Alkylester of andiroba oil

Abstract

The present invention relates to a process of manufacturing an alkylester mixture obtained from Andiroba oil, which comprises a two step esterification with a first esterification in the presence of an acidic catalyst followed by an alkaline transesterification of the remaining glyceridester. Further, the present invention relates to a mixture of C1 to C3 - alkylesters obtained from Andiroba oil, characterized in that the alkylesters contains less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms, which has perfect properties for use as an emollient in cosmetic compositions.

Description

[0001] Alkylester of Andiroba Oil

[0002] The present invention relates to a mixture of C1 to C3 - alkylesters obtained from Andiroba oil, characterized in that the alkylester contains less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms and the use thereof in personal are and cosmetic applications, especially as an emollient. Further, the present invention relates to a process of manufacturing an alkylester mixture obtained from Andiroba oil.

[0003] Emollients, also known as oil bodies, are used by the cosmetics and personal care industry in a multitude of formulations especially for moisturizing, protecting, lubricating and thereby soften the skin. Emollients can be separated in chemical groups, such as mineral, animal or vegetable oils, (partly synthetic) triglycerides, fatty acid ester, fatty acid ether, fatty acid carboxylates, hydrocarbons, fatty alcohols, long chain fatty acids and silicones. The latter have been banned for toxicological, ecological and safety reasons, so that there is a demand for alternative raw materials for such formulation tasks.

[0004] It was an object of the invention to find emollient raw materials which are ecologically and toxicologically uncontroversial. These raw materials should be obtainable on the basis of renewable sources and have an improved CO2 balance compared to the prior art raw materials. They should be usable directly in typical cosmetic and / or pharmaceutical formulations without application-related restrictions. Furthermore, the raw materials should have improved sensory properties, and it would also be desirable that these raw materials have a favorable skin compatibility. It was of particular interest to provide raw materials whose possible uses with regard to formulation or sensory properties are comparable to those of silicone oils, especially to those of low-viscosity silicone oils, for example dimethicones and cyclomethicone. It was desirable, more particularly, to provide raw materials which are suitable as substitutes for silicone oils but based on renewable raw materials.

[0005] Andiroba oil extracted from the seeds of Carapa Guianensis - synonyms are Bastard mahagony, Cedro Bateo, Crabwood, Toldo White Crabwood, Krappa tree, Masabaol, Quassia Bigeleaf - was traditionally used for the production of insect repellent and in traditional medicine. Meanwhile it is a commodity sold industrially for cosmetic use and well-known as cosmetic ingredient.

[0006] Several Brazilian patent applications such as BR9903830 A and BR 102021023565 A2 disclose the use of andiroba oil in hair care compositions and creams (BRPI0803939 A2) especially as an insect repellent (BR8605739 A2, BRPI0804327 A2 and CN 107468561 A). The oil was as well used as active for the treatment of psoriasis as described in US8545904 B1 . According to Korean patent KR10-1044597B1 andiroba oil, in an amount of 0.0001% to 10 % by weight of the total weight of the composition, is useful as a cosmetic ingredient for skin lightening and wrinkling. However, the sensory skin feeling of the oil on the skin is less pleasant as it leaves a greasy film for a longer time period while keeping its moisturizing properties. It was thus an object of the present invention to improve the moisturizing properties for a longer time after application without leaving an oily film on the skin.

[0007] In addition andiroba oil is a raw material that can suffer high quality variations, mainly depending on its acidity index, thus its derivatives suffer from this variation too. Only if andiroba oil has a low acidity index, it can efficiently be used as an active ingredient for the production of cosmetic products. If the acidity index is high, it is mainly used as a raw material undergoing the saponification reaction, thus replacing palm kernel oil.

[0008] It was another object to provide Andiroba oil derivatives with a better stability and consistent quality for the use in cosmetic products guaranteeing a product of 100% renewable raw material for cosmetic and personal care application.

[0009] It has surprisingly been found that an improved skin moisturizing with a less oily appearance as well as a highly stable cosmetic agent can be achieved by a C1 to C3-alkylester obtained from Andiroba oil. This can be obtained by a process comprising two esterification steps a first esterification with acidic catalysis and a second subsequent transesterification step catalyzed by an alkaline catalyst.

[0010] Detailed Description

[0011] Carapa guianensis of the family of Meliaceae (synonyms are Andiroba, Andiroba do igapo, Andiroba saruba, Andirova, Bastard mahagony, Brazilian mahogany, Bois caille, Cachipou, Camacari, Carapa, Carapa rouge, Carapinha, Cedro Bateo, Cedro Macho, Crabwood, Crapo, Fiqueroa, Guino, landiroba, Karaba, Krapa, Krappa, Mandiroba, Masabaol, Masabolo, Najesi, Nandiroba, Nhandiroba, Noix de Crab, Paramahogany, Penaiba, Quassia Bigeleaf, Randiroba, Requia, Sopo, Tangare, Toldo White Crabwood, Yandiroba or Y-andiroba) is a large tree growing up to 35 m (maximum 55 m) on marshlands or other hydromorphic soils throughout eastern Amazonia, the Caribbean, Central America up to Nicaragua, and Africa. It has flowers from August to October, which produce capsule fruits of about 6-12 centimeters in size containing two to four angular, brown seeds (nuts) in each compartment.

[0012] Andiroba oil is easily produced by either mechanical or chemical extraction of the cultivated seeds. On average, a tree delivers around 125 kg of seeds per year, from which, depending on the method, around 8-22 liters of oil are extracted. The oil contained in the carapa seed is light yellow and extremely bitter and solidifies compared to petroleum jelly when subjected to a temperature below 25 °C.

[0013] Currently andiroba oil is consumed in the cosmetics market for the manufacture of soaps, moisturizing creams and shampoos among others. As andiroba oil suffers from high variations, especially in its acidity index, it was one object to achieve a biobased ingredient of the oil with better stability and of consistent quality for cosmetic use.

[0014] It was another object to provide a cosmetic ingredient with good emollient properties.

[0015] Surprisingly this object was solved with a C1 to C3 - alkylester mixture obtained from Andiroba oil, characterized in that the alkylester contains less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms. The term “C1 to C3 - alkylester” comprises the methyl, ethyl, propyl- or isopropylester obtained from Andiroba oil.

[0016] Surprisingly this ester is an emollient that has improved sensory and moisturizing properties. Very often, emollients leave an oily film on the skin after application, which on the one hand results in the requested moisturization of the treated skin, but on the other hand leaves an uncomfortable sensory feeling. Usually, a few hours after application the film is no longer on the skin, but hydration is also reduced. Contrary to this behavior the ester according to the invention leaves a pleasant skin feeling after 4 hours without an oily film on the skin and still shows an excellent moisturizing effect.

[0017] Preferably the C1 to C3-alkylester mixture according to the invention contains less than 5% saturated and unsaturated fatty acids with 6 to 14 carbon atoms, 15 to 35 % palmitic (C16:0) fatty acid and 40 to 60 % unsaturated fatty acids with 18 carbon atoms.

[0018] More preferably the C1 to C3 - alkylester mixture is characterized in that it contains the specific distribution of fatty acids caproic (C6:0), caprilic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), palmitic (C16:0), palmitoleic (C16: 1 ), stearic (C18:0), oleic (C18: 1), linoleic (C18:2) and linolenic (C18:3) acids in the following proportion with numbers given as relative content in (%):

[0019] Caproic (C6:0) < 2.0 caprilic acid (C8:0) < 2.0 capric acid (C10:0) < 2.0 lauric acid (C12:0) < 2.0 myristic acid (C14:0) < 2.0 palmitic acid (C16:0) 15.0 - 35.0 stearic acid (C18:0) 5.0 - 15.0 oleic acid (C18:1) 40.0 - 60.0 linoleic C18:2 5.0 - 10.0 and linolenic C18:3 < 3.

[0020] Most preferably it contains the specific distribution of fatty acids caproic (C6:0), caprilic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), palmitic (C16:0), palmitoleic (C16:1), stearic

[0021] (C18:0), oleic (C18: 1 ), linoleic (C18:2) and linolenic (C18:3) acids in the following proportion with numbers given as relative content in (%):

[0022] Caproic (C6:0) < 1.0 caprilic acid (C8:0) < 1.0 capric acid (C10:0) < 1.0 lauric acid (C12:0) < 1.0 myristic acid (C14:0) < 1.0 palmitic acid (C16:0) 20.0 - 30.0 stearic acid (C18:0) 7.0 - 12.0 oleic acid (C18:1) 45.0 - 55.0 linoleic C18:2 7.5 - 9.0 and linolenic C18:3 < 2 .

[0023] The determination of the relative composition of carbon chains was carried out using a gas chromatographic system with a flame ionization detector. The percentages of the fatty acid distribution are determined as commonly analyzed by gas chromatography (GC) after conversion to fatty acid methyl esters (FAMEs). Gas chromatography was conducted with a G16 Phase Fused Silica Column (WAX-PEG - 0.53 mm x 30 m x 0.50 pm)

[0024] A standard solution and the sample solution are analyzed. The identification of carbon chains is done by comparing the retention times of the sample peaks with the standard. Reporting is done as a percentage area (relative content) for each peak based on the total area.

[0025] Preferably the C1 to C3 - alkylester mixture is an ethylester obtained from Andiroba oil. The term “ethylester” and “ethylester mixture” is identically used as the ethylester is always a mixture of ethanol with different fatty acids.

[0026] The ethylester obtained from Andiroba oil is completely based on raw materials of renewable origin. Using ethanol enables a higher quality and stability of andiroba oil derivatives. It is characterized in that it contains less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms.

[0027] Preferably the ethylester mixture according to the invention contains less than 5% saturated and unsaturated fatty acids with 6 to 14 carbon atoms, 15 to 35 % palmitic (C16:0) fatty acid and 40 to 60 % unsaturated fatty acids with 18 carbon atoms.

[0028] More preferably the ethylester mixture is characterized in that it contains the specific distribution of fatty acids caproic (C6:0), caprilic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), palmitic (C16:0), palmitoleic (C16: 1), stearic (C18:0), oleic (C18: 1), linoleic (C18:2) and linolenic

[0029] (C18:3) acids in the following proportion with numbers given as relative content in (%):

[0030] Caproic (C6:0) < 2.0 caprilic acid (C8:0) < 2.0 capric acid (C10:0) < 2.0 lauric acid (C12:0) < 2.0 myristic acid (C14:0) < 2.0 palmitic acid (C16:0) 15.0 - 35.0 stearic acid (C18:0) 5.0 - 15.0 oleic acid (C18:1) 40.0 - 60.0 linoleic C18:2 5.0 - 10.0 and linolenic C18:3 < 3.

[0031] Most preferably the ethylester contains the specific distribution of fatty acids caproic (C6:0), caprilic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), palmitic (C16:0), palmitoleic

[0032] (C16: 1 ), stearic (C18:0), oleic (C18: 1), linoleic (C18:2) and linolenic (C18:3) acids in the following proportion with numbers given as relative content in (%):

[0033] Caproic (C6:0) < 1.0 caprilic acid (C8:0) < 1.0 capric acid (C10:0) < 1.0 lauric acid (C12:0) < 1.0 myristic acid (C14:0) < 1.0 palmitic acid (C16:0) 20.0 - 30.0 stearic acid (C18:0) 7.0 - 12.0 oleic acid (C18:1) 45.0 - 55.0 linoleic C18:2 7.5 - 9.0 and linolenic C18:3 < 2. The C1 to C3 alkylester mixture according to the invention has specific characteristics in respect of the acid value (also named as acid number), iodine value and saponification value.

[0034] Acid Value

[0035] The acid value or acid number is defined as the milligrams of KOH required to completely neutralize free acid present in 1 g of the oil. The accurately weighted quantity of oil is taken in a conical flask and 50 mL neutral alcohol is added, the mixture is heated over bath using water condenser for one hour. The contents are cooled titrated with KOH solution using phenolphthalein indicator.

[0036] The acid value is calculated as follows: Acid value of oil = (volume of KOH used (mL)) x normality of KOH) / (weight of oil taken (g))

[0037] Andiroba oil is an oil with a high acid number varying extremely depending on the way of harvesting and production of the oil. However, the acid value of the inventive C1 to 03 alkylester mixture obtained from Andiroba oil is below 10 mg KOH / g sample, preferably the acid value is below 8 mg KOH I g sample, more preferably it is below 6 mg KOH / g sample.

[0038] Iodine value

[0039] The iodine value (also iodine absorption value, iodine number or iodine index) is the mass of iodine in grams that is consumed by 100 grams of a chemical substance. Iodine numbers are often used to determine the degree of unsaturation in fats, oils and waxes. In fatty acids, unsaturation occurs mainly as double bonds which are very reactive towards halogens, the iodine in this case. Thus, the higher the iodine value, the more unsaturations are present in the fat.

[0040] The iodine value of the C1 to C3 alkylester mixture obtained from Andiroba oil was determined according to ASTM D 1959

[0041] Despite the high amount of oleic acid andiroba oil belongs to the group of non-drying oils with a iodine value below 125 g lodine / 100 g. The inventive ester should preferably have a iodine value below 90 g lodine / 100 g ester, more preferably below 80 g lodine / 100 g sample and most preferably below 70 g lodine / 100 g sample.

[0042] Saponification Value

[0043] Saponification value or saponification number (SV or SN) represents the number of milligrams of potassium hydroxide (KOH) or sodium hydroxide (NaOH) required to saponify one gram of fat The saponification value was determined according to DIN ISO 660 The saponification value of the C1 to C3 alkylester mixture obtained from Andiroba oil is between 170 and 210 mg KOH I g sample (OK), preferably between 175 and 205 mg KOH I g sample and most preferably between 180 and 200 mg KOH / g sample.

[0044] Another object of the invention is the use of a mixture of C1 to 03 - alkylesters obtained from andiroba oil in cosmetic, personal care and / or pharmaceutical formulations.

[0045] The cosmetic compositions according to the invention can be in particular formulations for bodycare, facecare, suncare and haircare as well as decorative cosmetics e.g. a body milk, creams, lotions, aftershave lotions, sprayable emulsions, tonics and scented waters, products for eliminating body odor such as deodorants and antiperspirants, make-up removers, conditioners, styling products, foam and shower baths, hair shampoos and care rinses.

[0046] Personal care composition refers to any topical and oral product that can be used at least once daily by the consumer as an everyday care product for caring, cleaning, protecting, maintaining, perfuming or changing the appearance or feel of the human body, e.g. for face, hair, body, or oral care. The personal care composition may comprise one or more active agents, e.g., organic and / or inorganic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances. Suitable daily care composition are according to the present invention, e.g. leave-on face and body care products and rinse-off face and body care products.

[0047] The term “pharmaceutical formulation” as used herein refers to any suitable pharmaceutical formulation, which may e.g. be administered in any suitable manner such as by oral, transdermal, parenteral, nasal, vaginal, or rectal application. Suitable solid pharmaceutical formulation can be in form of tablets, suppositories, or capsules or in form of a spray. Suitable transdermal pharmaceutical formulations encompass patches or formulations such as sprays, lotions, creams, oils, foams, ointments, powders, or gels. Liquid pharmaceutical formulations are preferably administered orally, parenterally, or nasal.

[0048] Surprisingly the mixture of C1 to C3-alkyl esters obtained from andiroba ester has improved moisturizing and sensory properties and could thus preferably be used as emollient or dispersant. The term “emollient” relates to cosmetic specific oils used for protecting, moisturizing and lubricating the skin. The word emollient is derived from the Latin word mollire, to soften. In general, emollients prevent evaporation of water from the skin by forming an occlusive coating. They can be divided into different groups depending on their polarity index. Accordingly, another object of invention are cosmetic, personal care and / or pharmaceutical compositions comprising 0.1 to 80 % by weight of a mixture of C1 to C3 -alkylesters obtained from Andiroba oil, preferably of the ethylester obtained from andiroba oil.

[0049] Before describing in detail exemplary embodiments of the present invention, definitions which are important for understanding the present invention are given.

[0050] As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates a deviation from the indicated numerical value of ±10 %, preferably ±8 %, more preferably ±5 %, even more preferably ±2 %. It is to be understood that the term "comprising" and “encompassing” is not limiting. For the purposes of the present invention the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.

[0051] As used herein the term “does not comprise”, “does not contain”, or “free of’ means in the context that the composition of the present invention is free of a specific compound or group of compounds, which may be combined under a collective term, that the composition does not comprise said compound or group of compounds in an amount of more than 0.8 % by weight, based on the total weight of the composition. Furthermore, it is preferred that the composition according to the present invention does not comprise said compounds or group of compounds in an amount of more than 0.5 % by weight, preferably the composition does not comprise said compounds or group of compounds at all.

[0052] When referring to compositions and the weight percent of the therein comprised ingredients it is to be understood that according to the present invention the overall amount of ingredients does not exceed 100% (± 1 % due to rounding).

[0053] Suitable cosmetic and personal care compositions are leave-on face and body care products, e.g. sunscreen compositions, decorative preparations, and skin care preparations and rinse-off face and body care products.

[0054] The term “sunscreen composition” or “sunscreen” refers to any topical product, which absorbs and which may further reflect and scatter certain parts of UV radiation. Thus, the term “sunscreen composition” is to be understood as not only including sunscreen compositions, but also any cosmetic compositions that provide UV protection. The term “topical product” refers to a product that is applied to the skin and can refer, e.g., to sprays, lotions, creams, oils, foams, powders, or gels. According to the present invention the sunscreen composition may comprise one or more active agents, e.g., organic and inorganic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances.

[0055] Suitable decorative preparations are, e.g., lipsticks, lip gloss, nail varnishes, eye shadows, mascaras, eye pencils (Kohl), dry and moist make-up, rouge, powders, coversticks, depilatory agents and suntan lotions.

[0056] Suitable skin care preparations are e.g., moisturizing, refining, and lifting preparations. The cited daily care compositions can be in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.

[0057] Suitable rinse-off face and body care products are, e.g. shampoo, conditioner, shower gel, body scrub, face scrub, and hand soap. In particular rinse-off products are hair shampoos, shower gels, soaps, syndet bars, washing pastes, washing lotions, scrub preparations, facial cleansers, intimate hygiene washes, foam baths, oil baths, shower baths, shaving foams, shaving lotions, shaving creams, foaming powders / tabs and dental care products (for example toothpastes, mouthwashes and the like). Also baby care products like baby shampoo and baths are suitable rinse-off products. A preferred embodiment of the invention relates to cosmetic, personal care and / or pharmaceutical formulations comprising 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of the mixture of C1 to C3 -alkylesters obtained from andiroba oil.

[0058] A more preferred embodiment of the invention relates to cosmetic, personal care and / or pharmaceutical formulations comprising 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of an ethylester obtained from andiroba oil.

[0059] Preferably these cosmetic, personal care and / or pharmaceutical formulations are comprising additional auxiliaries and additives selected from the group consisting of surface-active substances (surfactants, emulsifiers), other oil components, pearlizing waxes, consistency factors, thickeners, superfatting agents, stabilizers, polymers, fats, waxes, lecithins, phospholipids, biogenic agents, UV protection factors, antioxidants, deodorizers, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanning agents, tyrosinase inhibitors (depigmenting agents), hydrotropes, solubilizers, preservatives, perfume oils, pigments, dyes and mixtures thereof.

[0060] A preferred object of the invention is a cosmetic composition containing 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a mixture of C1 to C3 alkylesters, preferably ethylester, obtained from Andiroba oil and at least one antiperspirant / deodorant active ingredient. According to the invention, suitable antiperspirant / deodorant active ingredients are all active ingredients which counteract, mask or eliminate body odors. Body odors arise as a result of the action of skin bacteria on apocrine perspiration, which forms unpleasant-smelling degradation products. Suitable antiperspirant / deodorant active ingredients are especially compounds selected from the group consisting of antiperspirants, esterase inhibitors, bactericidal or bacteriostatic active ingredients and / or perspiration-absorbing substances.

[0061] Antiperspirants

[0062] Antiperspirants are salts of aluminum, of zirconium or of zinc. Such suitable antihydrotic active ingredients are, for example, aluminum chloride, aluminum ch loro hydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and complexes thereof, for example with 1 ,2- propylene glycol, aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complexes thereof, for example with amino acids such as glycine. Preference is given to using aluminum ch loro hydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium bicarbonate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium pidolate, magnesium gluconate, magnesium glutamate, magnesium heptagluconate, magnesium ketogluconate, magnesium lactate, magnesium ascorbate, magnesium citrate, magnesium aspartate, magnesium pantothenate, magnesium sorbate, magnesium nitrate, magnesium lactate gluconate, magnesium fulvate and complexes thereof.

[0063] The inventive formulations may comprise the antiperspirants in amounts of 0.5 to 50%, preferably

[0064] 1 to 25% and especially 1 to 10% by weight - based on the total weight of the cosmetic and / or pharmaceutical formulation.

[0065] Esterase inhibitors

[0066] In the presence of perspiration in the underarm region, bacteria form extracellular enzymes - esterases, preferably proteases and / or lipases - which cleave esters present in the perspiration and thus release odorants. Suitable esterase inhibitors are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen® CAT, Cognis GmbH, Dusseldorf / FRG). The substances inhibit enzyme activity and hence reduce odor formation. Further substances which are possible esterase inhibitors are sterol sulfates or phosphates, for example sulfates or phosphates of lanosterol, of cholesterol, of campesterol, of stigmasterol and of sitosterol, dicarboxylic acids and esters thereof, for example glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

[0067] The inventive formulations may comprise the esterase inhibitors in amounts of 0.01 to 20%, preferably 0.1 to 10% and especially 0.3 to 5% by weight - based on the total weight of the cosmetic and / or pharmaceutical formulation.

[0068] Bactericidal or bacteriostatic active ingredients

[0069] Typical examples of suitable bactericidal or bacteriostatic active ingredients are especially chitosan and phenoxyethanol. 5-Chloro-2-(2,4-dichlorophenoxy)phenol has also been found to be particularly effective, and is sold under the Irgasan® brand by Ciba-Geigy, Basle, Switzerland. Suitable germicides are in principle all substances which act against Gram-positive bacteria, for example 4 hydroxybenzoic acid and the salts and esters thereof, N-(4-chlorophenyl)-N’-(3,4- dichlorophenyl)urea, 2,4,4’-trichloro-2’-hydroxydiphenyl ether (triclosan), 4 chloro-3,5- dimethylphenol, 2,2’-methylenebis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)phenol,

[0070] 2 benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1 ,2-propanediol, 3-iodo-2-propynylbutyl carbamate, chlorhexidine, 3,4,4’-trichlorocarbanilide (TTC), antibacterial odorants, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate (GML), diglyceryl monocaprate (DMC), N- alkylsalicylamides, for example n-octylsalicylamide or n-decylsalicylamide.

[0071] The inventive formulations may comprise the bactericidal or bacteriostatic active ingredients in amounts of 0.01 to 5% and preferably 0.1 to 2% by weight - based on the total weight of the cosmetic and / or pharmaceutical formulation.

[0072] Perspiration-absorbing substances

[0073] Useful perspiration-absorbing substances include modified starches, for example Dry Flo Plus (from National Starch), silicates, talc and other substances of similar polymorphism, which appear suitable for absorption of perspiration. The inventive formulations may comprise the perspirationabsorbing substances in amounts of 0.1 to 30%, preferably 1 to 20% and especially 2 to 8% by weight - based on the total weight of the cosmetic and / or pharmaceutical formulation.

[0074] The inventive mixture of C1 to C3 alkylesters obtained from Andiroba oil, characterized in that the alkylester contains less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms, has very good UV-filter dissolving and dispersing properties.

[0075] Another preferred object of the invention is therefore a cosmetic composition containing 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a mixture of C1 to C3 alkylesters, preferably ethylester, with less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms obtained from Andiroba oil and at least one UV light protection filter.

[0076] The term “UV light protection filter” or “ultraviolet (UV) filter” as used herein refers to organic or inorganic compounds, which can absorb and may further reflect and scatter UV radiation caused by sunlight. UV-filter can be classified based on their UV protection curve as UV-A, UV-B, or broadband filters.

[0077] In general, UV light can be divided into UV-A radiation (320 - 400 nm) and UV-B radiation (290 - 320 nm). The definition of “broadband” protection (also referred to as broad-spectrum or broad protection) is based on the “critical wavelength”. For broadband coverage, UV-B and UV-A protection must be provided. According to the US requirements, a critical wavelength of at least 370 nm is required for achieving broad spectrum protection. The term “critical wavelength” is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) represents 90 % of the total area under the curve in the UV region (290-400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 290-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 370 nm.

[0078] According to a preferred embodiment of the present invention, the cosmetic composition further comprises at least one organic or inorganic UV filter. The presence of at least one organic or inorganic UV filter provides protection of the skin from dangerous UVA and UVB radiation.

[0079] It is preferred that the at least one organic or inorganic UV filter is selected from the group consisting of:

[0080] UVA absorbing filters

[0081] 4-(tert.-butyl)-4’-methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate),

[0082] [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-1-(sulfomethyl)-3-bicyclo[2.2.1] heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-2-oxo-1- bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 1 ,T-(1 ,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (INCI Bis-(diethylaminohydroxybenzoyl benzoyl) piperazine),

[0083] 2-ethoxyethyl (2Z)-2-cyano-2-[3-(3-methoxypropylamino)cyclohex-2-en-1-ylidene]acetate (INCI methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate);

[0084] Broad spectrum (UVA+UVB) absorbing filters 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1 ,3,5 triazine (INCI bisethylhexyloxyphenyl methoxyphenyl triazine), 2,2’-methylenebis[6-(2H-1 ,2,3-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol] (INCI methylene bis-benzotriazolyl tetramethylbutylphenol), 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1- disiloxanyl]propyl]phenol (INCI drometrizole trisiloxane), phenylene bis-diphenyltriazine, Zinc oxide, UVB absorbing filters

[0085] 2-phenyl-1 H-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), Tris-biphenyl triazine,

[0086] 4,4’,4”-(1 ,3,5-triazin-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone),

[0087] (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), Dimethicone diethyl benzalmalonate (INCI Polysilicone-15), diethylhexyl butamido triazone, Titanium dioxide, Cerium oxide; and mixtures thereof. These UV filters are commonly employed UV filters with excellent UV protection properties.

[0088] According to a further preferred embodiment of the invention, the at least one organic or inorganic UV filter is an organic UV filter selected from the group consisting of 4-(tert.-butyl)-4’- methoxydibenzoylmethane (INCI butyl methoxydibenzoylmethane), hexyl 2-[4-(diethylamino)-2- hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4-bis-{[4-(2- ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1 ,3,5 triazine (INCI bisethylhexyloxyphenyl methoxyphenyl triazine), 4,4’,4”-(1 , 3, 5-triazin-2 ,4,6-triyltriim ino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), and mixtures thereof. These UV filters absorb UV radiation particularly effectively and have a good ecological footprint.

[0089] In a particularly preferred embodiment of the invention, the cosmetic composition comprises at least one UV-A filter and at least one UV-B filter. It is further preferred that the cosmetic composition also comprises at least one broadband UV filter. The most preferred UV-A filter are hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate) and / or butyl methoxydibenzoylmethane. The most preferred UV-B filter is 4, 4’, 4”- (1 ,3,5-triazin-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone). The most preferred broadband UV filter is 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4- methoxyphenyl)-1 ,3,5 triazine (INCI bis-ethylhexyloxyphenyl methoxyphenyl triazine). The combination of hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4- methoxyphenyl)-1 ,3,5 triazine (INCI bis-ethylhexyloxyphenyl methoxyphenyl triazine), and 4,4’,4”-(1 ,3,5-triazin-2,4,6-triyltriimino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone) is particularly preferred since it covers the entire UV absorption spectrum relevant to skin protection in a highly effective manner. However, combinations of other UV filters for optimal UV-A as well as UV B protection are also possible. According to another preferred embodiment, the cosmetic composition is free of all of the UV- filters 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI octocrylene), (RS)-2-ethylhexyl- (2E)-3-(4-methoxyphenyl)prop-2-enoate (INCI ethylhexyl methoxycinnamate), and 3,3,5- trimethyl-cyclohexyl salicylate (INCI Homosalate). There is a growing concern that these UV filters may have negative health and / or environmental effects. Consequently, it is preferable that the cosmetic composition is free of these filters.

[0090] A preferred embodiment of the invention relates to cosmetic and / or pharmaceutical formulations comprising 0.1 to 80% by weight, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a C1 to C3 alkylester, preferably ethylester, obtained from Andiroba oil, and at least one UV light protection filter selected from the group consisting of hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), butyl methoxydibenzoylmethane, 4,4’,4”-(1 , 3, 5-triazin-2 ,4,6-triyltriim ino)tris-benzoic acid tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]- phenyl}-6-(4-methoxyphenyl)-1 ,3,5 triazine (INCI bis-ethylhexyl-oxyphenyl methoxyphenyl triazine) and mixtures thereof.

[0091] Another preferred object of the invention is thus a cosmetic formulation containing 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a mixture of C1 to C3 alkylesters, preferably ethylester, obtained from Andiroba oil and at least one pigment and / or dye.

[0092] It has been shown that the mixture of C1 to C3 -alkylesters obtained from andiroba oil provides an improvement in the distribution of pigments and dyes in decorative cosmetics.

[0093] The term pigment encompasses particles of any kind which are white or colored, organic or inorganic, are insoluble in the formulations, and serve the purpose of coloring the formulation.

[0094] The pigments may be present in a proportion of 0.1 to 15% by weight, especially 1 to 10% by weight, and in particular from 2 to 8% by weight, relative to the total weight of the cosmetic composition.

[0095] In a preferred embodiment, inorganic pigments are used, particular preference being given to metal oxides.

[0096] Examples of inorganic pigments include: titanium dioxide, optionally surface-coated, zirconium or cerium oxides, and zinc, iron (black, yellow or red) and chromium oxides, manganese violet, ultramarine blue, Prussian blue, chromium hydrates and iron(lll) blue, metal powders such as aluminum powder or copper powder. In a preferred embodiment of the invention, the pigment is selected from the inorganic pigments, preferably from the metal oxides. In a preferred embodiment, the pigment is selected from the group consisting of titanium dioxide, zinc oxide, iron oxide and mixtures thereof.

[0097] The pigments may be present either individually or in mixtures.

[0098] Preference is given in the context of the present invention to pigment mixtures composed of white pigments (e.g. kaolin, titanium dioxide or zinc oxide) and inorganic color pigments (e.g. iron oxide pigments, chromium oxides), and the pigments may be present in coated or uncoated form. Among the color pigments, iron oxides are particularly preferred.

[0099] Advantageously in the context of the present invention, the pigment(s) may also be selected from the group of the effect pigments which impart to the cosmetic formulation, in addition to the pure color, an additional property - for example angular dependence of the color (flop), luster (not surface luster) or texture. Such effect pigments are used in accordance with the invention advantageously in addition to one or more white and / or color pigments.

[0100] The most important group of the effect pigments is that of the luster pigments, which, according to DIN 55944: 2003-11 , include the metal effect pigments and the pearlescent pigments. Some specific effect pigments cannot be assigned to these two groups, for example graphite platelets, iron oxide platelets and micronized titanium dioxide, the latter not giving a luster effect, but rather an angle-dependent light-scattering effect. The luster pigments to DIN 55943: 2001-10 are predominantly effect pigment platelets. Aligned in parallel, luster pigments exhibit a characteristic luster. The visual effect of luster pigments is based on the directed reflection on metallic particles (metal effect pigments), on transparent particles with a high refractive index (pearlescent pigments) or on the phenomenon of interference (interference pigments) (DIN 55944: 2003 11). Examples of commercial effect pigments preferred in accordance with the invention are: Timiron and #174; from Merck, Iriodin and #174; from Merck (pearlescent and color luster pigments for decorative industrial applications), Xirallic and #174; from Merck (intense-color crystal effect pigments).

[0101] In addition, the inventive formulations may advantageously also comprise organic color pigments, i.e. organic dyes which are virtually insoluble in the formulation. According to DIN 55944: 1990- 04, organic pigments can be divided according to chemical aspects into azo pigments and polycyclic pigments, and according to color aspects into chromatic or black pigments. Organic white pigments are of no practical significance.

[0102] It is also advantageous in the context of the present invention when the inventive formulation comprises one or more dyes. The dyes may be either of synthetic or natural origin.

[0103] A list of suitable dyes can be found in EP 1 371 359 A2, page 8, lines 25-57, page 9 and page 10, and also page 11 , lines 1 to 54, to which reference is hereby explicitly made.

[0104] The inventive formulations comprise typically 0.01 to 5% and preferably 0.1 to 1.0% by weight of dyes - based on the total weight of the cosmetic and / or pharmaceutical formulation. The inventive formulations typically comprise a total amount of dyes and pigments in the range from 0.01 to 30% by weight, especially 0.1 to 15% by weight, preferably 1 to 10% by weight, based on the total weight of the cosmetic and / or pharmaceutical formulation.

[0105] Suitable dyes and pigments are especially the dyes and pigments approved according to Annex IV of the Commission Directive (in the version: Commission Directive 2007 / 22 / EC of 17 April 2007 amending Council Directive 76 / 768 / EEC, concerning cosmetic products, for the purposes of adapting Annexes IV and VI thereto to technical progress), to which reference is hereby explicitly made.

[0106] Another preferred object of the invention is a cosmetic formulation containing 0.1 to 80% by weight, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a mixture of C1 to C3 alkylesters, preferably ethylester, with less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms obtained from Andiroba oil and at least one polyol and / or emulsifier and / or a surfactant and / or a wax component and / or a polymer and / or a further emollient.

[0107] More preferably the polyols are selected from the group consisting of Glycerin, Propylene Glycol, 1 , 3-Butylene Glycol, Dipropylene Glycol, Neopentyl Glycol, 1 , 2-Pentanediol or 1 , 2-Hexanediol.

[0108] Emulsifier

[0109] The inventive formulations may comprise emulsifier(s) typically in an amount of 0 to 40% by weight, preferably 0.1 to 20% by weight, preferably 0.1 to 15% by weight and especially 0.1 to 10% by weight, based on the total weight of the formulation.

[0110] Every emulsifier is assigned a so-called HLB value (a dimensionless number between 0 and 20) which specifies whether there is a preference for water or oil solubility. Numbers below 9 indicate preferentially oil-soluble, hydrophobic emulsifiers, numbers above 11 water-soluble, hydrophilic emulsifiers. The HLB value says something about the equilibrium of the size and strength of the hydrophilic and lipophilic groups of an emulsifier. The HLB value of an emulsifier can also be calculated from increments, and the HLB increments for the different hydrophilic and hydrophobic groups from which a molecule is composed can be found in tabular works (e.g. H.P. Fiedler, Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik und angrenzende Gebiete [Lexicon of the Excipients for Pharmacy, Cosmetics and Related Fields], Editio Cantor Verlag, Aulendorf, 4th Ed. 1996) or manufacturer data. The solubility of the emulsifier in oil or water effectively determines the emulsion type and the number of phases. When the emulsifier has better solubility in water, an O / W emulsion is obtained. When the emulsifier, in contrast, has better solubility in the oil phase, a W / O emulsion arises under otherwise identical production conditions. Adjusting the hydrophilicity and lipophilicity of the emulsifier e.g. one oil phase, one water phase, two separated phases of oil and water or a bi-continuous emulsion are obtained.

[0111] In one embodiment of the invention, the inventive formulation comprises more than one emulsifier. Depending on the other components, the person skilled in the art uses customary emulsifier systems (for example emulsifier and coemulsifier).

[0112] Nonionic emulsifiers

[0113] The group of nonionic emulsifiers includes, for example:

[0114] (1) Addition products of 2 to 50 mol of ethylene oxide and / or 1 to 20 mol of propylene oxide onto linear fatty alcohols having 8 to 40 carbon atoms, onto fatty acids having 12 to 40 carbon atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group.

[0115] (2) C12-C18 fatty acid mono- and diesters of addition products of 1 to 50 mol of ethylene oxide onto glycerol.

[0116] (3) Sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and ethylene oxide addition products thereof.

[0117] (4) Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and ethoxylated analogs thereof.

[0118] (5) Addition products of 7 to 60 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil.

[0119] (6) Polyol and especially polyglyceryl esters, for example polyglyceryl- 10 monostearate, polyglyceryl-10-monooleate, polyglyceryl-10 monomyristate, polyglyceryl- 10 monolaurate, polyol poly-12-hydroxystearates, polyglyceryl polyricinoleate, polyglyceryl diiso_,stearate or polyglyceryl dimerate. Likewise suitable are mixtures of compounds of two or more of these substance classes.

[0120] (7) Addition products of 2 to 15 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil.

[0121] (8) Partial esters based on linear, branched, unsaturated or saturated C6-C22-fatty acids, ricinoleic acid and 12-hydroxystearic acid and polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose), or mixed esters, for example glyceryl stearate citrate and glyceryl stearate lactate.

[0122] (9) Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerol or polyglycerol.

[0123] The addition products of ethylene oxide and / or of propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glyceryl mono- and diesters and also sorbitan mono- and diesters of fatty acids and onto castor oil are known, commercially available products. These are homolog mixtures whose mean degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Depending on the degree of ethoxylation, they are W / O or O / W emulsifiers. C12 / 18 fatty acid mono- and diesters of addition products of ethylene oxide onto glycerol are known as refatting agents for cosmetic formulations.

[0124] Mild emulsifiers which are particularly suitable in accordance with the invention are polyol poly- 12-hydroxystearates and mixtures thereof, which are sold, for example, under the “Dehymuls® PGPH” (W / O emulsifier) or “Eumulgin® VL 75” (blend with Lauryl Glucosides in a weight ratio of 1 :1 , O / W emulsifier) or Dehymuls® SBL (W / O emulsifier) brands by Cognis Deutschland GmbH. In this connection, reference may be made especially to European patent EP 766 661 B1. The polyol component of these emulsifiers may derive from substances which have at least two, preferably 3 to 12 and especially 3 to 8 hydroxyl groups and 2 to 12 carbon atoms.

[0125] Particularly preferred emulsifiers are, for example, Polyglyceryl-2 Dipolyhydroxystearate (e.g. Dehymuls PGPH), Polyglyceryl-3 Diisostearate (e.g. Lameform TGI), Polyglyceryl-4 Isostearate (e.g. Isolan Gl 34), Polyglyceryl-3 Oleate (e.g. Isolan GO 33), Diisostearoyl Polyglyceryl-3 Diisostearate (e.g. Isolan PDI), Polyglyceryl-3 Methylglucose Distearate (e.g. Tego Care 450), Polyglyceryl-3 Beeswax (e.g. Cera Beilina), Polyglyceryl-4 Caprate (e.g. Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (e.g. Chimexane NL), Polyglyceryl-3 Distearate (e.g. Cremophor GS 32) and Polyglyceryl Polyricinoleate (e.g. Admul WOL 1403), Glyceryl Oleate (e.g. Monomuls 90-0 18), Alkyl Glucoside (e.g. Plantacare 1200, Emulgade PL 68 / 50, Montanov 68, Tego Care CG 90, Tego Glucosid L 55), Methyl Glucose Isostearate (e.g. Tego Care IS), Methyl Glucose Sesquistearate (Tego Care PS), Sodium Cocoyl Hydrolyzed Wheat Protein (e.g. Gluadin WK), Potassium Cetyl Phosphate (e.g. Amphisol K, Crodafos CKP), Sodium Alkylsulfate (e.g. Lanette E), Sucrose Ester (e.g. Crodesta F-10, F-20, F-50, F-70, F-110, F-160, SL-40, Emulgade® Sucro), ethoxylated and / or propoxylated fatty alcohols, fatty acids, castor oils and hydrogenated castor oils (e.g. Eumulgin B2, B2, B3, L, HRE 40, HRE 60, RO 40, Cremophor HRE 40, HRE 60, L, WO 7, Dehymuls HRE 7, Arlacel 989), PEG-30 Dipolyhydroxystearate (e.g. Arlacel P 135, Dehymuls LE), sorbitan esters, sorbitan esters ethoxylated and / or propoxylated, and mixtures thereof. A particularly effective mixture consists of Polyglyceryl-2 Dipolyhydroxystearate and Lauryl Glucoside and glycerol (e.g. Eumulgin VL 75). Also suitable are Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate (Isolan® GPS), Diisostearoyl Polyglyceryl-3 Diisostearate (e.g. Isolan PDI), alkali metal acylglutamates (e.g. Eumulgin SG).

[0126] Suitable lipophilic W / O emulsifiers are in principle emulsifiers with an HLB value of 1 to 8, which are summarized in numerous tabular works and are known to the person skilled in the art. Some of these emulsifiers are listed, for example, in Kirk-Othmer, “Encyclopedia of Chemical Technology”, 3rd edition, 1979, volume 8, page 913. For ethoxylated products, the HLB value can also be calculated according to the following formula: HLB = (100 - L):5, where L is the weight fraction of the lipophilic groups, i.e. of the fatty alkyl or fatty acyl groups in percent by weight, in the ethylene oxide adducts.

[0127] Particularly advantageous from the group of W / O emulsifiers are partial esters of polyols, especially of C4-C6-polyols, for example partial esters of pentaerythritol or sugar esters, e.g. sucrose distearate, sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxy-stearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical-grade mixtures thereof. Also suitable as emulsifiers are addition products of 1 to 30 and preferably 5 to 10 mol of ethylene oxide onto the specified sorbitan esters.

[0128] Depending on the formulation, it may be advantageous to additionally use at least one emulsifier from the group of nonionic O / W emulsifiers (HLB value: 8-18) and / or solubilizers. These are, for example, the ethylene oxide adducts already mentioned in the introduction and having a correspondingly high degree of ethoxylation, e.g. 10-20 ethylene oxide units for O / W emulsifiers and 20-40 ethylene oxide units for solubilizers. According to the invention, Ceteareth-12 and PEG- 20 Stearate are particularly advantageous as O / W emulsifiers. Preferentially suitable solubilizers are Eumulgin® HRE 40 (INCI: PEG-40 Hydrogenated Castor Oil), Eumulgin® HRE 60 (INCI: PEG-60 Hydrogenated Castor Oil), Eumulgin® L (INCI: PPG-1-PEG-9 Lauryl Glycol Ether), and Eumulgin® SML 20 (INCI: Polysorbate-20). Nonionic emulsifiers from the group of alkyl oligoglycosides are particularly skin-friendly and therefore preferentially suitable as O / W emulsifiers. C8 C22-alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. Their preparation takes place especially by reacting glucose or oligosaccharides with primary alcohols having 8 to 22 carbon atoms. As regards the glycoside radical, either monoglycosides, in which a cyclic sugar radical is glycosidically bonded to the fatty alcohol, or oligomeric glycosides with a degree of oligomerization up to preferably about 8 are suitable. The degree of oligomerization here is a statistical average based on a homolog distribution customary for such technical-grade products. Products which are available under the name Plantacare® comprise a glucosidically bonded C8- C16-alkyl group onto an oligoglucoside radical whose average degree of oligomerization is 1 to 2. The acylglucamides derived from glucamine are also suitable as nonionic emulsifiers. According to the invention, preference is given to a product which is sold under the name Emulgade®PL 68 / 50 by Cognis Deutschland GmbH and is a 1 :1 mixture of alkyl polyglucosides and fatty alcohols. According to the invention, it is also advantageously possible to use a mixture of Lauryl Glucoside, Polyglyceryl-2 Dipolyhydroxystearate, glycerol and water, which is commercially available under the name Eumulgin® VL 75.

[0129] Also suitable as emulsifiers are substances such as lecithins and phospholipids. Examples of natural lecithins which may be mentioned are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1 ,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipids are usually understood to mean mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally included in the fats. In addition, sphingosines and sphingolipids are also suitable.

[0130] More preferably the emulsifier is selected from alkyl mono- and oligoglycosides and polyglycerol fatty acid esters selected from the group consisting of polyglyceryl-2 isostearate, polyglyceryl-2 oleate, polyglyceryl-3 diisostearate, polyglyceryl-6 dicaprate, polyglyceryl-10 laurate, polyglyceryl-10 myristate, polyglyceryl-10 stearate, polyglyceryl-10 distearate, polyglyceryl-10 oleate, polyglyceryl-10 dioleate, polyglyceryl-10 pentaoleate, polyglyceryl-10 isostearate, polyglyceryl-10 Diisostearate, polyglyceryl-10 triisostearate, polyglyceryl-20 triisostearate and non-ionic emulsifiers selected from the group consisting of PEG-8 glyceryl isostearate, PEG-7 glyceryl cocoate, PEG-7 caprylic / capric glycerides, PEG-20 glyceryl triisostearate, PEG-12 laurate, sorbeth-30 tetraoleate, sorbitan oleate, polyoxyethylene sorbitan trioleate, PEG-5 laureth- 5, PPG-1-PEG-9 lauryl glycol ether, PEG-40 hydrogenated castor oil, laureth-7 citrate.

[0131] Surfactants

[0132] In one embodiment of the invention, the inventive formulations comprise at least one surfactant. Surfactants are amphiphilic substances which can dissolve organic, nonpolar substances in water. They cause, as a result of their specific molecular structure with at least one hydrophilic and a hydrophobic molecular moiety, a lowering of the surface tension of the water, the wetting of the skin, the facilitation of soil removal and dissolution, easy rinse-off and - if desired - foam regulation.

[0133] Surfactants are typically understood to mean surface-active substances which have an HLB value of greater than 20.

[0134] The surface-active substances present may be anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. In surfactant-containing cosmetic formulations, for example shower gels, foam baths, shampoos, etc., at least one anionic surfactant is preferably present.

[0135] Zwitterionic surfactants refer to those surface-active compounds which bear at least one quaternary ammonium group and at least one -COO(-) or -SO3(-) group in the molecule. Particularly suitable zwitterionic surfactants are the betaines, such as the N-alkyl-N,N- dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N- acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylamino- propyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and also cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

[0136] Likewise suitable, especially as cosurfactants, are ampholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which, apart from a C8-C18-alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or - SO3H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N- alkylimino-'dipropionic acids, N-hydroxyethyl-N-alkylamidopropyhglycines, N-alkyltaurines, N- alkylsarcosines, 2-alkyhaminopropionic acids and alkylaminoacetic acids having in each case about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl-aminopropionate and C12-18-acylsarcosine. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The specified surfactants are exclusively known compounds. With regard to the structure and preparation of these substances, reference may be made to relevant review works in this field. Typical examples of particularly suitable mild, i.e. particularly skin-friendly, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides and / or mixtures thereof with alkyl oligoglucoside carboxylates, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins or salts thereof.

[0137] Anionic surfactants are characterized by a water-solubilizing, anionic group, for example a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic radical. Skin-compatible anionic surfactants are known to the person skilled in the art in a large number from relevant handbooks and are commercially available. These are especially alkyl sulfates in the form of their alkali metal, ammonium or alkanolammonium salts, alkyl ether sulfates, alkyl ether carboxylates, acyl isethionates, acyl sarcosinates, acyltaurines with linear alkyl or acyl groups having 12 to 18 carbon atoms, and also sulfosuccinates and acyl glutamates in the form of their alkali metal or ammonium salts.

[0138] Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin-sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, a-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ethercarboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, for example acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants comprise polyglycol ether chains, these may have a conventional homolog distribution, but preferably have a narrow homolog distribution.

[0139] Cationic surfactants which can be used are especially quaternary ammonium compounds. Preference is given to ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethyhammonium chlorides and trialkylmethylammonium chlorides, e.g. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, the very readily biodegradable quaternary ester compounds, for example the dialkylammonium methosulfates and methylhydroxyalkyldialkyloxyalkylammonium methosulfates sold under the trade name Stepantex® and the corresponding products of the Dehyquart® series can also be used as cationic surfactants. The term “ester quats” are generally understood to mean quaternized fatty acid triethanolamine ester salts. They can impart an exceptional soft feel to the preparations according to the invention. These are known substances which are prepared by the relevant methods of organic chemistry. Further cationic surfactants which can be used in accordance with the invention are the quaternized protein hydrolyzates.

[0140] Wax component

[0141] In one embodiment of the invention, the inventive formulations comprise at least one wax component.

[0142] The inventive formulations comprise the wax component(s) typically in an amount of 0 to 40% by weight, especially of 0 to 20% by weight, preferably 0.1 to 15% by weight and especially 0.1 to 10% by weight, based on the total weight of the formulation.

[0143] The term “wax” is typically understood to mean all natural or synthetic substances and substance mixtures having the following properties: they are of solid to brittle and hard consistency, coarse to finely crystalline, transparent to cloudy and melt above 30°C without decomposition. They are low in viscosity even a little above the melting point and do not string, and exhibit a strongly temperature-dependent consistency and solubility. According to the invention, it is possible to use a wax component or a mixture of wax components which melt at 30°C or higher.

[0144] The waxes used in accordance with the invention may also be fats and fat-like substances with waxy consistency, provided they have the required melting point. These include, inter alia, fats (triglycerides), mono- and diglycerides, natural and synthetic waxes, fatty and wax alcohols, fatty acids, esters of fatty alcohols and fatty acids and also fatty acid amides or any desired mixtures of these substances.

[0145] Fats are understood to mean triacylglycerols, i.e. the triple esters of fatty acids with glycerol. They preferably comprise saturated, unbranched and unsubstituted fatty acid radicals. They may also be mixed esters, i.e. triple esters of glycerol with different fatty acids. According to the invention, it is possible to use hydrogenated fats and oils, which are obtained by partial hydrogenation and are particularly suitable as consistency regulators. Vegetable hydrogenated fats and oils are preferred, e.g. hydrogenated castor oil, peanut oil, soybean oil, rapeseed oil, colza oil, cottonseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, corn oil, olive oil, sesame oil, cocoa butter and coconut fat.

[0146] Suitable examples include the triple esters of glycerol with C12-C60-fatty acids and especially C12-C36-fatty acids. These include hydrogenated castor oil, a triple ester of glycerol and a hydroxystearic acid, which is commercially available, for example, under the Cutina HR name. Glyceryl tristearate, glyceryl tribehenate (e.g. Syncrowax HRC), glyceryl tripalmitate or the triglyceride mixtures known under the Syncrowax HGLC name are likewise suitable, with the proviso that the melting point of the wax component or of the mixture is 30°C or higher.

[0147] According to the invention, usable wax components are especially mono- and diglycerides and mixtures of these partial glycerides. Glyceride mixtures which can be used in accordance with the invention include the Novata AB and Novata B (mixture of C12-C18-mono-, di- and triglycerides) and Cutina MD or Cutina GMS (glyceryl stearate) products sold by Cognis Deutschland GmbH & Co. KG.

[0148] Fatty alcohols which can be used in accordance with the invention as the wax component include the C12-C50-fatty alcohols. The fatty alcohols can be obtained from natural fats, oils and waxes, for example myristyl alcohol, 1 -pentadecanol, cetyl alcohol, 1 -heptadecanol, stearyl alcohol, 1- nonadecanol, arachidyl alcohol, 1 heneicosanol, behenyl alcohol, brassidyl alcohol, lignoceryl alcohol, ceryl alcohol or myricyl alcohol. Preference is given in accordance with the invention to saturated unbranched fatty alcohols. However, it is also possible in accordance with the invention to use unsaturated, branched or unbranched fatty alcohols as the wax component, provided they have the required melting point. It is also possible in accordance with the invention to use fatty alcohol cuts, as produced in the reduction of naturally occurring fats and oils, for example bovine tallow, peanut oil, colza oil, cottonseed oil, soybean oil, sunflower oil, palm kernel oil, linseed oil, castor oil, corn oil, rapeseed oil, sesame oil, cocoa butter and coconut fat. However, it is also possible to use synthetic alcohols, e.g. the linear, even-numbered fatty alcohols from the Ziegler synthesis (alfols) or the partially branched alcohols from the oxo process (dobanols). Particular preference is given in accordance with the invention to C14-C22-fatty alcohols, which are sold, for example, by Cognis Deutschland GmbH under the Lanette 18 (C18-alcohol), Lanette 16 (C16- alcohol), Lanette 14 (C14-alcohol), Lanette O (C16 / C18-alcohol) and Lanette 22 (C18 / C22- alcohol) names. Fatty alcohols impart a drier skinfeel to the formulations than triglycerides and are therefore preferred over the latter.

[0149] The wax components used may also be C14-C40-fatty acids or mixtures thereof. These include, for example, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, erucic acid and elaeostearic acid, and also substituted fatty acids, for example 12 hydroxystearic acid, and the amides or monoethanolamides of the fatty acids, this list being illustrative and nonlimiting in character.

[0150] It is possible in accordance with the invention to use, for example, natural vegetable waxes, such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ wax, sugarcane wax, ouricury wax, montan wax, sunflower wax, fruit waxes such as orange waxes, lemon waxes, grapefruit wax, bayberry wax, and animal waxes, for example beeswax, shellac wax, spermaceti, wool wax and uropygial grease. In the context of the invention, it may be advantageous to use hydrogenated or hardened waxes. The natural waxes which can be used in accordance with the invention also include mineral waxes, for example ceresin and ozokerite or the petrochemical waxes, for example petrolatum, paraffin waxes and microwaxes. Usable wax components also include chemically modified waxes, especially the hard waxes, for example montan ester waxes, sasol waxes and hydrogenated jojoba waxes. Synthetic waxes which can be used in accordance with the invention include, for example, wax-like polyalkylene waxes and polyethylene glycol waxes. Vegetable waxes are preferred in accordance with the invention.

[0151] The wax component can likewise be selected from the group of the wax esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols, from the group of esters of aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids and hydroxycarboxylic acids (e.g. 12- hydroxystearic acid) and saturated and / or unsaturated, branched and / or unbranched alcohols, and also from the group of lactides of long-chain hydroxycarboxylic acids. Examples of such esters are the C16-C40-alkyl stearates, C20-C40-alkyl stearates (e.g. Kesterwachs K82H), C20- C40-dialkyl esters of dimeric acids, C18-C38-alkylhydroxystearoyl stearates or C20-C40-alkyl erucates. It is also possible to use C30-C50-alky I beeswax, tristearyl citrate, triisostearyl citrate, stearyl heptanoate, stearyl octanoate, trilauryl citrate, ethylene glycol dipalmitate, ethylene glycol distearate, ethylene glycol di(12-hydroxystearate), stearyl stearate, palmityl stearate, stearyl behenate, cetyl ester, cetearyl behenate and behenyl behenate. Fatty acid partial glycerides, i.e. technical-grade mono- and / or diesters of glycerol with fatty acids having 12 to 18 carbon atoms, for example glycerol mono / dilaurate, -palmitate, -myristate or stearate, are also useful for this purpose.

[0152] Suitable waxes are additionally pearlescent waxes. Useful pearlescent waxes, especially for use in surface-active formulations, are, for example: alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially laurone and distearyl ethers; fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof. Polymers

[0153] In one embodiment of the invention, the inventive formulations comprise at least one polymer. The inventive formulations comprise the polymer(s) typically in an amount of 0 to 20% by weight, preferably 0.1 to 15% by weight and especially 0.1 to 10% by weight, based on the total weight of the formulation.

[0154] Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternized hydroxyethylcellulose, which is available under the Polymer JR 400® name from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grunau), quaternized wheat polypeptides, polyethyleneimine, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, cationic chitin derivatives for example quaternized chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkylene, for example dibromobutane with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, for example Mirapol® A-15, Mirapol® AD- 1 , Mirapol® AZ-1 from Miranol.

[0155] Useful anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinyhcaprolactam terpolymers and optionally derivatized cellulose ethers.

[0156] Likewise suitable polymers are polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses and also, for example, Aerosil grades (hydrophilic silicas), carboxymethylcellulose and hydroxyethylcellulose and hydroxypropylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and bentonites, for example Bentone® Gel VS-5PC (Rheox).

[0157] Likewise suitable are quaternary polymers, for example with the INCI name Polyquaternium-37, which conform to the following general formula: Alternatively, it is also possible to use other dialkylaminoalkyl (meth)acrylates and their ammonium salts obtainable by alkylation or protonation, or dialkylaminoalkyl(meth)acrylamides and their ammonium salts obtainable by alkylation or protonation. Particular preference is given to polymers comprising MAPTAC, APTAC, MADAME, ADAME, DMAEMA and TMAEMAC. Moreover, it is also possible to use copolymers with anionic, further cationic or uncharged monomers in accordance with the invention, in particular those which, as well as the specified alkylaminoalkyl (meth)acrylate or alkylaminoalkyl(meth)acrylamide monomers, additionally comprise (meth)acrylic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and / or acrylamide and / or vinylpyrrolidone and / or alkyl (meth)-'acrylates. By way of example, mention may be made of those polymers with the INCI name Polyquaternium-11 , Polyquaternium-13, Polyquaternium- 14, Polyquaternium-15, Polyquaternium-28, Polyquaternium-32, Polyquaternium-43, Polyquaternium-47.

[0158] Further oil bodies

[0159] In one embodiment of the invention, the inventive formulations comprise at least one oil body. Typically, the inventive formulations comprise the andiroba oil based ester as the oil body. In the embodiment specified here as preferred, the formulations thus comprise an oil body other than the inventive andiroba ester, also referred to as “further oil body”.

[0160] The invention therefore further provides cosmetic and / or pharmaceutical formulations comprising 0.1 to 80% by weight based on the weight of the composition, preferably 0.5 to 50% by weight, more preferably 5 to 25 % and most preferably 1 to 5 % by weight of a mixture of C1 to C3 alkylesters, preferably ethylester, with less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms obtained from Andiroba oil and at least one (further) oil body.

[0161] The oil bodies (inventive hydrocarbon mixture plus further oil bodies) are typically present in a total amount of 0.1-90%, especially 0.1-80%, especially 0.5 to 70%, preferably 1 to 60%, especially 1 to 50%, especially 1 to 40%, preferably 5-25% and especially 5 15% by weight. The further oil bodies are typically present in an amount of 0.1 to 40% by weight, based on the total weight of the formulation.

[0162] Suitable further oil bodies are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, and also further additional esters such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Additionally suitable are esters of C18 C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, especially dioctyl malate, esters of linear and / or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimerdiol or trimertriol), triglycerides based on C6 C1O-fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-C12-dicarboxylic acids with polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, for example dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, for example dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols and hydrocarbons or mixtures thereof.

[0163] Process of manufacturing the mixture of C1 to C3-alkylesters obtained from Andiroba oil

[0164] To ensure a better stability and quality of the cosmetic product obtained from andiroba oil, the applicant used a unique esterification process of the oil, thus guaranteeing an ester based on 100 % renewable raw material for cosmetic application.

[0165] In order to manufacture the mixture of C1 to C3-alkyl esters obtained from andiroba oil, the oil has to undergone a transesterification. Hereby it is disadvantageous that Andiroba oil has a high amount of free fatty acids.

[0166] Basic catalysts used to increase the reaction rate of transesterification are more active than acidic catalysts and are therefore preferred. However, if an alkaline catalyzed transesterification is carried out with crude oil containing a high amount of free fatty acids by weight, soaps are formed in a detrimental manner, either by neutralization of free fatty acids with the basic catalyst, for example sodium hydroxide, or by saponification of acylglycerides, which is done in the presence of water. Soap formation is undesirable because it consumes and deactivates the catalyst, hinders phase separation, and also complicates the purification of the alkyl ester and thus reduces the process yield. Hence, an alkaline catalyzed transesterification can only efficiently be conducted if the oil used is comparatively pure and dry and contains only very small proportions of free fatty acids, in particular less than 3% by weight, preferably less than 1 % by weight and little water, preferably less than 0.5% by weight. Therefore, pre-treatment of andiroba oil is required to reduce the free fatty acid content if an alkaline catalyzed transesterification is to be performed without significant loss of yield.

[0167] One possible method of reducing the acidity of the oil is physical refining or deacidification. Here, the low-boiling free fatty acids are physically stripped away from the crude oil by using steam in a counterflow to the crude oil used. This process results in a low content of free fatty acids in the oil, which can then be fed into the alkaline catalyzed process without having to worry about catalyst consumption and soap formation. However, the physical deacidification method has the main disadvantage that the separated free fatty acids have to be esterified again with the alcohol in order to form fatty acid alkyl esters and avoid a loss of yield of the end product.

[0168] In order to simplify the process andiroba oil can undergo a two-step esterification process in a single reaction vessel. The first stage (step a)) is an esterification with a C1 - C3-alcohol in the presence of an acidic catalyst under pressure and temperature, so that the process is repeated continuously, removing the C1-C3-alcohol from the reaction and feeding it with pure C1 to C3- alcohol, until the residual acidity of the product is at maximum 6 mg KOH / g. The second stage (step b)) consists of the transesterification phase by alkaline catalysis, followed by separation, washing, temperature vacuum drying and optionally cold filtration.

[0169] In a first step andiroba oil is reacted with a molar excess, which is 1.5 - 5 mol oil to 1 to 3 mol C1- C3-alcohol (methanol, ethanol, n-propanol or isopropanol), preferably 1.8 - 2.2 mol oil to 0.8 to 1.2 mol C1-C3 alcohol, more preferably 2 mol oil to 1 mol C1-C3 alcohol by acid catalysis in order to transform the free fatty acids of the andiroba oil into the respective alkylester. For acid catalysis any acidic known esterification catalyst can be added, preferably para sulfonic acid or, more preferably methane sulfonic acid is chosen as this catalyst seems to be less corrosive for the reaction vessel.

[0170] The first esterification step is conducted at a temperature of 110 to 150 °C and a pressure of 3.5 to 11 .5 bar until the acid value of the reaction mixture reaches a value of 6 mg KOH / g.

[0171] Preferably the alcohol for esterification is ethanol, being also a raw material of renewable source. In known pre-esterification processes usually methanol is the alcohol used, being a raw material of petrochemical origin. Using ethanol enables a higher quality and stability of andiroba oil using only raw materials of renewable origin. Using ethanol for the esterification and manufacturing an ethylester obtained from Andiroba oil the first process step is conducted at a temperature of 120-125 °C and a pressure of 4 ± 1 bar, which is maintained until an acid value of 6 mg KOH / g is reached.

[0172] The azeotropic mixture of water and alcohol is removed up to a water content below 0.15 wt %, more preferably below 0.12 wt %.

[0173] Subsequently a transesterification step of the alkylester of step a) with a water content below 0.15 wt % or lower is started by addition of further alcohol and sodium methylate as alkaline catalyst under reflux conducted at 60 to 90 °C, preferably 65 to 85 °C for 2 to 5 hours. Preferably ethanol is used as C1-C3-alcohol in step a) and step b) and the transesterification step b) is conducted under reflux at 78 to 82 °C for 3 hours.

[0174] When the andiroba oil is fully (minimum 98 %) converted into the ester excess alcohol is distilled off. Subsequently 50 wt% based on the total weight of the C1 to C3 alkylester of a mixture comprising an aqueous solution of 10 wt % sodium sulfate and 0.5 wt% phosphoric acid obtained from the aqueous solution are added and the mixture is left to rest for at least 3 hours at 70 - 80°C for separation of glycerol.

[0175] Preferably the esterification step a) is conducted in a nitrogen atmosphere in the presence of hypophosphoric acid (0.2 % based on the total weight of the oil at the start of the reaction) in order to improve the color of the final alkylester.

[0176] The process further comprises at least one washing step, drying step and optionally filtration after separating the C1-C3 alkylesters.

[0177] Preferably after glycerol removal two to three washing steps with hot water are added until water pH is neutral (pH = 7). Thereafter the resulting ester is vacuum dried at 100 °C and a pressure of 600 mmHg until reaching a water content of 0.1 wt% and below.

[0178] Examples

[0179] The present invention is further illustrated by the following examples:

[0180] Method for extracting the oil from the fruit

[0181] The seeds according to Brazilian SisGen-registration no. AC2AD3F were collected, washed, classified, drained, dried and stored to be crushed in room temperature expeller presses, filtered in a press filter and packaged.

[0182] Example 1 : Manufacturing of an ethylester obtained from Andiroba oil

[0183] The harvested andiroba oil was then reacted at a temperature of 120-125°C and a pressure of 4 bar with a molar excess of 2 mol ethanol to 1 mol of the oil in the presence of methane sulfonic acid as catalyst in a nitrogen atmosphere and the presence of 0.2 wt % hypophosphoric acid based on the weight of the andiroba oil until an acid value of 6 mg KOH / g was reached.

[0184] The azeotropic mixture of water and alcohol was removed up to a water content below 0.15 wt %.

[0185] At a water content below 0.15 wt % subseguently a transesterification step of this mixture was started in the same reaction vessel by addition of further ethanol and sodium methylate as alkaline catalyst under reflux at 78 to 82 °C for 3 hours.

[0186] Afterwards the excess alcohol was distilled off and 50 wt% based on the total weight of the C1 to C3 alkylester of a mixture comprising an agueous solution of 10 wt % sodium sulfate and 0.5 wt% phosphoric acid based on the agueous solution were added and the mixture was left to rest for at least 3 hours at 70 - 80 °C for separation of glycerol.

[0187] After glycerol removal two to three washing steps with hot water were added until the water's pH was neutral (pH = 7). Thereafter the resulting ester was vacuum dried at 100 °C and a pressure of 600 mmHg until reaching a water content of 0.1 wt% and below.

[0188] A dark yellow ester according to Table 1 with an acidity value of maximum 5.2 mgKOH / g, saponification value of 184.9 mgKOH / g and iodine value max 60.8 gl / 100g was achieved.

[0189] Table 1 : Fatty acid distribution of the andiroba ethylester according to example 1 :

[0190] Cosmetic Test

[0191] Cosmetic formulations in form of O / W emulsions comprising the Andiroba ester of example 1 were applied to the skin aiming to investigate emollient properties of the Andiroba ester in topical applications. The tests evaluated were:

[0192] Skin hydration (30 minutes and 4 hours after application) and residual oil on the skin (after 5 minutes and 4 hours) using emulsion formulations containing different emollients.

[0193] The investigated formulations were comprising:

[0194] * Placebo: No addition of emollient

[0195] Emollients in an amount of 1 wt % based on the weight of the composition:

[0196] * Cyclomethicone: cyclomethicone, a widely used emollient in cosmetic formulas having high volatility;

[0197] * Dimethicone: dimethicone, a widely used emollient in cosmetic formulas aiming at a pleasant sensory feeling of skincare;

[0198] * Cetiol® C5 (Coconut-Caprylate): Ester-Emollient of BASF's portfolio, offered as a sensory alternative to cyclomethicone;

[0199] * Andiroba oil: Oil from Brazilian andiroba seeds, pure oil not transesterified

[0200] * Andiroba ester: Ester according example 1 Gel-cream prototype formulations were developed to compare the selected emollients: cyclomethicone, dimethicone, Cetiol 05 (Coco-Caprylate), Andiroba Oil and Andiroba Ester.

[0201] Test Formulations

[0202] The formulations according to table 2 were manufactured by the following steps: 1) Pre-mixing phase B; 2) Pour phase A into B under high agitation of 1000 - 1200 rpm; 3) After emulsification and complete homogenization, add phase C, at a speed of 700-800rpm. 4) Adjust the pH with phase D to 6.2-6.5.

[0203] Table 2: cosmetic test formulations Part 2 of table 2:

[0204] Measurement Methods a) Skin hydration measurement

[0205] The tests were carried out in an air-conditioned room with a temperature of 22°C and relative humidity of 40%, equipped with HEPA filters. In total, 6 volunteers participated in the tests, starting with air conditioning for 5 minutes in the controlled environment. Next, the initial reading (TO) of the skin's hydration measurement was taken, using a CORNEOMETER CM 825 - C&K probe. The volunteer's forearms were wetted for 10 seconds and then cleaned with 1 mL of neutral soap using circular movements for 20 seconds, then rinsed for 10 seconds. Once dry, the forearms were demarcated and 0.08 g of the gel-cream formulations according to table 2 were applied with circular movements for 30 seconds. Skin hydration measurements were carried out after 30 minutes and 4 hours, using the CORNEOMETER CM 825 - C&K probe

[0206] Skin hydration: 30 minutes after application of the gel-cream formulation (results in table 4a)) superior skin hydration results were obtained for the gel-cream with Cetiol C5 (+27%), Andiroba Ester (+26%) and Andiroba Oil (+24%) in relation to silicones and control. 4 hours after application (results in table 4 b)), the samples with Andiroba Ethylester maintained the highest hydration capacity of +16% in relation to the other compositions. Table 3 a): Skin Hydration after 30 min

[0207] Table 3 b): Skin hydration after 4 h b) Residual Oil Measurement

[0208] The tests were carried out in an air-conditioned room with a temperature of 22°C and relative humidity of 40%, equipped with HEPA filters. In total, 6 volunteers participated in the tests, starting with air conditioning for 5 minutes in the controlled environment. Next, the initial reading (TO) of the residual oil in the skin was taken, using a SEBUMETER SM 815 - C&K probe. The volunteer's forearms were wetted for 10 seconds and then cleaned with 1 mL of neutral soap using circular movements for 20 seconds and afterwards rinsed for 10 seconds. Once dry, the forearms were demarcated and 0.08 g of the gel-cream formulation according to table 2 was applied with circular movements for 30 seconds. New skin residual oil measurements were carried out after 5 minutes and 4 hours, using the SEBUMETER SM 815 - C&K probe.

[0209] Residual oil in the skin: 30 minutes after application of the gel-cream formulation (results in table 4 a)), a lower residual oil value was obtained for the Gel Cream Control (2 pg / cm2) and Gel Cream Cyclomethicone (4 pg / cm2) samples. The following values were found for the other formulations tested: Dimethicone - 19 pg / cm2, Cetiol C5 - 27 pg / cm2, Andiroba Ester - 34 pg / cm2and Andiroba Oil - 22 pg / cm2. Four hours after applying the test compositions (results in table 4 b)), it was possible to notice a great reduction in residual oil on the skin for the samples with Andiroba ethylester, while the samples with silicone had an increase, especially the sample with cyclomethicone, which had shown little oiliness 5 minutes after application. The following values were found for the formulations tested: Control - 1 pg / cm2, Dimethicone - 16 pg / cm2, Cyclomethicone - 18 pg / cm2, Cetiol C5 - 1 u pg / cm2, Andiroba Ester - 2 pg / cm2, Andiroba oil - 5 pg / cm2. Table 4 a) - Residual Oil - Sebumeter 5 min after application

[0210] Table 4 b) - Residual Oil - Sebumeter 4 h after application

[0211] As a result, andiroba ester showed greater skin hydration capacity than the control, dimethicone and cyclomethicone; and similar moisturizing capacity compared to Cetiol® C5 and andiroba oil directly after application but clearly improved moisturization compared to silicone derivatives, the oil and a standard emollient still several hours after application.

[0212] In respect of the residual oil values, the composition comprising Andiroba ester also provided data equivalent to compositions with Cetiol® C5 and andiroba oil, these results are higher than placebo, dimethicone and cyclomethicone.

[0213] These data prove that andiroba ester shows an improved hydration power over the longterm with less residual oil values compared to andiroba oil, resulting in a very nutritious emollient with a good sensory feeling.

Claims

Claims1. A mixture of C1 to C3 - alkylesters obtained from Andiroba oil, characterized in that the alkylesters contain less than 10 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 40 to 60 % unsaturated fatty acids with 18 carbon atoms.

2. Alkylester mixture according to claim 1 , characterized in that the alkylesters contain less than 5 % saturated and unsaturated fatty acids with 6 to 14 carbon atoms and 15 to 35 % palmitic (016:0) fatty acid.

3. Alkylester mixture according to claim 1 , characterized in that the alkylesters contain the specific distribution of fatty acids caproic (C6:0), caprilic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), palmitic (C16:0), palmitoleic (C16: 1), stearic (C18:0), oleic (C18: 1), linoleic(018:2) and linolenic (018:3) acids in the following proportion in (%) relative contentCaproic (C6:0) < 2.0 caprilic acid (C8:0) < 2.0 capric acid (C10:0) < 2.0 lauric acid (C12:0) < 2.0 myristic acid (C14:0) < 2.0 palmitic acid (C16:0) 15.0 - 35.0 stearic acid (C18:0) 5.0 - 15.0 oleic acid (C18:1) 40.0 - 60.0 linoleic C18:2 5.0 - 10.0 and linolenic C18:3 < 3.

4. Alkylester mixture according to any of claims 1 to 3, characterized in that it is an ethylester mixture.

5. Alkylester mixture according to any of claims 1 to 4, characterized in that it has a iodine value of maximum 90 g / 100g, an acid value of maximum 10 mg KOH / g and a saponification value of 170 - 210 mg KOH / g.

6. Alkylester mixture according to any of claims 1 to 5, characterized in that it has a saponification value of 170 - 210 mg KOH / g.

7. The use of an alkylester mixture as claimed in any of claims 1 to 6 as an emollient or dispersant in cosmetic and / or pharmaceutical formulations.

8. A cosmetic and / or pharmaceutical formulation comprising 0.1 to 80% by weight of an alkylester mixture as claimed in any of claims 1 to 6.

9. The cosmetic and / or pharmaceutical formulation according to claim 8, comprising at least one antiperspirant / deodorant active ingredient.

10. The cosmetic and / or pharmaceutical formulation according to claim 8, comprising at least one at least one UV light protection filter.

11. The cosmetic and / or pharmaceutical formulation according to any of claims 8 to 10, comprising at least one polyol and / or emulsifier and / or a surfactant and / or a wax component and / or a polymer and / or a further emollient.

12. A process of manufacturing an alkylester mixture obtained from Andiroba oil according to claim 1 , the process comprising a) a first esterifying step treating an oil extracted from Andiroba palm with ethanol in the presence of an acidic catalyst until the mixture reaches an acid value below 6 mg KOH / g and b) a subsequent second esterifying step conducting a transesterification of the reaction mixture in the presence of ethanol and an alkaline catalyst.

13. The process according to claim 12, characterized in that the first esterifying step a) and the second transesterification step b) are conducted in the same reaction vessel.

14. The process according to claim 12 or 13, characterized in that the first esterifying step a) is conducted at a temperature of 110 -150 °C and a pressure of 3.5 to 11.5 bar.

15. The process according to any one of claims 12 to 14, characterized in that water is removed from the reaction mixture of a) to reach a water content below 0.15 wt % before starting step b).

16. The process according to any one of claims 12 to 15, characterized in that the esterification of step a) is conducted in the presence of methane sulfonic acid as catalyst.

17. The process according to any one of claims 12 to 16, characterized in that the second step - the transesterification - is conducted at 60 to 90°C, preferably 65 to 85 °C more preferably 78 to 82 °C in the presence of sodium methylate as catalyst.

18. The process according to any one of claims 12 to 17, characterized in that step a) is conducted in a nitrogen atmosphere in the presence of hypophosphoric acid.

19. The process according to any one of claims 12 to 18, characterized in that after complete transesterification (b) excess alcohol is distilled off, water and phosphoric acid are added and the reaction mixture is left at 70 - 80 °C to rest for at least 3 hours for separation.

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