Patent Application
20140086861
The present application relates to the incorporation of pigment into cosmetic compositions. In the sense of the present application, by <<cosmetic composition>> is meant any cosmetic formulation intended to be applied on the skin, hair and/or nails. The formulations may be in the form of a powder, a fluid solution or thickened with thickeners (gel) or aqueous or fatty gelling agents (stick), a water-in-oil or oil-in-water emulsion.
In particular, the invention relates to the incorporation of pigment into aqueous cosmetic compositions. In the sense of the present application, by <<aqueous cosmetic composition>>, is meant a cosmetic composition for which the medium is an aqueous medium, i.e. it comprises from 1 to 95% by mass of water, notably 10 to 70% by mass of water, for example from 20 to 60% by mass of water, said aqueous medium may be a fluid or thickened aqueous solution or an oil-in-water emulsion.
Many cosmetic compositions comprise solids dispersed in a divided state, notably pigments. The more the pigments are dispersed homogeneously in the cosmetic composition, the more homogeneous and intense is the color of the cosmetic composition. The homogeneous dispersion of the pigments in a cosmetic composition is ensured by a step of grinding the pigment in one of the liquid phases of the cosmetic composition.
In order to allow good dispersion of pigment into non-aqueous cosmetic compositions, treatment of the pigments with hydrogenated lecithin has been proposed. Hydrogenated lecithin includes phosphate mono- and di-esters including fatty chains. Once it is deposited on the pigment, hydrogenated lecithin promotes dispersion of the latter in the oily phase. The use of pigments treated with hydrogenated lecithin in a cosmetic composition, the medium of which is oily, therefore gives the possibility of obtaining adequate coloration without any grinding step. However, the pigments treated with hydrogenated lecithin are not easily dispersible in aqueous compositions.
The dispersion of pigments in aqueous cosmetic compositions is more delicate and to this day, only very few treated pigments exist which are easily dispersible in an aqueous medium.
One of the goals of the present invention is to provide a solution for easily and efficiently dispersing a pigment in a cosmetic composition notably an aqueous cosmetic composition.
For this purpose, the present invention provides a pigment composition comprising, in addition to a pigment, an additive making this pigment easily dispersible within aqueous cosmetic compositions.
More specifically, according to a first aspect, the object of the invention is a pigment composition comprising, among other possible components:
an additive of the following formula (I):
wherein:
This pigment composition is suitable for introduction into a cosmetic composition such as an aqueous cosmetic composition. It generally appears as a powder comprising the intimately mixed pigment and additive, the additive being generally adsorbed or precipitated at the surface of the pigment.
A pigment composition in the form of a powder is particularly advantageous over a composition in liquid form (suspension, emulsion or solution).
First of all, it does not comprise any liquid phase and is therefore more lightweight. The costs for transport and storage, and a fortiori the cost of the pigment composition are therefore lower.
Further, it does not comprise any liquid phase based on solvents, which may be toxic or flammable.
Finally, a pigment composition as a powder may advantageously be dispersed regardless of the medium of the composition in which dispersion is desired. On the contrary, for a pigment composition in liquid form, it should be ascertained that the liquid phase of the pigment composition and that of the composition into which dispersion is desired, are compatible and may mix together in order to form a homogeneous medium. Further, a pigment composition in liquid form imposes the introduction of an amount of liquid phase which, either by its chemical nature or by its organoleptic properties, may not be desired in the composition in which dispersion is desired. Thus, the possibilities of formulating a pigment composition as a powder are much more extended than those of a pigment composition in liquid form.
It is found that the pigment compositions according to the invention disperse very easily and efficiently in an aqueous medium or in the continuous aqueous phase of an oil-in-water emulsion. Without being bound to a particular theory, the investigations made by the inventors within the scope of the invention give the possibility of putting forward that the hydrophilic group R of the additive of formula (I) would facilitate dispersion of the pigment composition in an aqueous medium.
Moreover, the pigment composition according to the invention advantageously has an improved water retention capacity, relatively to that of the pigment alone. Thus, the pigment composition according to the invention and therefore the cosmetic composition in which it is dispersed, have good moisturizing power. The water retention capacity may notably be demonstrated by tracking the loss of mass over time (thermogravimetry analysis), which may be directly correlated with the evaporation of water, of an aqueous dispersion of a pigment composition according to the invention as compared with that of an aqueous dispersion of the pigment alone.
Without intending to be bound by a particular theory, it seems that this property may be related to the presence, in the chemical formula of the additives of the pigment composition (which are located at the surface of the pigment), of groups which may be engaged into hydrogen bounds (oxygen atom or hydroxyl group for example) and therefore may form hydrogen bonds with water, which would explain the increased water retention capacity.
The group —[CH2—CHR1—O]q—R2 with R1 representing H corresponds to a polyethylene glycol (PEG). The group —[CH2—CHR1—O]q—R2 with R1 representing a methyl corresponds to a polypropylene glycol (PPG). The group —[CH2—CH(CH2OH)—O]q—R′ corresponds to a polyglycerol.
Typically q is an integer from 1 to 500, notably from 1 to 100, preferably from 1 to 60.
Preferably, n represents 2 and the additive has the following formula (I′)
wherein M, m and R are as defined above.
In the sense of the present application, a hydrocarbon chain comprises from 1 to 500 carbon atoms, notably from 1 to 50, typically from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. The hydrocarbon chains may be linear, branched or cyclic. The preferred hydrocarbon chains are alkyl groups (preferably having from 1 to 10 carbon atoms, notably from 1 to 5 carbon atoms, preferably from 1 to 3, such as methyl, ethyl, n-propyl and isopropyl groups), alkenyl groups (preferably having from 2 to 10 carbon atoms, in particular from 2 to 6), aryl groups (preferably having from 6 to 10 carbon atoms), arylalkyl groups (preferably having from 7 to 10 carbon atoms) or alkylaryl groups (preferably having from 7 to 10 carbon atoms). The vinyl group is the preferred alkenyl group. The phenyl group is the preferred aryl.
A saccharide may be a mono- or poly-saccharide. The preferred saccharides are mono- or di-saccharides, in particular mono-saccharides such as glucose, galactose or fructose.
M may notably be an inorganic cation such as Ag3+, Al3+, Fe3+, Fe2+, Ag2+, Zn2+, Sn2+, Ca2+, Ba2+, Ag+, Na+ or an organic cation, such as diethanolammonium (DEA) (H3N+−(CH2)2—OH) or a quaternary ammonium.
The following additives of the following formulae (II), (III) or (IV) are particularly adapted to carry out the invention:
The additives of formula (III) (and in particular of formula (III′) as defined below), are particularly advantageous in that the pigment composition comprising them:
Therefore, a cosmetic composition comprising such a pigment composition is not wetted by the sebum of the skin and is particularly suitable for being applied on an oily skin.
The following additives of formula (V) and (VI) are also suitable for carrying out the invention:
The additives of formula (V) (and in particular of formula (V′) as defined below), are particularly advantageous in that the pigment composition comprising them:
The following additives are more preferred:
The pigment present in the composition according to the invention may be an organic, inorganic pigment or of an organic-inorganic hybrid nature or a mineral filler. It is typically an inorganic pigment.
As pigments adapted for carrying out the invention, mention may notably be made of titanium dioxide, zinc dioxide, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue and mixtures thereof. The preferred mineral pigments are iron oxides, notably red iron oxide, yellow iron oxide, brown iron oxide, black iron oxide, titanium dioxide and mixtures thereof.
In an embodiment, the pigment is an iron oxide, notably red iron oxide, yellow iron oxide, brown iron oxide, black iron oxide and mixtures thereof.
As mineral fillers suitable for carrying out the invention, mention may notably be made of talcum, mica, kaolin, alumina, silica.
Generally, the pigment composition comprises from 0.01% to 20% by weight, typically from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, in particular of the order of 1% by weight, of additive of formula (I) based on the weight of the combination pigment/additive of formula (I).
The pigment composition according to the invention is hydrophilic and easily disperses in aqueous media, even viscous media, and in the continuous aqueous phase of an oil-in-water emulsion. The inventors have discovered that the use of the pigment composition according to the invention in a cosmetic composition comprising an aqueous medium or an oil-in-water emulsion gives the possibility of obtaining intense and homogeneous coloration. The coloration may for example be measured by spectrocolorimetry and/or spectrophotocolorimetry.
The pigment composition may also contain in addition to the additive of formula (I) and to the pigment, other additives such as polyacrylates or polyacrylic acids, polyethoxylated alkosilanes, surfactants, carboxylic acids comprising ethylene oxide chains, amino acids, chitosan, cellulose and its derivatives (cellulose ether, microcrystalline cellulose, carboxymethylcellulose and hydroxypropyl methylcellulose (HPMC)), sugars such as galactoarabinan or xanthan gum, silica and alumina.
According to a second aspect, the object of the invention is a method for preparing a pigment composition as defined above. This method comprises the following steps:
The solvent is generally an aqueous solution preferably water.
Generally, all the steps of the method are carried out at room temperature (of the order of 25° C.) and at atmospheric pressure.
Step a) may be carried out either by mixing the pigment and the additive in the solvent simultaneously, or by preparing a mixture of the additive in a solvent (mixture 1) on the one hand, preparing a mixture of the pigment and of the solvent (mixture 2) and then mixing together both mixtures (mixtures 1+2) on the other hand. No difference in the quality of the pigment composition obtained was observed by varying the addition order of the additive, of the pigment and of the solvent.
During the mixing, the additive is more or less adsorbed on the pigment. It is however preferable that the additive is adsorbed on the pigment. Thus, when adsorption is insufficient, it is advantageous to add a step b), i.e. acidifying the mixture obtained at step a) to a pH of less than or equal to 2 and/or adding a salt to the mixture obtained at step a).
According to the additive and the aqueous medium used:
The method may also comprise a step b) of adding a salt to the mixture of step a). This salt is typically a salt which may cause precipitation of the additive according to the invention. Generally, the salt is added in a stoichiometric amount of the phosphate groups of the additive.
Without intending to be bound to a particular theory, during the addition of the salt, an exchange of ions would take place between the initial anion of the additive and the anion of the salt, as illustrated in the following scheme:
Scheme: Postulated mechanism: Anion exchange between the anion Minitial of the additive (of charge minitial) with the anion Msalt (of charge msalt) of the added salt, leading to the precipitation of the additive of formula:
The method may also comprise a step b) consisting of acidifying the mixture to a pH of less than or equal to 2 and of adding a salt to the mixture, the acidification and the addition of a salt may be simultaneous or successive, and in this case the addition of the salt and of the acidification may be performed in any order at step b).
In this embodiment, the method also comprises a subsequent step c) of basification to a pH from 3 to 8, preferably of the order of 5.5. The basification may be carried out by adding a base (for example sodium hydroxide) to the medium, under conditions known to one skilled in the art. Thus, the pH before filtration of the powder is of the order of a pH close to that of the skin, which is suitable for a cosmetic application.
One or several steps of stirring the medium may be added between the steps of the method, typically for 30 minutes to one hour.
At the end of the preparation method, a pigment composition is obtained, which corresponds to a pigment treated with the additive of formula (I). The invention also relates to the pigment compositions which may be obtained by the method defined above.
According to a third aspect, the object of the invention is the use of the pigment composition or of a pigment composition which may be obtained according to the aforementioned method for introduction into a cosmetic composition, notably an aqueous composition (or for preparing a cosmetic composition, notably an aqueous composition), as well as a cosmetic composition comprising the pigment composition.
The cosmetic composition may for example be mascara, foundation, eyeliner, eyeshadow or blush, lipstick, lip gloss, optionally liquid soap, shampoo, conditioner, nail varnish, preferably mascara or foundation. The cosmetic composition may appear as a mono-phasic or bi-phasic lotion, as a water-in-oil or oil-in-water emulsion, gel, cream, or powder.
In an embodiment, the cosmetic composition comprises a pigment composition, the pigment of which is iron oxide, a sequestering agent and a cosmetically acceptable anionic polymer.
The pigments based on iron oxide have the drawback of being incompatible with anionic polymers. Thus, cosmetic compositions comprising iron oxide as a pigment and an anionic polymer are difficult to formulate, since the iron oxide is poorly dispersed therein.
The inventors have discovered that in particular in the presence of a sequestering agent, a pigment composition according to the invention, comprising iron oxide and one of the additives defined above, is very well dispersed in a cosmetic composition comprising a cosmetically acceptable anionic polymer.
It is known that a sequestering agent contributes to the dispersion of the iron oxide in a cosmetic composition comprising a cosmetically acceptable anionic polymer. This being the case, in this embodiment of the invention, the inventors have demonstrated the existence of a synergistic effect of the sequestering agent and of the additive on the dispersion of the iron oxide pigment, since the dispersibility of a pigment composition comprising iron oxide in a cosmetic composition comprising a sequestering agent and an anionic polymer unexpectedly goes beyond the sum of the dispersibilities:
The sequestering agent is notably selected from phytic acid, citric acid, gluconic acid, pentetic acid, ethylene diamine tetraacetic acid (EDTA), cyclodextrin, salts thereof and a mixture thereof, preferably citric acid or one of its salts.
The salts are preferably formed with an alkaline or earth alkaline metal, preferably an alkaline metal, sodium or potassium salts being more preferred. Mention may notably be made of potassium or sodium citrate, potassium or sodium gluconate, pentasodium pentetate, disodium EDTA salt, trisodium EDTA salt or tetrasodium EDTA salt as a sequestering agent in the form of a salt.
The cosmetically acceptable anionic polymer is typically xanthan gum, carboxymethylcellulose or polyacrylate.
According to a fourth aspect, the object of the invention is a method for preparing a cosmetic composition comprising a pigment comprising a step of dispersing a pigment composition as defined above in an aqueous medium.
Advantageously, starting with the pigment composition as starting product, the method for preparing the cosmetic composition is generally free from grinding step. Therefore it may be applied without a grinder, which is an advantage since grinding equipment is not necessary and the production cost of the cosmetic composition is lower.
According to a fifth aspect, the object of the invention is a cosmetic composition which may be obtained with this method.
The cosmetic composition typically comprises the pigment composition as defined above and at least one cosmetically acceptable excipient.
The examples and the figure hereafter illustrate the invention.
The appended figure illustrates the % ratio of the mass of a 40% aqueous dispersion at instant t over the mass of this aqueous dispersion at t=0 (i.e. at the beginning of the heating, the temperature then being 25° C.) versus time in minutes, either for a 40% aqueous dispersion of a pigment composition of Example 2 Experiment 8 (solid line) or for a 40% aqueous dispersion of red iron oxide (dotted line).
Examples 1 to 4 relate to the preparation of pigment compositions according to the invention and to their introduction into a cosmetic composition of the oil-in-water type.
Examples 5 to 13, 15 and 16 relate to cosmetic compositions according to the invention comprising pigment compositions.
Example 14 relates to the improvement of the water retention capacity of a pigment composition as compared with pigment alone.
Components of the Pigment Composition
Four additives of formula (II′), (III′), (IV′) and (V′) were used in the Examples.
Four pigments were used: black, yellow, red iron oxides, titanium dioxide.
Suppliers of the Various Components Used
Methods for Preparation of Pigment Compositions:
Introduction of the Pigment Composition into an Oil-in-Water Emulsion
After preparation of the pigment composition, the latter was introduced into an aqueous cosmetic composition of the oil-in-water emulsion type prepared as follows:
The introduction of the pigment composition into the cosmetic composition does not comprise any grinding step.
Covasop corresponds to a pigment dispersion in propylene glycol. It allows degradation of the color of the mixture [emulsion/pigment composition] in order to further reveal the colorimetric differences. When the pigment composition comprises a black, red or yellow iron oxide pigment, the dispersion used is Covasop W9775 White (Sensient®) containing titanium dioxide. When the pigment composition comprises titanium dioxide, the dispersion used is Covasop W3774 Red containing red iron oxide.
Colorimetric Test
The apparatus used is a Minolta Spectrophotometer CM-3300d, and allows measurement of the color in the Lab reference system. The measurement of the color of a colored aqueous cosmetic composition containing the treated pigment relatively to the measurement of the color of a colored aqueous cosmetic composition containing the untreated pigment, called a reference, gives the possibility of obtaining color differences, ΔL* being the luminosity difference, Δa* the difference in the red/green hues and Δb* the difference in the yellow/blue hues.
The references used for calculating color differences were prepared by using the same procedure as the one described above in <<Introduction of the pigment composition in an oil-in-water emulsion>>, except that 2% by mass of reference pigment (pure pigment without any additive, this pigment being the same as the one used in the pigment composition) were added instead of the pigment composition in the last step.
As a white pigment dispersion is added to the emulsion in order to attenuate the color (cf above), the values of ΔL* (luminosity, black and white) are especially those which are important and which indicate that the obtained emulsion is more or less black. A negative ΔL* is synonymous with a blacker coloration than the reference, and all the blacker since the absolute value of the ΔL* is significant. The more the emulsion is black (more intense black color) the better the iron oxide is dispersed in the emulsion.
The results illustrated in Table 2 show that regardless of the operating procedure used for preparing the pigment composition, the pigment composition is better dispersed in an oil-in-water emulsion than the untreated pigment alone (reference).
The results illustrated in Table 3 show that the use of a pigment composition comprising from 1 to 6 wt % of additive gives the possibility of obtaining a better dispersion in an oil-in-water emulsion than with the pigment alone (reference).
B. With other Pigments
The results of Table 4 show that the additive used in the pigment composition is also efficient for other pigments.
The results illustrated in Table 5 show that this additive is also efficient for improving the dispersion of the powder in an oil-in-water emulsion as compared with the pigment used alone (reference).
The results of Table 6 show that the additive used in the pigment composition is also efficient for other pigments.
The results illustrated in Table 7 show that this additive is also efficient for improving the dispersion of the powder in an oil-in-water emulsion as compared with the pigment used alone (reference).
The results of Table 8 show that the additive used in the pigment composition is also efficient for other pigments.
The results illustrated in Table 9 show that this additive is also efficient for improving dispersion of the powder into an oil-in-water emulsion as compared with the pigment used alone (untreated) (reference).
The results of Table 10 show that the additive used in the pigment composition is also efficient for other pigments.
Thus, Examples 1 to 4 demonstrate that the pigment compositions according to the invention are easily dispersed in a cosmetic composition of the oil-in-water type, without any grinding step being necessary for incorporating the pigment composition during the preparation of the cosmetic composition.
The pigment compositions containing the additive of formula (V′) were introduced into water. Unipure Red LC381 HLC (hydrophobic red iron oxide) and Unipure White LC981 HLC (hydrophobic titanium dioxide) were introduced in the mineral oil. The fatty phase was then poured onto the aqueous phase in order to form a biphasic medium. The obtained biphasic foundation comprises the pigment composition according to the invention in the aqueous phase while Unipure Red LC381 HLC and Unipure White LC981 HLC are in the oily phase. The foundation should be stirred before use.
This example illustrates the affinity for water of the pigment composition containing phytic acid (additive of formula (V′)) in a cosmetic composition of the biphasic foundation type.
Macadamia Ternifolia Seed Oil
Covathick 2009 was dispersed in glycerol and then introduced into water with stirring, and the four premixed pigment compositions were then introduced without grinding into the gelled aqueous phase. Natpure SF was introduced into the aqueous phase containing the pigment compositions. The aqueous phase containing the pigment compositions was heated to 60° C. and introduced with stirring into macadamia oil heated to 60° C. Finally, Submica FL was added to the final emulsion.
This example illustrates the compatibility of the pigment composition containing glycerophosphate (additive of formula (III′)) with the anionic polymers in a cosmetic composition of the oil-in-water foundation emulsion type.
Examples 7 to 9 illustrate the property of very low water absorption of the pigment composition containing the additive of formula (V′) in a cosmetic composition of the mascara, foundation and eyeliner type.
The oily phase consisting of the base RW136 and of dimethicone was heated to 85° C. The water and the preservatives were also heated to 85° C., and the thickener based on xanthan gum was introduced into this aqueous phase. This aqueous phase was introduced with stirring into the oily phase. Next, the water containing triethanolamine was heated to 70° C. and added to the previous mixture. Cyclopentasiloxane was then introduced into the emulsion. The pigment composition was then introduced without any grinding. Next, the acrylic copolymer was added to the emulsion.
All the ingredients were mixed and cast into a cup. The dispersion was then dried at 60° C. The thereby obtained solid foundation is used with an applicator moistened with water.
The Thickagent LC was dispersed in monopropylene glycol and then introduced with stirring into the water. The obtained gel was diluted in phase B. The pigment composition was dispersed in glycerol and then introduced into the gel. Covavryl MS11 was introduced.
Examples 7 to 9 above illustrate the property of very low water absorption of the pigment composition containing the additive of formula (V′) in a cosmetic composition of the mascara, foundation and eyeliner type.
color changing
type
The ingredients of phase A were mixed and heated to 80° C., and then cooled to 50° C. The cyclopentasiloxane was then introduced into the mixture. The water, the salt, the propylene glycol and the preservative were mixed and heated to 50° C. and then slowly introduced into the oily phase with stirring (vortex). The mica and the titanium dioxide treated with lecithin were then introduced into the emulsion. The mixture of the three pigment compositions containing the additive (V′) was added into the mixture of water, glycerol and next Covacryl SJ5 was added. This phase was then introduced into the emulsion. The foundation has an off-white aspect and the beige color develops during application on the skin.
This example shows that the pigment composition containing sodium glycerophosphate (additive of formula (III′)) may be encapsulated and used in cosmetic compositions of the color-changing type.
Sodium Laureth Sulfate, Cocamidopropyl Betaine, water and the preservative were mixed and heated to 65° C. The mixture of Cocamide MIPA (and) Glyceryl Stearate was melted and then introduced into the previous mixture. Tetrasodium EDTA and then Polyquaternium-10 were introduced into the mixture. At room temperature, the pH was adjusted with citric acid.
This example illustrates the capability of the pigment composition containing phytic acid (additive of formula (V′)) of forming colored foams when it is introduced into a cosmetic composition of the shampoo type.
The preservative was introduced into the demineralized water, and then the four pigment compositions containing the additive (V′) were incorporated without grinding into the aqueous phase. The thickener based on xanthan gum was introduced with stirring, followed by Saccaluronate LC, Serica 5 and Covabead PMMA2MUSI.
The four pigment compositions were dispersed in isononyl isononanoate with stirring. Phase B was heated to 90° C. until the waxes had melted and then cooled to 80° C. Phase A was incorporated into phase B with stirring until a homogeneous mixture was obtained. Phase C was introduced into the mixture kept at 80° C. Once the mixture had cooled to 60° C., phases D, E, F and G were introduced one after the other with stirring.
Examples 12 and 13 illustrate the capability of the pigment composition containing the additive of formula (III′) or (V′) of absorbing a large amount of oil in a cosmetic composition of the aqueous gel correcting foundation type for oily skins (Example 12) and an oily gel foundation (Example 13).
A 40% dispersion in water of the pigment composition of Example 2 reference 8 (comprising red iron oxide and the additive of formula (III′)) on the one hand, and a 40% dispersion in water of red iron oxide on the other hand were brought from an initial temperature of 25° C. to a temperature of 50° C. by heating at 1° C./min (a temperature of 50° C. reached in 25 mins), and the temperature of 50° C. was then maintained. The mass loss over time was tracked with a Perkin Elmer TGA7 thermogravimeter.
The appended figure shows that the 40% dispersion in water of the pigment composition according to the invention loses less rapidly the 40% water than the iron oxide dispersion.
The following operating procedure was followed:
Phase A was incorporated into phase B by stirring with a propeller at room temperature (25° C.). The stirring was maintained until a homogeneous gel was obtained. Phase C was incorporated by stirring with a propeller at room temperature. Stirring was maintained for 5 mins at 800 rpm.
Visual observation shows that the dispersion of the pigment composition into the obtained composition is excellent. The coloration of the composition is intense and homogeneous. The experiment was reproduced in the absence of sodium citrate (sequestering agent) on the one hand, by replacing the pigment composition of Experiment No. 2 of Example No. 2 with black iron oxide on the other hand.
Visual observation shows that the iron oxide is not as well distributed in the obtained compositions, and that their colorations are low.
Macadamia oil
Phase B was dispersed into phase A with strong stirring. Phase C was added to the obtained mixture. A Covathick 2009 gel was prepared by dispersing the powder in water with a Rayneri apparatus and then by stirring for 1 minute at 13,500 rpm with an Ultraturrax apparatus. Phase D was then added to the mixture of phases A, B and C. The obtained mixture was then heated to 60° C. in a water container. Phase E was then added with stirring, followed by phase F. The obtained mixture was homogenized for 5 minutes.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1151922 | Mar 2011 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2012/054045 | 3/8/2012 | WO | 00 | 12/10/2013 |
