emulsions shown in Table 1 were prepared.

[0083] [Table 1-1] [Table 1-2]

[0084] The viscosities of the formulations are comparable (10-12 Pa·s; Brookfield viscosity, measured at 10 rpm with spindle 5 at 25°C). All formulations prepared are viscous and homogeneous. After storage for 2 months at ambient temperature, clear phase separation is observed for the emulsions containing non-inventive examples ##005#, ##006#, ##007#, and ##008#, but not for the emulsions containing inventive alkyl carboxylates according to examples ##001# and ##003#.

[0085] Application example ##112#: Pigment dispersions The alkyl carboxylates according to the present invention can make hydrophobized pigments wettable, and therefore can be widely used in color cosmetics. The pigment wetting properties of cosmetic oils can be determined by measuring the viscosity of the pure oil and comparing it with the viscosity of the oil after dispersing a given amount of pigment. The smaller the increase in viscosity thus determined, the better the oil's ability to wet the pigment on the surface, and therefore the better the oil's ability to disperse.

[0086] A standard pigment mixture is investigated, as shown in Table 2.

[0087] [Table 2]

[0088] The viscosity of the oil before the addition of the pigment / powder mixture is measured in a Brookfield viscometer using spindle 5 at 50 rpm and 20° C. After dispersion of the pigment / powder mixture, the viscosity is measured again in the same way. The increase in viscosity is:

[0089] [Table 3]

[0090] The increase in viscosity of the pigment / powder dispersion is greatest in mineral oil, i.e. the dispersibility in mineral oil is very low. The use of cetyl ethylhexanoate or dermofeel® sensolv (isoamyl laurate well known for its pigment dispersing ability, see EP 2 691 157) allows a clear reduction in the increase in viscosity, thus improving the dispersibility, but still not reaching the level achieved when using examples ##001# and ##003# according to the invention. The pigment / powder mixtures of examples ##008# and ##007# not according to the invention show (partial) crystallization and thus a viscosity increase or a maximum viscosity (not measurable with spindle 5 at 20° C. and 50 rpm).

[0091] Additionally, mixtures of cosmetic oils and pure pigments were prepared as shown in Table 2a. Again, the pigment wetting properties of the cosmetic oils can be determined by measuring the viscosity of the pure oil and comparing it with the viscosity of the oil after dispersing a given amount of pure pigment. The smaller the increase in viscosity thus determined, the better the oil's ability to wet and therefore disperse the pigment on the surface.

[0092] [Table 4]

[0093] The mixture is then stirred at 3500 rpm for 3 minutes and placed on a rheometer (Anton Paar, Modular Compact Rheometer, model MCR302, 20°C, 1 / 100 sec) for measurement. The viscosity of the pure cosmetic oil is also measured. The viscosity of the pigment mixture and the pure cosmetic oil are measured three times and the results are averaged.

[0094] The comparative viscosity increase between pure cosmetic oil and the pigment / cosmetic oil mixture is shown below (in mPa·s):

[0095] [Table 5-1] [Table 5-2]

[0096] The increase in viscosity of the pigment / cosmetic oil mixture is greatest when mineral oil is used, i.e. dispersibility in mineral oil is very low. The use of cetyl ethylhexanoate or dermofeel® sensolv (isoamyl laurate) allows the increase in viscosity to be significantly reduced, and thus improves dispersibility, but still does not reach the level achieved when using examples ##001# and ##003# according to the invention. The pigment / cosmetic oil mixtures of examples ##008# and ##007#, which are not according to the invention, show (partial) crystallization and thus a viscosity increase, or a maximum viscosity (not measurable).

[0097] Application Example ##113#: Sensory evaluation of a W / O lotion compared to mineral oil The formulations shown in Table 3 were prepared. The effect of the formulations on skin sensation was investigated by a test panel. A defined amount of approximately 25 μL of the formulation was applied to each of 14 trained individuals at defined test sites on the inner forearm. The composition of the formulations was blinded. The formulations were spread over the test sites using circular finger movements (maximum 60 times) until obvious absorption. Five minutes after applying the samples to the skin, the parameters of oiliness and absorbency were evaluated on a scale of 0 to 10.

[0098] [Table 6]

[0099] Figure 2 shows that the formulation of Example ##001# is noticeably less oily and has better absorbency compared to mineral oil. Non-inventive Examples ##005# and ##006# also show improved properties compared to mineral oil, but do not reach the level of the inventive examples.

[0100] Application Example ##114#: Sensory evaluation of an O / W lotion compared to mineral oil and cetyl ethylhexanoate The formulations shown in Table 4 were prepared. The effects of the formulations on skin sensation were investigated by a test panel. Ten trained individuals applied a defined amount of the formulation, approximately 25 μL, to defined test sites on the inner forearm of each individual. The composition of the formulations was blinded. The formulations were spread over the test sites using a circular finger motion (maximum 60 times) until absorption was evident. The parameters of whitening, oiliness, absorption, and stickiness were evaluated on a scale of 0 to 10 while the samples were being spread on the skin, and again after 5 minutes for the parameters of oiliness, absorption, and stickiness.

[0101] [Table 7]

[0102] FIG. 3 shows that the formulation of Example #002a# exhibits less whitening, less oiliness, faster absorption, and less stickiness in comparison to cetyl ethylhexanoate and mineral oil.

[0103] FIG. 4 shows that after 5 minutes of application, the formulation of Example #002a# felt less oily, absorbed more completely, and was less sticky in comparison to cetyl ethylhexanoate and mineral oil.

[0104] These results show that O / W lotions containing an oil according to the invention are of higher sensory quality than O / W lotions containing an oil not according to the invention.

[0105] Application example ##114a#: Sensory evaluation of make-up foundations in comparison with castor oil The formulations shown in Table 4a were prepared. The effects of the formulations on skin sensation were investigated by a test panel. Ten trained individuals applied a defined amount of the formulation, approximately 25 μL, to defined test sites on the inner forearm of each individual. The composition of the formulations was blinded. The formulations were spread over the test sites using a circular finger motion (maximum 60 times) until obvious absorption was observed. The parameters of stickiness, oiliness, absorbency, and tackiness were evaluated on a scale of 0 to 10 during the spreading of the samples on the skin, and again after 5 minutes for the parameters of stickiness, oiliness, absorbency, and tackiness.

[0106] [Table 8]

[0107] [Table 9]

[0108] Table X shows that formulation C03-4.6-1221, in which part of the castor oil (not according to the invention) is replaced with Example ##001# (according to the invention), shows slightly increased absorbency and reduced stickiness, oiliness and tackiness compared to C03-4.7-0122, and also shows reduced stickiness, oiliness and tackiness 5 minutes after application to the skin, as well as particularly higher absorbency.

[0109] These results show that make-up formulations containing an oil according to the invention are of higher organoleptic quality than make-up formulations containing an oil not according to the invention.

[0110] Application example ##115#: Dissolving ability of UV protection filters To test the dissolving ability of UV protection filters, the following crystalline UVA or UVB protection filters were selected: Bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT) Butyl methoxydibenzoylmethane (BMDM) Diethylamino hydroxybenzoyl hexyl benzoate (DHHB) Ethylhexyl triazone (EHT) To measure the dissolving ability of UV protection filters, a given amount (50 g) of one of the compounds according to the invention was introduced in each case and heated to 22° C. 1% by weight of UV protection filter was added and stirred until this amount was completely and homogeneously dissolved. This operation was repeated until the maximum soluble amount of UV protection filter was exceeded. At higher concentrations, longer stirring times of several hours are often required to achieve complete dissolution. When the maximum concentration was thus roughly measured, a fine concentration range was determined by repeating around this maximum concentration using smaller amounts of UV protection filter.

[0111] [Table 10]

[0112] Compared with examples ##005# and ##006#, as well as other oils commonly used in sunscreen applications, such as cetearyl ethylhexanoate or ethylhexyl palmitate, example ##001# according to the invention is characterized by the lowest overall UV filter solubility. This relatively low UV filter solubility is an ideal property of the oil according to the invention in sunscreen applications, where it is sometimes used in combination with other oils that exhibit very high UV filter solubility. In this context, a high UV filter solubility is necessary to sufficiently dissolve the UV filter and prevent its crystallization. The oil according to the invention behaves neutrally in this respect, i.e. its UV filter solubility is not so low as to cause UV filter crystallization, but is not so high as to risk promoting UV filter penetration through the skin barrier.

[0113] Application example: Smell recognition Specimens of the samples of Examples ##006#, ##007# and ##008# not according to the invention and Example ##001# according to the invention are fed to an odor panel. For this, the samples are transferred each time into separate sample bottles, which are half filled. The samples are then stored at ambient temperature with a closed lid for 2 hours. The odor test is carried out in an odor-free area. Four testers sniff the samples in succession, after which each sample is individually rated and classified as good (1), medium (2) and bad (3). The average of the ratings is the test result.

[0114] [Table 11]

[0115] These results show that Example ###001# according to the invention leads to a better odor perception than the product not according to the invention.

[0116] Formulation example: The mixed composition according to the invention can be used in various cosmetic formulations, such as oil-in-water emulsions, water-in-oil emulsions, or anhydrous systems. The formulation examples are intended to illustrate the possible use of the mixed composition in cosmetic emulsions as examples, and do not limit the subject matter of the present invention.

[0117] All quantitative data expressed in % are parts by weight unless otherwise stated. Preparation and homogenization steps are carried out according to conventional methods.

[0118] The following formulation examples are described by Example ##001#.

[0119] All of the formulation examples given below are further represented by replacing the component Example ##001# with Example ##002# and Example ##003# in each example.

[0120] [Table 12-1] [Table 12-2] [Table 12-3] [Table 12-4] [Table 12-5] [Table 12-6] [Table 12-7] [Table 12-8] [Table 12-9] [Table 12-10]

Table 12-11

Table 12-12

Table 12-13

Table 12-14

Table 12-15

Table 12-16

Table 12-17

Table 12-18

Table 12-19

Table 12-20

Table 12-21

Table 12-22

Table 12-23

Table 12-24

Table 12-25

Table 12-26

Table 12-27

Table 12-28

Table 12-29

Table 12-30

Table 12-31

Claims

1. A mixed composition, General formula (Ia) 【Chemistry 1】 The first alkylcarboxylate group, and General formula (Ib) 【Chemistry 2】 The second alkylcarboxylate group [During the ceremony R １ａ and R １ｂ These are selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon acyl groups having 6 to 30 carbon atoms. R ２ａ and R ２ｂ These are selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon groups having 12 to 18 carbon atoms. however, R ２ａ is R ２ｂ Unlike, The alkyl carboxylates of the first and second groups are present in the mixed composition in an amount totaling at least 55% by weight, based on all alkyl carboxylates present in the mixed composition. In a mixed composition containing, A mixed composition characterized in that the weight ratio of all the alkyl carboxylates of the first group to all the alkyl carboxylates of the second group is 10.0:1.0 to 1.0:1.

0.

2. R in which the number of carbon atoms is odd １ａ , R １ｂ , R ２ａ , and R ２ｂ The amount of the group is 40% by weight or less in total based on all R １ａ , R １ｂ , R ２ａ , and R ２ｂ groups, and the mixed composition according to claim 1, characterized in that

3. R ２ａ The lauryl group is R ２ｂ The mixed composition according to claim 1 or 2, characterized in that the group is a myristyl group.

4. R １ａ and R １ｂ The mixed composition according to claim 1 or 2, characterized in that it is selected from saturated or unsaturated linear hydrocarbon acyl groups having 18 carbon atoms.

5. The mixed composition according to claim 3, characterized in that the alkyl carboxylates of the first group and the second group are present in an amount totaling 70% to 99% by weight, based on all alkyl carboxylates present in the mixed composition.

6. The mixed composition according to claim 3, characterized in that the alkyl carboxylate of the second group is present in an amount of 15% to 35% by weight, based on all alkyl carboxylates present in the mixed composition.

7. The mixed composition according to claim 3, characterized in that it contains lauryl palmitate and / or myristyl myristate in an amount totaling 0.5% to 7.0% by weight, based on all alkyl carboxylates present in the mixed composition.

8. A) A method step of supplying a first alcohol and a second alcohol different from the first alcohol, wherein the first and second alcohols are selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted hydrocarbon alcohols having 12 to 18 carbon atoms. B) A method for supplying at least one acid selected from saturated or unsaturated, linear or branched, optionally hydroxy-substituted, carboxylic acids having 6 to 30 carbon atoms, C) A method step of esterifying the first and second alcohols with the acid to obtain an ester composition, and optionally, D) A step of purifying the ester composition, In a method including, The weight ratio of the amount of the first alcohol to the amount of the second alcohol is 85.0:15.0 to 1.0:1.

0. A method characterized in that the sum of the amounts of the first alcohol and the second alcohol is at least 55% by weight of all alcohol used in the method.

9. The method according to claim 8, characterized in that the first alcohol is selected from lauryl alcohol and the second alcohol is selected from myristyl alcohol.

10. The method according to claim 8, characterized in that the acid is selected from oleic acid and linoleic acid.

11. The method according to claim 8, characterized in that step C) is carried out by an enzyme-catalyzed reaction.

12. Use of the mixed composition according to claim 1 for preparing cosmetic formulations.

13. Use of the mixed composition according to claim 1 for dispersing a solid pigment and / or dissolving an organic ultraviolet shielding agent.

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