Patent Application
20150315123
The present invention relates to polyglycerol partial esters of a specific composition which are capable of solubilizing very hydrophobic, oil-soluble substances in aqueous solution. The present invention also relates to the preparation and use of these polyglycol ether-free solubilizers in cosmetic formulations.
Non-ionic surfactants having hardly any foam-generating effect are usually employed as solubilizers of oil-soluble, hydrophobic substances in water.
Polyethoxylated triglycerides, particularly based on castor oil, e.g., PEG-40 hydrogenated castor oil, are used as standard solubilizers. The latter is virtually able to clearly solubilize oil-soluble substances of a wide variety of structures and hydrophobicity in water. Polyglycol ether-free polyglycerol partial esters have also been used for some years as alternative solubilizers.
The disadvantage of all polyglycerol partial esters available to date is that their use as solubilizers of oil-soluble substances in water cannot cover as wide a substance spectrum as the previously mentioned polyethoxylated triglycerides. The polyglycerol esters are thus mainly suitable for solubilizing “small” molecules such as, for example, short-chain terpenes. In contrast, oils based on fatty acids and triglycerides of long-chain fatty acids such as jojoba oil, almond oil, soybean oil or avocado oil cannot, to date. be clearly solubilized in water using the commercial products based on polyglycerol partial esters.
JP 2008-119568 describes the use of polyglycerol partial esters as solubilizers of oils in which the polyglycerol partial esters are based on mixtures of saturated fatty acids having 8 to 22 carbon atoms and unsaturated fatty acids having 16 to 22 carbon atoms, wherein the molar ratio of saturated to unsaturated fatty acids is in a range of 0.2 to 0.8 to 0.8 to 0.2. In addition, polyglycerol partial esters of polyricinoleic acid may be admixed with this polyglycerol partial ester.
One object of the present invention is to provide solubilizers based on polyglycerol partial esters which, in contrast to the products available on the market to date, are able to clearly solubilize, in particular, hydrophobic, oil-soluble substances, such as long-chain triglycerides, in water and to solubilize cosmetic formulations.
It has been surprisingly found that the polyglycerol partial esters described in the present invention are able to rectify the disadvantages of the prior art and thus enable to achieve the object of the present invention mentioned above.
In one embodiment of the present invention, polyglycerol partial esters are provided which are prepared from polyglycerol by esterification of a specifically selected fatty acid mixture. The products are able to clearly solubilize very hydrophobic, oil-soluble substances, such as long-chain triglycerides, in water or to solubilize a cosmetic formulation. The preparation and use of these solubilizers in cosmetic formulations is also part of this invention.
An advantage of the present invention is that the polyglycerol partial esters described herein are able to clearly solubilize strongly hydrophobic, oil-soluble substances, such as long-chain triglycerides, in water or to solubilize a cosmetic formulation, which is not possible using the products based on polyglycerol esters available to date.
A further advantage of the present invention is that the polyglycerol partial esters described herein may be prepared exclusively from renewable raw materials in contrast to polyethoxylated triglycerides.
A yet further advantage of the present invention is that the polyglycerol partial esters described herein are liquid, and thus readily processable, in contrast to polyethoxylated triglycerides.
An even further advantage of the present invention compared to the polyethoxylated triglycerides is that the polyglyceryl esters described herein lead to particularly clear dispersions of the oil in the water, and also no cloudiness occurs on storage, in contrast to polyethoxylated triglycerides (PEG-40 hydrogenated castor oil).
Another advantage of the present invention is that formulations may be provided that are polyglycol ether-free.
A further advantage of the polyglycerol partial esters described herein is that the polyglycerol partial esters of the present invention can produce a pleasant skin sensation in cosmetic formulations.
Another advantage of the polyglycerol partial esters described herein is that the polyglycerol partial esters of the present invention exhibit only a very low foam formation on stirring in water.
A further advantage is that the polyglycerol partial esters described herein show only a very low effect on foamability and foam quantity in surfactant formulations, but the foam creaminess can, however, improve.
Another advantage is that the polyglycerol partial esters described in the present invention may lead to attenuation of the skin irritancy in surfactant formulations.
A further advantage of the polyglycerol partial esters described herein is that the polyglycerol partial esters of the present invention can have a stabilizing effect in emulsions.
A further advantage of the inventive products is that they are relatively stable to oxidation and more stable with respect to color, odor and appearance.
The present invention provides polyglycerol partial esters of general formula I
A person skilled in the art is aware that the polyglycerol base skeleton present in general formula I, owing to its polymeric property, represents a random mixture of various compounds. Polyglycerol may have formed ether bonds between two primary, one primary and one secondary and also two secondary positions of the glycerol monomers. For this reason, the polyglycerol base skeleton does not usually consist exclusively of linearly linked glycerol units, but may also comprise branches and rings. For details see, e.g., “Original synthesis of linear, branched and cyclic oligoglycerol standards”, Cassel et al., J Org. Chem. 2001, 875-896.
Structures of this kind are covered in this respect in the simplified, general formula I.
From the term “the molar ratio of the acyl residues R4 to R5 is in a range of 95:5 to 5:95”, it is clear that residues R4 and R5 are present in the polyglycerol partial esters according to the invention.
Preferred polyglycerol partial esters according to the invention are characterized in that they comprise structures of general formula 1) each having at the same time at least one R4 residue and one R5 residue.
The acyl residues R4 and R5 can be randomly attached to the polyglycerol base skeleton both via primary and via secondary hydroxyl groups.
All conditions such as, for example, pressure and temperature, if not stated otherwise, are standard conditions (20° C., 1 bar). Percentages are indicated, if not described otherwise, in mass percent.
The degree of polymerisation ‘n’ can thus be determined, whereby the hydroxyl number of the polyglycerol used for the synthesis of the inventive ester is determined, in which the mean degree of polymerisation n is related to the hydroxyl number of the polyglycerol on which it is based via the following equation:
where M=molar mass; OHZ=hydroxyl number of the free polyglycerol.
Alternatively, the degree of polymerisation ‘n’ can also be determined by determining the hydroxyl number of the polyglycerol obtained after complete ester hydrolysis.
Suitable methods for determining the hydroxyl number are particularly those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.
The acyl residues R4 and R5 are preferably acyl residues of fatty acids. R4 and R5 may also represent mixtures of such acyl residues, particularly technical mixtures such as, in the case of R4, coconut fatty acid cuts.
For R4, it is with particular preference that at least 50 mol %, preferably at least 75 mol %, of the R4 acyl residues are selected from capryloyl, caproyl and lauroyl residues, based on all R4 residues in the polyglycerol partial ester.
R5 is particularly preferably selected from ricinoyl and hydroxystearoyl residues, their oligomers and mixtures thereof, particularly preferably at least 90 mol % of the R5 acyl residues comprise ricinoyl residues or a mixture of ricinoyl and hydroxystearoyl residues, based on all R5 residues in the polyglycerol partial ester, in which it is preferred that the mixture of ricinoyl and hydroxystearoyl residues has a molar ratio of ricinoyl to hydroxystearoyl residues in a range of 100 to 0.1 to 50 to 50.
As an alternative, R5 is preferably selected from ricinoyl residues.
Preferred polyglycerol partial esters according to the invention are characterized in that the weight ratio of the polyglyceryl residue to the sum total of the acyl residues R4 and R5 is 85:15 to 55:45, preferably 80:20 to 60:40, particularly preferably 75:25 to 65:35.
Preferred polyglycerol partial esters according to the invention are further characterized in that the molar ratio of saturated to unsaturated acyl residues in the sum total of all R4 and R5 residues is 99:1-1:99, preferably 95:5-50:50, particularly preferably 90:10-60:40.
The polyglycerol partial esters of the present invention can be prepared by classical esterification and transesterification methods, preferably by the inventive method described hereinafter.
The present invention further relates to a method for preparing polyglycerol partial esters comprising the method steps of:
The carboxylic acid derivatives preferably used in the method according to the invention are fatty acid derivatives.
In the method according to the invention, therefore, in method step B)
A preferred method according to the invention is characterized in that at least 50 mol %, preferably at least 75 mol %, of the first carboxylic acids are selected from caprylic acid, capric acid and lauric acid, based on the acyl residues of all the first carboxylic acid derivatives.
It is preferred in accordance with the invention, in the method according to the invention, that at least 90 mol % of the second carboxylic acids are selected from ricinoleic acid and hydroxystearic acid, based on the acyl residues of all the second carboxylic acid derivatives.
A preferred method according to the invention is characterized in that at least 90 mol % of the second carboxylic acids comprise ricinoleic acid and/or hydroxystearic acid, wherein the second carboxylic acids preferably have a molar ratio of ricinoleic acid residues to hydroxystearic acid residues in a range of 100 to 0.1 to 50 to 50, based on the acyl residues of all the second carboxylic acid derivatives.
Alternatively, the second carboxylic acid derivative is preferably selected from ricinoleic acid or castor oil.
It is preferred, in the method according to the invention, that the weight ratio of the polyglycerol to the calculated sum total of the acyl residues of the first and second carboxylic acid derivatives used is 85:15 to 55:45, preferably 80:20 to 60:40, particularly preferably 75:25 to 65:35.
A preferred method according to the invention is characterized in that the molar ratio of the acyl residues of saturated to those of the unsaturated carboxylic acid derivatives used in method step B) is 99:1-1:99, preferably 95:5-50:50, particularly preferably 90:10-60:40.
The present invention furthermore relates to polyglycerol partial esters, obtainable by the method according to the invention, wherein the preferred partial esters according to the invention are those which are obtainable by the preferred method according to the invention.
The present invention further relates to formulations, particularly cosmetic and pharmaceutical formulations, wherein particular preference is given to cosmetic formulations which comprise at least one polyglycerol partial ester according to the invention and/or at least one polyglycerol partial ester obtainable by the method according to the invention.
Particular preference is given to formulations which are essentially polyglycol ether-free and essentially free of alkoxylated compounds. The term “essentially free of alkoxylated compounds” and “essentially polyglycol ether-free”, in connection with the present invention, are understood to mean that the formulations have no notable amounts of alkoxylated compounds or compounds comprising polyglycol ethers which exert a surface-active effect. This is particularly understood to mean that these compounds are present in amounts of less than 1% by weight, preferably less than 0.1% by weight, particularly preferably less than 0.01% by weight, based on the total formulation, in particular no detectable amounts.
The polyglycerol partial esters of the present invention can be used advantageously for preparing care and cleaning formulations, particularly for skin and skin appendages, such as liquid soaps, shower gels, oil baths, make-up removers or shampoos, shower gels, foam baths, liquid soaps, hair shampoos, 2-in-1 shampoos, hair conditioners, permanent wave fixing solutions, hair colouring shampoos, hair setting compositions, hair treatments, hair arranging compositions, hair styling compositions, blow-drying lotions, setting foams, hair treatments, leave-in conditioners, hair smoothing compositions, shine improving compositions and compositions for colouring the hair. The present invention therefore also relates to such uses.
The present invention thus also provides care and cleaning formulations, in particular for skin and skin appendages, comprising polyglycerol partial esters according to the invention.
The term “care formulation” is herein understood to mean a formulation which satisfies the purpose of restoring an object to its original form, of reducing or avoiding the effects of external influences (e.g., time, light, temperature, pressure, soiling, chemical reaction with other reactive compounds that come into contact with the object) such as ageing, soiling, material fatigue, bleaching or even of improving desired positive properties of the object. For the last point, mention may be made for example of a shine of the object under consideration.
Cosmetic care and cleaning formulations according to the invention can, for example, comprise at least one additional component selected from the group of:
Substances which can be used as exemplary representatives of the individual groups are known to a person skilled in the art and can be found, for example, in EP2273966A1. This patent application is herewith incorporated as reference and thus forms part of the disclosure.
As regards to further optional components and the amounts of these components used, reference is made expressly to the relevant handbooks known to a person skilled in the art, e.g., K. Schrader, “Grundlagen and Rezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics]”, 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.
The amounts of the particular additives are governed by the intended use. Typical guide formulations for the respective applications are known prior art and are contained for example in the brochures of the manufacturers of the particular basic materials and active ingredients. These existing formulations can usually be adopted unchanged. If necessary, the desired modifications can, however, be undertaken without complication by means of simple experiments for the purposes of adaptation and optimization.
Preferred formulation according to the invention comprise preferred polyglycerol partial esters according to the invention as set out above or preferred polyglycerol partial esters according to the invention obtainable by the method according to the invention as set out above.
It is preferred if the formulation according to the invention additionally comprise at least one oil-soluble substance and water.
In the present invention, oil-soluble substances are understood to mean substances having a log P (logarithm of n-octanol/water partition coefficient, also known as log KOW) of at least 2.
Preference is given to oil-soluble substances having a log P of at least 5. Particular preference is given to oil-soluble substances selected from the group comprising oils based on fatty acids, triglycerides of long-chain fatty acids, cosmetic ester oils, pure hydrocarbons such as jojoba oil, almond oil, soybean oil, avocado oil, olive oil, argan oil, rapeseed oil, sunflower oil, neem oil, caprylic/capric acid triglyceride, shea butter, decyl cocoate, isopropyl palmitate, myristyl myristate and isohexadecane.
Particularly preferred formulations according to the invention comprise 0.1% by weight to 40% by weight, preferably 0.3% by weight to 35% by weight, particularly preferably 0.5% by weight to 10% by weight, of polyglycerol partial ester according to the invention and/or polyglycerol partial ester obtainable by the method according to the invention,0.01% by weight to 40% by weight, preferably 0.1% by weight to 30% by weight, particularly preferably 0.2% by weight to 2% by weight, of oil-soluble substance and 10% by weight to 98% by weight, preferably 20% by weight to 95% by weight, particularly preferably 45% by weight to 90% by weight, of water.
The present invention also relates to the use of at least one polyglycerol partial ester according to the invention and/or at least one polyglycerol partial ester obtainable by the method according to the invention for solubilizing at least one oil-soluble substance in water, wherein it is preferable in accordance with the invention that preferred polyglycerol partial esters according to the invention as set out above or preferred polyglycerol partial esters according to the invention obtainable by the method according to the invention as set out above are used.
The examples listed below describe the present invention by way of example, without any intention of restricting the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.
Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number=935 mg KOH/g) were stirred with 39.4 g of caprylic/capric acid and 20.8 g of refined coconut fatty acid and 22.1 g of ricinoleic acid and 15.5 g of hydroxystearic acid at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number=996 mg KOH/g) were stirred with 39.4 g of caprylic/capric acid and 20.8 g of refined coconut fatty acid and 22.1 g of ricinoleic acid and 15.5 g of hydroxystearic acid at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number=935 mg KOH/g) were stirred with 47.3 g of caprylic/capric acid and 20.8 g of refined coconut fatty acid and 17.7 g of ricinoleic acid and 12.4 g of hydroxystearic acid at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Under a nitrogen atmosphere, 202 g of polyglycerol (hydroxyl number=884 mg KOH/g) were stirred with 37.7 g of caprylic/capric acid and 24.9 g of refined coconut fatty acid and 23.5 g of ricinoleic acid and 12.4 g of hydroxystearic acid at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number=935 mg KOH/g) were stirred with 39.4 g of caprylic/capric acid and 23.0 g of refined coconut oil and 41.5 g of castor oil at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number=935 mg KOH/g) were stirred with 39.4 g of caprylic/capric acid and 23.0 g of refined coconut oil and 23.0 g of castor oil and 14.2 g of castor wax at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
In a first reaction, 225 g of polyglycerol (hydroxyl number=935 mg KOH/g) were stirred under a nitrogen atmosphere with 38.0 g of caprylic acid and 60 g of castor oil at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off.
In a second reaction, 225 g of polyglycerol (hydroxyl number=1060 mg KOH/g) were reacted under identical reaction conditions with 41.0 g of capric acid, 23 g of castor oil and 46.0 g of refined coconut oil.
The two products were then combined and stirred at 90° C. until a clear, homogeneous mixture was formed, which, after cooling to room temperature, was in the form of a turbid liquid.
Under a nitrogen atmosphere, 394 g of polyglycerol (hydroxyl number=1061 mg KOH/g) were stirred with 51.3 g of caprylic/capric acid and 23.0 g of refined coconut fatty acid and 32.8 g of oleic acid at 240° C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid.
Standard solubilizer, polyether-free. INCI: Polyglyceryl-4 caprate. Commercial product of Evonik Industries AG.
Solubilizer for oils, polyether-free. INCI: Polyglyceryl-4 laurate/sebacate (and) polyglyceryl-4 caprylate/caprate (and) water. Commercial product of Croda.
Standard solubilizer, polyether-containing. INCI: PEG-40 Hydrogenated castor oil. Commercial product of Evonik Industries AG.
The products described above were tested in cosmetic formulations below.
The formulation constituents are named in the compositions in the form of the generally recognized INCI nomenclature using the English terms. All concentrations are given in the application examples in percent by weight.
In order to investigate the dissolving power of the inventive polyglycerol partial esters, these were mixed with cosmetic oils and treated with water. The oils tested were avocado oil (supplier: Gustav Heess) and caprylic/capric triglycerides (TEGOSOFT® CT, Evonik Industries AG). The proportion of solubilizer required to completely dissolve 0.5% of the respective oil in water was investigated. For this purpose, the solubilizer (various amounts) was thoroughly mixed with the oil (0.5 g) and then slowly treated with water (made up to 100 g) with stirring. The mixture was stirred for one hour at 45° C. After cooling to 20° C., a “clear mixture” must not become turbid again over a period of 1 week.
In Table 1, the resulting mass ratios of solubilizer to oil which were required to obtain clear mixtures are summarized.
It is evident from the results in Table 1 that the inventive polyglycerol partial esters A, E, F and G have distinctly better solubilizing properties than the polyether-free comparative examples polyglycerol partial ester H and TEGOSOFT® PC 41. Surprisingly, similar solubilizer-to-oil ratios are even achieved as with the polyether-containing standard solubilizer TAGAT® CH 40 and whose performance is to some extent even exceeded.
In addition to the dissolving properties of the inventive polyglycerol partial esters for oil in water shown in example 4, the dissolving power for oils in surfactant formulations was also investigated.
For this purpose, the respective solubilizer was mixed with 0.5 g of caprylic/capric triglycerides (TEGOSOFT® CT, Evonik Industries AG) at 60° C. for 5 min. The water was then slowly added at 60° C. with stirring and the mixture was stirred for 10 min. The mixture was then cooled to 30° C. over a period of 30 min. The mixture was then treated with the surfactants with stirring.
The proportion of solubilizer required to completely dissolve 0.5% of the oil in the respective surfactant system was investigated. Two surfactant systems were used: a standard lauryl ether sulphate/betaine mixture (Table 2) and a polyether-free formulation (Table 3). In Table 4, the resulting mass ratios of solubilizer-to-oil which were required to obtain clear mixtures are summarized.
The results in Table 4 show that the inventive polyglycerol partial esters A and F have distinctly improved solubilizer properties in comparison to the comparative products NATRAGEM® S 150 NP-LQ-(CM) and TEGOSOFT® PC 41. Surprisingly, better results were also obtained to some extent with the inventive polyglycerol partial esters A and F than with the polyether-containing product TAGAT® CH 40.
To evaluate the skin care benefit and the foam properties of the inventive polyglycerol partial ester G in aqueous surfactant formulations, a sensory handwashing test was conducted in comparison to the comparative example TEGOSOFT® PC 41 according to the prior art.
A group consisting of 10 trained test personnel washed their hands in a defined manner and assessed foam properties and skin feel using a grading scale from 1 (poor) to 5 (very good).
The products were tested in each case in a standardized surfactant formulation, using the standard surfactant system of 9% active sodium laureth sulphate and 3% active cocamidopropyl betaine (Table 5).
The sensory test results are summarized in Table 6.
It is evident from the test results in Table 6 that the inventive formulation V using the inventive polyglycerol partial ester G is superior, surprisingly, in all application properties in comparison to the comparative formulation W according to the prior art. In this light, the results of the inventive formulation V can be designated as very good and show a distinct improvement compared to the prior art.
It is evident from the measurements that the inventive polyglycerol partial ester G in formulation V led especially to a significant improvement specifically of the foam creaminess and also the skin smoothness and the skin softness.
The formulation examples given in the tables below show exemplary representatives of a large number of possible compositions according to the invention.
If the preparation of the formulation requires the separate preparation or mixing of formulation constituents beforehand, this is termed multiphase preparation. If a two-phase preparation is required, the two phases are labelled A and B in the stated tables. In the case of three- or more-phase processes, the phases are called A, B, C etc. Unless stated otherwise, the data in the tables are data in % by weight. In the following formulation examples, the data or % by weight are based on the respective active substance. Some products, however, are commercially available as solutions, especially in water, such that in these cases more of the commercial products were used accordingly, depending on the active content.
“Product example A to G” corresponds to the “polyglycerol partial esters A to G of example 1”.
Argania spinosa kernel oil
Citrus aurantifolia (lime) oil
Ricinus communis seed oil seed)
Argania spinosa kernel oil
Butyrospermum parkii butter extract
Helianthus
annuus seed oil
Ricinus
communis seed oil
Prunus
amygdalus
dulcis oil
Argania
spinosa kernel oil
Argania
spinosa oil
Glycine soya oil
Helianthus
annuus seed oil
Simmondsia
chinensis (jojoba) seed oil
Simmondsia
chinensis (jojoba) seed oil
Argania
spinosa kernel Oil
Glycine
soja (soybean) oil
Persea
gratissima (avocado) oil
Zea
mays (corn) germ oil
Argania
spinosa oil
Camellia
oleifera seed oil
Glycine soya oil
Simmondsia
chinensis seed oil
Prunus
amygdalus
dulcis (sweet almond) oil
Triticum
vulgare germ oil
Glycine soya oil
Butyrospermum
parkii butter extract
Helianthus
annuus seed oil
Prunus
cerasus fruit extract
Mangifera
indica (mango) fruit extract
Malva sylvestris leaf extract
Cistus incanus extract; Maltodextrin
Aloe barbadensis leaf juice
Prunus amygdalus dulcis oil
Prunus amygdalus dulcis oil
Helianthus annuus seed oil
Olea europaea fruit oil
Prunus amygdalus dulcis oil
Simmondsia chinensis seed oil
Helianthus annuus seed oil
Argania spinosa oil
Prunus amygdalus dulcis oil
Olea europaea fruit oil
Butyrospermum parkii butter
Persea gratissima oil
Helianthus annuus seed oil
Olea europaea fruit oil
Persea gratissima (avocado) oil
Butyrospermum parkii butter
Prunus amygdalus dulcis oil
Aloe barbadensis leaf juice
Argania spinosa oil (Argania
spinosa kernel oil)
Butyrospermum parkii
Camellia oleifera seed oil
Camellia Sasanqua Oil, Ikeda Corporation
Chamomilla recutita
Citrus aurantifolia (lime) oil
Cistus incanus extract;
Glycine soya (soybean) oil
Helianthus annuus
Malva sylvestris leaf extract
Mangifera indica (mango)
Olea europaea (olive) fruit oil
Persea gratissima
Prunus amygdalus dulcis
Prunus cerasus (bitter cherry)
Prunus Cerasus Fruit, Kirschen Extract,
Ricinus communis seed oil
Simmondsia chinensis
Triticum vulgare germ oil
Zea mays (corn) germ oil
While the present invention has been particularly shown and described with respect to various embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in forms and details may be made without departing from the spirit and scope of the present invention. It is therefore intended that the present invention not be limited to the exact forms and details described and illustrated, but fall within the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102013224957.8 | Dec 2013 | DE | national |
