Patent Application
20140039071
The invention relates to the esters of a mixture of 2-methyl-1-butanol and 3-methyl-1-butanol and to the use thereof for producing formulations.
Cosmetic, dermatological or pharmaceutical formulations are manufactured in large amounts and consumed worldwide by consumers. Recently, requirements have increased as regards the sustainability of the formulations and their ingredients. In particular, there is a need to produce as many as possible of the components used on the basis of renewable raw materials.
At the same time, however, consumer requirements are also increasing as regards the sensory properties of the formulations to be used, especially the haptic properties (e.g. oiliness, waxiness) and olfactory properties. This is especially true for formulations which have a high fraction of active ingredients in dispersed form (for example inorganic UV filters such as TiO2 or ZnO) or dissolved form (e.g. organic UV filters or urea).
EP2243517A1 describes the use of esters of isoamyl alcohol (3-methyl-1-butanol), especially of lauric acid esters of 3-methyl-1-butanol, in selected sunscreen formulations, i.e. in cosmetic formulations comprising inorganic UV filters and/or organic UV filters from the group of so-called “triazines”. Here, it is described how such sunscreen formulations have an improved skin feel compared to formulations based on established components, e.g. based on butylene glycol esters or C12-C15 alkyl benzoate.
However, EP2243517A1 does not describe by way of example which specific sensory properties are improved through the use of the esters according to the invention. Furthermore, only sunscreen formulations are expressly mentioned.
“Emollients in Personal Care for Solubilizing Organic UV Absorbers” (IP.COM Journal, IP.COM Inc., West Henrietta, N.Y., US, 22 February 2006, XP013112931, ISSN 1533-0001) likewise discloses a number of components which are suitable for producing sunscreen formulations with good spreadability on skin and good absorption capacity into skin, for example isoamyl laurate (cf. p. 8).
Here too only sunscreen formulations are expressly mentioned.
There is also a need for components for cosmetic, dermatological or pharmaceutical formulations which bring about improved sensory properties of precisely these formulations.
It was therefore an object of the present invention to develop new types of cosmetic ingredients which permit production of cosmetic, dermatological or pharmaceutical formulations with improved sensory properties.
Surprisingly, it has been found that esters based on a mixture of 3-methyl-1-butanol and 2-methyl-1-butanol meet these requirements. Such an isomer mixture of isopentyl alcohol can be obtained from the residues of alcoholic fermentation and therefore constitutes a natural raw material.
Compared to formulations based on known ingredients, e.g. esters of pure 3-methyl-1-butanol, the formulations according to the invention exhibit less of an oily skin feel, less stickiness, and an improved odour.
The present invention therefore provides ester mixtures of at least one optionally branched, optionally unsaturated, optionally substituted carboxylic acid with a chain length of 6 to 30, in particular 8 to 22, preferably 10 to 16, carbon atoms with 2-methyl-1-butanol and 3-methyl-1-butanol, where the weight ratio of 2-methyl-1-butanol and 3-methyl-1-butanol is from 0.05:1 to 1:0.05, in particular from 0.1:1 to 1:1, preferably from 0.1:1 to 0.67:1.
The acid components preferably used for producing the esters according to the invention are optionally branched, optionally unsaturated, optionally substituted acids having 6 to 30 carbon atoms, in particular with 8 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, petroselic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, arachidonic acid, which can be used on their own or in a mixture, in particular lauric acid, myristic acid, palmitic acid and stearic acid, mixtures of coconut fatty acids, in particular completely hydrogenated coconut fatty acids, particularly preferably completely hydrogenated coconut fatty acids with a content of fatty acids of chain lengths C12 to C18 of together >98% by weight, based on the sum of all carboxylic acids.
Here, particular preference is given to using monobasic, optionally unsaturated fatty acids having 12-18 carbon atoms, such as lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, which can be used alone or in a mixture.
Particular preference is given here to lauric acid, myristic acid, palmitic acid and stearic acid, which can be used alone or in a mixture.
In a further embodiment, dibasic acids with 4 to 20 carbon atoms, for example adipic acid or sebacic acid, are used as acid component.
The alcohol mixture used is a mixture of 2-methyl-1-butanol and 3-methyl-1-butanol with a weight ratio of 2-methyl-1-butanol to 3-methyl-1-butanol of 0.05:1 to 1:0.05, in particular from 0.1:1 to 1:1, preferably from 0.1:1 to 0.67:1.
The mixing ratio of the alcohols used can be determined both for this mixture and also for the resulting esterification products by means of 1H-NMR spectroscopy using standard methods and standard solvents (e.g. CDCl3 or DMSO-d6).
The esters can be produced by the methods known to the person skilled in the art, as described for example in ORGANIKUM (Wiley-VCH, 22nd Edition 2004, pages 474-480). Typical processes for producing cosmetic esters utilize acids, e.g. p-TSA, or metal salts (e.g. tin or titanium salts) or enzymes (for example lipases), as catalyst, see e.g. EP1816154A1.
The ester mixtures according to the invention can be obtained directly either as described in the examples by esterification of the mixture of 2-methyl-1-butanol and 3-methyl-1-butanol, although it is likewise possible in accordance with the invention to synthesize the esters of 2-methyl-1-butanol and 3-methyl-1-butanol separately and then to mix them accordingly, although preference is given according to the invention to the first-mentioned one-pot reaction.
The present invention further provides cosmetic, dermatological or pharmaceutical formulations comprising an ester mixture according to the invention.
The formulations according to the invention can be produced as water-in-oil, oil-in-water or water-in-silicone emulsions.
The invention further provides the use of the ester mixtures according to the invention for producing optionally dispersed-solids-containing cosmetic, dermatological or pharmaceutical formulations or care and cleaning compositions for the home or industry, in particular for hard surfaces, leather or textiles. Consequently, the cosmetic, dermatological or pharmaceutical formulations, care and cleaning compositions for the home or industry and the care and cleaning compositions for hard surfaces, leather or textiles comprising an ester mixture according to the invention are likewise provided by the present invention.
The formulation according to the invention can comprise for example at least one additional component selected from the group of
emollients,
emulsifiers,
thickeners/viscosity regulators/stabilizers,
antioxidants,
hydrotropes (or polyols),
solids and fillers,
pearlescent additives,
deodorant and antiperspirant active ingredients,
insect repellents,
self-tanning agents,
preservatives,
conditioners,
perfumes,
dyes,
cosmetic active ingredients,
care additives,
superfatting agents,
solvents.
Substances which can be used as exemplary representatives of the individual groups are known to the person skilled in the art and can be found for example in EP2273966A1. This patent application is hereby incorporated by reference and thus forms part of the disclosure.
As regards further optional components and the amounts of these components used, reference is made expressly to the relevant handbooks known to the person skilled in the art, for example K. Schrader, “Grundlagen and Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics]”, 2nd Edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.
The amounts of the respective additives are governed by the intended use.
Typical guide formulations for the respective applications are known prior art and are contained for example in brochures from the manufacturers of the particular basic materials and active ingredients. These existing formulations can generally be adopted unchanged. If required, the desired modifications can, however, be undertaken without complication by simple experiments for the purposes of adaptation and optimization.
The present invention is described by way of example in the examples listed below without any intention of limiting the invention, the scope of application of which arises from the entire description and the claims, to the embodiments specified in the examples.
Unless stated otherwise, all of the stated percentages (%) are percentages by mass.
160 g of 2-methyl-1-butanol and 300 g of lauric acid are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction which is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. By means of subsequent steam distillation (2 hours, 120° C.), the residual content of 2-methyl-1-butanol is reduced to 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is produced as a colourless liquid without further work-up.
160 g of 3-methyl-1-butanol and 300 g of lauric acid are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 3-methyl-1-butanol is reduced to 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
64 g of 2-methyl-1-butanol, 96 g of 3-methyl-1-butanol and 300 g of lauric acid are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 2-methyl-1-butanol and 3-methyl-1-butanol is reduced to together 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
150 g of 2-methyl-1-butanol and 300 g of coconut fatty acid (completely hydrogenated, distilled coconut fatty acid with a content of fatty acids of chain lengths C12 to C18 of together >98%) are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 2-methyl-1-butanol is reduced to 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
150 g of 3-methyl-1-butanol and 300 g of coconut fatty acid (completely hydrogenated, distilled coconut fatty acid with a content of fatty acids of chain lengths C12 to C18 of together >98%) are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 3-methyl-1-butanol is reduced to 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
64 g of 2-methyl-1-butanol, 96 g of 3-methyl-1-butanol and 300 g of coconut fatty acid (completely hydrogenated, distilled coconut fatty acid with a content of fatty acids of chain lengths C12 to C18 of together >98%) are charged to a multineck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 2-methyl-1-butanol and 3-methyl-1-butanol is reduced to together 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
125 g of 3-methyl-1-butanol, 25 g of 2-methyl-1-butanol and 300 g of coconut fatty acid (completely hydrogenated, distilled coconut fatty acid with a content of fatty acids of chain lengths C12 to C18 of together >98%) are charged to a multi-neck round-bottomed flask and heated to 60° C. After adding 1.5 g of Novozym 435, a vacuum is applied (ca. 120 mbar) until the reaction mixture boils. The water of reaction that is formed is separated off with the help of a water separator and the distilled-off alcohol is returned. After 10 hours, the immobilized enzyme is filtered off and the excess alcohol is removed by distillation. As a result of subsequent steam distillation (2 hours, 120° C.), the residual content of 2-methyl-1-butanol and 3-methyl-1-butanol is reduced to together 20 ppm. The product is dried (1 hour, 120° C., 20 mbar) and is formed as a colourless liquid without further work-up.
All concentrations in the application examples are given in percentages by weight. To produce the emulsions, customary homogenization processes used for oil-in-water and water-in-oil emulsions and known to the person skilled in the art are used.
These experiments aim to show that the mixed esters according to the invention of 2-methyl-1-butanol and 3-methyl-1-butanol and lauric acid bring about advantages with regard to sensory properties and the product odour compared to the respective pure esters.
The test formulations V1, V2 and 1 are O/W lotions. In this connection, oil phase A and water phase B were each heated to 75° C., combined and then homogenized using a suitable homogenizer (e.g. Ultraturrax) for ca. 1-2 minutes.
Stabilizing polymers (xanthan gum, carbomer) were stirred into the emulsion as an oily dispersion at temperatures of 50-60° C. Homogenization was carried out for one minute.
The addition of further ingredients (e.g. preservatives, active ingredients) preferably takes place at 40° C.
In the formulation examples, the individual raw materials are listed with their INCI name.
1)TEGO ® Care PSC 3 (Evonik Goldschmidt GmbH)
2)Euxyl ® PE 9010 (Schülke)
Test formulations 1, V1 and V2 were investigated by a trained sensory subject group (N=13). The skin feel of the cosmetic formulations described in the examples was determined by a so-called panel. For this, a defined amount of the test lotions were applied to a clearly defined area of the forearm. The subjects compared the sensory properties of the cosmetic formulations and of the respective comparison formulation without knowing the composition. Assessment was made on a scale from 0 (little) to 10 (a lot).
Whereas no differences as regards application properties such as “spreadability” and “lubricity” could be found relative to the formulations comprising the comparison emollients, there were noticeable differences as regards the properties “Absorption”, “oiliness” and “stickiness”.
Moreover, the group assessed the odour of the formulations on a scale of from 1 (good) to 3 (poor).
Table 2 summarizes the average values of the described tests.
Test formulations V3, V4 and 2 are W/O creams. To produce them, the oil phase A was heated to 80° C. The water phase was then added slowly to the oil phase with stirring and combined and then homogenization was carried out using a suitable homogenizer (e.g. Ultraturrax) for ca. 1-2 minutes.
After adding the preservative (below 40° C.), homogenization is again briefly carried out below 30° C.
3)ISOLAN ® PDI (Evonik Goldschmidt GmbH)
4)Euxyl ® K 712 (Schülke)
Table 4 summarizes the assessments of the sensory and olfactory panel for the W/O creams.
The comparison in both test emulsions consistently shows that the mixed esters according to the invention have sensory and olfactory advantages compared with the pure esters in the prior art.
1)TEGO ® Care PSC 3 (Evonik Goldschmidt GmbH)
2)TEGOSOFT ® CT (Evonik Goldschmidt GmbH)
3)Rokonsal ® BSB-N (ISP)
1)TEGO ® Care PSC 3 (Evonik Goldschmidt GmbH)
2)TEGIN ® M (Evonik Goldschmidt GmbH)
3)TEGO ® Alkanol 18 (Evonik Goldschmidt GmbH)
4)TEGOSOFT ® DC (Evonik Goldschmidt GmbH)
5)TEGOSOFT ® OER (Evonik Goldschmidt GmbH)
6)Rokonsal ® BSB-N (ISP)
1)AXOL ® C 62 (Evonik Goldschmidt GmbH)
2)TEGO ® Alkanol 1618 (Evonik Goldschmidt GmbH)
3)TEGOSOFT ® CT (Evonik Goldschmidt GmbH)
4)TEGOSOFT ® M (Evonik Goldschmidt GmbH)
5)Tinosorb ® S (BASF SE)
6)Uvinul ® A Plus (BASF SE)
7)TEGO ® Sun T 805 (Evonik Goldschmidt GmbH)
8)TEGO ® Carbomer 141 G (Evonik Goldschmidt GmbH)
9)Microcare ® MEM (Thor GmbH)
1)ABIL ® EM 90 (Evonik Goldschmidt GmbH)
2)ISOLAN ® GPS (Evonik Goldschmidt GmbH)
3)TEGOSOFT ® TN (Evonik Goldschmidt GmbH)
4)Euxyl ® PE 9010 (Schülke & Mayr)
The anhydrous concentrate from Example 8 can be combined with customary propellant gas mixtures such as e.g. propane/butane/isopropane/isobutane in the ratio of 25 to 50 parts of emulsion to 75 to 50 parts of propellant gas as aerosol.
1)ABIL ® WE 09 (Evonik Goldschmidt GmbH)
2)KSG-830 (Shin-Etsu)
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2011 006 362.5 | Mar 2011 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP12/55362 | 3/27/2012 | WO | 00 | 9/23/2013 |
