WO2013007599A2

WO2013007599A2 - A composition for coating keratinous fibers comprising an ester of behenic acid and of glycerol as a main emulsifying system

Info

Publication number: WO2013007599A2
Application number: PCT/EP2012/063142
Authority: WO
Inventors: Daovone BOUNLUTAY; Sophie Favre
Original assignee: Chanel Parfums Beaute
Priority date: 2011-07-08
Filing date: 2012-07-05
Publication date: 2013-01-17
Also published as: WO2013007599A3; FR2977488A1

Abstract

The object of the present invention is a cosmetic composition for coating keratinous fibers, notably eyelashes, in the form of a wax-in-water emulsion, characterized in that it further comprises one ester of behenic acid and of glycerol, said ester of behenic acid and of glycerol forming the main surfactant system of the composition. According to another of its aspects, the invention relates to a method for non-therapeutic care and/or make-up of keratinous fibers, notably eyelashes, comprising the application on said keratinous fibers of a composition as described earlier. The present invention is also directed to the use of a composition as described earlier in order to obtain on the keratinous fibers in particular eyelashes, a homogeneous and/or loading and/or volumizing make-up on the eyelashes.

Description

A composition for coating keratinous fibers comprising an ester of behenic acid and of glycerol as a main emulsifying system

The object of the present invention is a cosmetic composition for coating keratinous fibers, notably eyelashes, in the form of a wax-in-water emulsion and comprising at least one ester of behenic acid and glycerol as a main emulsifying system.

The composition according to the invention may be a make-up composition or a composition for taking care of keratinous fibers such as eyelashes, eyebrows, hair. More particularly, this is a composition for making up keratinous fibers.

More specially, the composition according to the invention is a composition intended to be applied on eyelashes, further called a « mascara ». This may be a make-up composition, a cosmetic composition for a base coating also called « basecoat », a composition to be applied on a cosmetic base coat composition, further called « top-coat ». The mascara is more particularly intended for eyelashes of human beings, but also for false eyelashes.

Among the formulations of mascaras, in particular mascaras said to be « mascara emulsions » or « washable mascara » are known, consisting of wax or of a mixture of waxes dispersed by means of at least one surfactant in an aqueous phase, moreover containing water-soluble polymers and pigments.

The loading nature of mascaras, represented by the thickness of the coat on the eyelash, is a property which is often sought with the purpose of underlining the look and of making it more intense.

For mascaras of the « washable » type, the principle for obtaining a volumizing or loading effect consists of depositing a maximum of solid materials on the eyelashes.

In particular, it is by adjusting the amount of dispersed solids, which allow the composition to be structured, that it is possible to adjust the sought application specificities of the compositions, such as for example fluidity or consistency, as well as the thickening power, further called the loading or making-up potential. These solid particles, and in particular the waxes, are generally dispersed by means of a surfactant system. The selection of the surfactant system is prominent in obtaining a stable dispersion, insofar that the surfactants play an important role at the interface of the emulsion, in interactions between the waxed particles within the formulation.

Among surfactants or conventional surfactant systems allowing stabilization of waxes-in-water emulsions, surfactant systems based on triethanolamine stearate are well-known, either used alone or in combination with other surfactants.

However, the introduction of these primary, secondary and tertiary alkanolamines in mascara compositions is less and less desirable for reasons of toxicity.

Therefore, there remains a need for cosmetic compositions for coating keratinous fibers, notably eyelashes, having a satisfactory loading power and which are preferably free of triethanolamine or of its derivatives, notably giving the possibility of obtaining a thick (or heavy) make-up of keratinous fibers, in particular eyelashes.

Specifically, the present invention has the goal of meeting this need.

As this is apparent from the description and from the examples presented hereafter, the inventors discovered that it is possible to obtain a particularly stable wax-in-water emulsion over time and having good loading properties, by applying an emulsifying system comprising at least one ester of behenic acid and of glycerol.

More specifically, the inventors were able to observe that the emulsifying system based on at least one ester of behenic acid and of glycerol, defined in the present application gave the possibility of obtaining a stable dispersion and preferably stable over time, of a large amount of waxes. The make-up compositions comprising these emulsions provide a make-up result comparable or even better than the one obtained with the compositions of the prior art.

In the sense of the present invention, the term of « keratinous fibers » covers hair, eyelashes, eyebrows and also extends to synthetic hair pieces and false eyelashes. A « wax-in-water emulsion » designates, in the sense of the present invention, a composition comprising at least one wax or a mixture of waxes dispersed by means of at least one surfactant in a continuous aqueous phase.

By « stable» composition, is meant in the sense of the present invention a composition which after having been placed in an oven at 5°C, 40°C and 45°C for two months, does not, after returning to room temperature, have any tactile grains when a thin layer of the composition is sheared between the fingers. Stability tests are performed on the formulations by storing the product for two months at 5°C, 40°C, 45°C. Rheology stability tests are performed by storing the product for 7 days, 1 month and 2 months at 20°C.

Thus, the invention according to one of its aspects relates to a cosmetic composition for coating keratinous fibers, in particular eyelashes, in the form of a wax-in-water emulsion, characterized in that it comprises at least one ester of behenic acid and of glycerol, said ester of behenic acid and of glycerol forming the main surfactant system of the composition.

Advantageously, the ester of behenic acid and of glycerol represents 90% to 100% by weight, preferably 95% to 99.5% by weight, and more preferentially from 98% to 99%, by weight, based on the total weight of the surfactant system of the composition according to the invention.

The compositions of the invention are particularly suitable for making up eyelashes, in particular favoring easy application on the eyelashes as well as obtaining a smooth and homogeneous coat.

According to another of its aspects, the invention relates to a make-up and/or non-therapeutic care method for keratinous fibers, notably eyelashes, comprising the application on said keratinous fibers of a composition as described earlier.

The present invention is also directed to the use of the composition as described earlier for obtaining on keratinous fibers, in particular eyelashes, a homogeneous and/or loading make-up.

In the sense of the present invention, the term of « loading » is intended to describe the notion of a heavy make-up on the eyelashes.

Other features, properties and advantages of the present invention will become more clearly apparent upon reading the description and the examples which follow.

The composition according to the invention, of course, comprises a physiologically acceptable medium.

By « physiologically acceptable compound or medium » in the sense of the present application, is meant a compound or a medium, the use of which is compatible with application on keratinous materials, and notably on eyelashes. Emulsifying system

The composition according to the invention comprises at least one ester of behenic acid and of glycerol forming the main surfactant system of said composition.

It should be noted that within the scope of the present application, the terms of « surfactant » and « emulsifying » are equally used.

By "main surfactant system", is meant a system which in its absence does not lead to the formation of a stable composition and/or a system forming more than 50% by weight of the total weight of the surfactant system of the composition.

In particular, the ester of behenic acid and of glycerol represents 90% to 100% by weight, preferably 95% to 99.5% by weight and more preferentially from 98% to 99% by weight, based on the total weight of the surfactant system of the composition according to the invention.

By an ester of behenic acid and of glycerol, is in particular meant the mixtures of mono-, di- and/or tri-esters of C22 carboxylic acid(s) and of glycerol. The ester of behenic acid and of glycerol is notably selected from glyceryl mono-behenate, glyceryl di-behenate, glyceryl tri-behenate and mixtures thereof.

The ester of a carboxylic acid and of glycerol may in particular be a mixture of glycerol mono-behenate, glyceryl di-behenate and glyceryl tri-behenate.

Such a mixture is notably available under the INCI name of « glyceryl dibehenate & tribehenin & glyceryl behenate », and notably marketed under the reference Compritol 888® by Gattefosse.

It is also present mixed in the raw material bearing the INCI name of « tribehenin PEG20 ester » marketed under reference Emulium® 22 by Gattefosse.

The ester of behenic acid and of glycerol may be present in the composition in a content ranging from 1 % to 12% by weight, preferably from 3% to 9% by weight and better around 6% by weight based on the total weight of the composition.

Advantageously, the ester of behenic acid and of glycerol forms the single surfactant system of the composition.

By « single » is meant that any additional surfactant other than the ester of behenic acid and of glycerol according to the invention, is present in a content not exceeding 1 % by weight, and preferably not exceeding 0.5% by weight based on the total weight of the composition. Still preferably, the composition does not comprise any additional surfactant other than the ester of behenic acid and of glycerol.

When the emulsifying system comprises an additional surfactant, the latter is, of course, suitably selected in order to obtain a wax-in-water emulsion. In particular, it is possible to use an additional surfactant agent having at 25°C, a hydrophilic-lipophilic balance (HLB) in the sense of GRIFFIN, greater than or equal to 8.

These additional surfactants may be selected from non-ionic, anionic, cationic, amphoteric surfactants or further emulsifying surfactants. Reference may be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", Volume 22, p.333-432, 3^rd Edition, 1979, WILEY, for the definition of the properties and (emulsifying) functions of surfactants, in particular p. 347- 377 of this reference, for anionic, amphoteric and non-ionic surfactants.

These additional surfactants may preferably be selected from a) non-ionic surfactants with an HLB of more than or equal to 8 at 25°C, used alone or as a mixture; mention may notably be made of:

- oxyethylene and/or oxypropylene ethers (which may include from 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol;

- oxyethylene and/or oxypropylene ethers (which may include from 20 to 1 ,000 oxyethylene and/or oxypropylene groups) of fatty alcohols (notably Cs-C2₄, and preferably C12-C18 alcohols) such as the oxyethylene ether of cetearyl alcohol with 30 oxyethylene groups (CTFA name: "Ceteareth-30"), the oxyethylene ether of stearyl alcohol with 20 oxyethylene groups (CTFA name: "Steareth-20") such as BRIJ 78 marketed by UNIQEMA, the oxyethylene ether of cetearyl alcohol with 30 oxyethylene groups (CTFA name "Ceteareth-30") and the oxyethylene ether of the mixture of C12-C15 fatty alcohols including 7 oxyethylene groups (CTFA name: "C12-15 Pareth-7") marketed under the name of NEODOL 25-7® by SHELL CHEMICALS,

- esters of fatty acid (notably of a Cs-C2₄, and preferably C16-C22 acid) and of polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units) such as PEG-50 stearate and PEG-40 monostearate marketed under the name of MYRJ52P® by ICI UNIQEMA,

- esters of fatty acid (notably of a Cs-C2₄, and preferably C16-C22 acid) and oxyethylene and/or oxypropylene glycerol ethers (which may include from 1 to 150 oxyethylene and/or oxypropylene groups), such as PEG-200 glyceryl monostearate sold under the name of Simulsol 220 TM® by SEPPIC; polyethoxylated glyceryl stearate with 30 ethylene oxide groups such as the product TAGAT S® sold by GOLDSCHMIDT, polyethyoxylated glyceryl oleate with 30 ethylene oxide groups such as the product TAGAT O® sold by GOLDSCHMIDT, polyethoxylated glyceryl cocoate with 30 ethylene oxide groups such as the product VARIONIC LI 13® sold by SHEREX, polyethoxylated glyceryl isostearate with 30 ethylene oxide groups such as the product TAGAT L® sold by GOLDSCHMIDT and polyethoxylated glyceryl laurate with 30 ethylene oxide groups such as the product TAGAT I ® from GOLDSCHMIDT, - the esters of fatty acid (notably of a Cs-C2₄, and preferably C16-C22 acid) and oxyethylene and/or oxypropylene sorbitol ethers (which may include from 1 to 150 oxyethylene and/or oxypropylene groups), such as polysorbate 60 sold under the name of Tween 60 ® by UNIQUEMA,

- dimethicone copolyol, such as the one sold under the name of Q2- 5220® by DOW CORNING,

- dimethicone copolyol benzoate (FINSOLV SLB 101® and 201® from FINTEX),

- ethylene oxide/propylene oxide copolymers, also called EO/PO polycondensates,

- and mixtures thereof.

The EO/PO polycondensates are more particularly copolymers consisting in polyethylene glycol and polypropylene glycol blocks, such as for example three-block polyethylene glycol/polypropylene glycol/polyethylene glycol polycondensates.

These three-block polycondensates for example have the following chemical structure:

H-(O-CH2-CH2)a-(O-CH(CH3)-CH2)_b-(O-CH2-CH₂)a-OH,

a formula wherein a ranges from 2 to 120 and b ranges from 1 to 100.

The EO/PO polycondensate preferably has a weight average molecular weight ranging from 1 ,000 to 15,000, and better ranging from 2,000 to 13,000. Advantageously, said EO/PO polycondensate has a cloud point temperature, at 10 g/L in distilled water, greater than or equal to 20°C, preferably greater than or equal to 60°C. The cloud point temperature is measured according to the IS0 1065 standard. As an EO/PO polycondensate which may be used according to the invention, mention may be made of three-block polyethylene glycol/polypropylene glycol/polyethylene glycol polycondensates sold under the names of SYNPERONIC® like SYNPERONIC PE/L44® and SYNPERONIC PE/F127® by ICI. b) non-ionic surfactants with HLB of less than 8 at 25°C, optionally associated with one or several non-ionic surfactants with an HLB of more than 8 at 25°C, as mentioned above such that:

- esters and ethers of oses such as saccharose stearate, saccharose cocoate, sorbitan stearate and mixtures thereof, such as Arlatone 2121® marketed by ICI

- esters of fatty acids (notably of a Cs-C2₄, and preferably C16-C22 acid) and of a polyol, notably glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name of TEGIN M® by GOLDSCHMIDT, glyceryl laurate such as the product sold under the name of IMWITOR 312® by HULS, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate;

- the cyclomethicone/dimethicone copolyol mixture sold under the name of Q2-3225C® by DOW CORNING. c) The anionic surfactants such as

- salts of C16-C30 fatty acids, notably those deriving from amines, such as triethanolamine stearate and/or am ino-2-methyl-2-propane-diol-1 ,3 stearate; but preferably the composition according to the present application comprises less than 1 % of triethanolamine stearate; - salts of polyoxyethylene fatty acids notably those derived from amines or the alkaline salts, and their mixtures;

- phosphoric esters and their salts such as "DEA oleth-10 phosphate" (Crodafos N 10N from CRODA) or monopotassium monocetyl phosphate (Amphisol K from Givaudan); - isethionates;

- and mixtures thereof.

The composition according to the invention may also contain in addition to the ester of behenic acid and of glycerol, one or more amphoteric surfactants such as N-acyl-aminoacids such as N-alkyl-amino-acetates and disodium cocoamphodiacetate and amine oxides such as stearamine oxide or further silicone surfactants such as dimethicone copolyol phosphates like the one sold under the name of PECOSIL PS 100 ® by PHOENIX CHEMICAL. In the composition according to the invention, the total content of surfactants, including the ester of behenic acid and of glycerol according to the invention, may range from 1 to 13% by weight based on the total weight of the composition, preferably from 3 to 10% and better around 6% by weight. According to an embodiment, the cosmetic composition according to the present application comprises less than 1 % by weight, preferably less than 0.5% by weight of triethanolamine based on the total weight of the composition, and better is free of triethanolamine.

According to an alternative, the composition according to the present application comprises less than 1 % by weight, preferably less than 0.5% by weight of triethanolamine stearate, based on the total weight of the composition, and better is free of triethanolamine stearate.

The composition may further comprise a co-surfactant selected from fatty alcohols, preferably comprising from 10 to 30 carbon atoms. By a fatty alcohol comprising from 10 to 30 carbon atoms, is meant any branched or not, saturated or not, pure fatty alcohol, including 10 to 30 carbon atoms.

A fatty alcohol comprising from 10 to 26 carbon atoms, better from 10 to 24 carbon atoms and still better from 14 to 22 carbon atoms is preferably used.

As fatty alcohols which may be used in the composition according to the invention, mention may notably be made of lauric, myristic, cetyl, stearyl, oleyl, cetearyl alcohols (mixture of cetyl alcohol and stearyl alcohol), carboxylic, erucyl alcohols and mixtures thereof. Cetyl alcohol is preferably used.

Such fatty alcohols are notably marketed under the name of NAFOL by SASOL.

The fatty acid may be present in a content ranging from 0.2 to 20% by weight, preferably from 0.3 to 10% by weight based on the total weight of the composition.

Aqueous phase

The composition according to the invention comprises an aqueous phase, which forms the continuous phase of the composition.

By composition with an aqueous continuous phase, is meant that the composition has cond uctivity, m easu red at 25°C, of g reater th an or eq ual to 23 S/cm (microSiemens/cm), the conductivity being for example measured by means of a MPC227 conductivity meter from Mettler Toledo and of a conductivity measurement cell Inlab730. The measurement cell is immersed in the composition so as to remove the air bubbles which may form between both electrodes of the cell.

Read-out of the conductivity is accomplished as soon as the value of the conductivity meter is stabilized. An average is made over at least 3 successive measurements.

The aqueous phase comprises water and optionally at least one water-soluble solvent.

By « water-soluble solvent », is designated in the present invention a liquid compound at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25°C and at atmospheric pressure).

The water-soluble solvents which may be used in the compositions according to the invention may further be volatile.

Among the water-soluble solvents which may be used in the compositions according to the invention, mention may notably be made of lower monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol , 1 ,3-butylene glycol and dipropylene glycol, C3-C₄ ketones and C2-C₄ aldehydes.

The aqueous phase (water and optionally the solvent miscible with water) is generally present in the composition according to the present application in a content ranging from 1 % to 95% by weight, preferably ranging from 3% to 80% by weight, and preferentially ranging from 5% to 60% by weight, based on the total weight of the composition.

Wax(es)

The composition according to the present application may comprise at least one wax.

By wax, in the sense of the present application, is meant a lipophilic, solid compound at room temperature (25°C), with a reversible solid/liquid state transition, having a melting point greater than or equal to 30°C, which may range up to 120°C.

The melting point of the wax may be measured by means of a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name of DSC 30 by METTLER. The waxes may be hydrocarbon, fluorinated and/or silicone waxes and be of plant, mineral, animal and/or synthetic origin. In particular the waxes have a melting temperature of more than 25°C and better of more than 45°C. This high wax content notably gives the possibility of giving the composition a sufficiently thick texture in order to obtain a volumizing, loading coating on the eyelashes.

It is notably possible to use hydrocarbon waxes such as beeswax, and notably white beeswax, lanolin beeswax, and Chinese insect waxes, rice wax and notably rice bran wax, earnauba wax, eandelilla wax, ouricurry wax, alfa wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax, montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers as well as their esters, such as esters of fatty acid (notably Cs-C2₄ and preferably C16-C22 fatty acids) and of polyol (notably glycerol or sorbitol) such as the product Compritol 888® by Gattefosse. Thus, when it is used as a surfactant in the sense of the present application, the product Compritol 888® may also play the role of a wax in the composition according to the invention.

In particular, a premix of waxes may be used, comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax, such as for example the copolymer premix in waxes comprising 80% by weight of ethylene/vinyl acetate copolymer marketed as Cerylene B72^® by Baerlocher, in which the vinyl acetate percentage is 13% by weight, based on the total weight of the copolymer, the copolymer being pre-dispersed in a mixture of waxes comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax. It is also possible to mention waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched fatty C8-C32 chains.

Among the latter, mention may notably be made of hydrogenated jojoba oil, isomerized jojoba oil such as trans isomerized partly hydrogenated jojoba oil made or marketed by Desert Whale under the commercial reference ISO-JOJOBA-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di-(trimethylol-1 , 1 ,1 -propane) tetrastearate sold under the name of HEST 2T-4S" by HETERENE, di-(trimethylol-1 ,1 ,1 propane) tetrabehenate sold under the name of HEST 2T-4B by HETERENE. Mention may further be made of silicone waxes such as alkyl or alkoxy-dimethicone having from 16 to 45 carbon atoms, of fluorinated waxes.

It is also possible to use the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name of "PHYTOWAX Olive 18 L 57" or else further the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the name of "PHYTOWAX ricin 16L64 and 22L73", by SOPHIM. Such waxes are described in patent application FR-A-2792190.

According to a particular embodiment, the compositions according to the invention may comprise at least one wax, a so-called tacky wax, i.e. having tack greater than or equal to 0.7 N.s and hardness of less than or equal to 3.5 MPa. The use of a tacky wax may notably give the possibility of obtaining a cosmetic composition which is easily applied on eyelashes, having good adherence on the eyelashes and which leads to the formation of a smooth, homogeneous and thickening make-up.

The tacky wax used may notably have tack ranging from 0.7 N.s to 30 N.s, in particular greater than or equal to 1 N.s, notably ranging from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, notably ranging from 2 N.s to 10 N.s and in particular ranging from 2 N.s to 5 N.s.

The tack of the wax is determined by measuring the time-dependent change in the force (compression or stretching force) at 20°C by means of the texturometer sold under the name of "TA-TX2i®" by RHEO, equipped with an acrylic polymer mobile with the shape of a cone forming an angle of 45°.

The measurement procedure is the following:

The wax is melted at a temperature equal to the melting point of the wax + 10°C. The molten wax is cast into a container with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at room temperature (25°C) for 24 hours so that the surface of the wax is planar and smooth, the wax is then kept for at least one hour at 20°C before carrying out the measurement of tack.

The mobile of the texturometer is displaced at the velocity of 0.5 mm/s, and then penetrates the wax down to a penetration depth of 2 mm. When the mobile has penetrated the wax to a depth of 2 mm, the mobile is maintained fixed for 1 second (corresponding to the relaxation time) and is then withdrawn at the velocity of 0.5 mm/s. During the relaxation time, the force (compression force) strongly decreases until it becomes zero and then, during withdrawal of the mobile, the force (drawing force) becomes negative and then again increases to the value 0. Tack corresponds to the integral of the curve of the force versus time for the portion of the curve corresponding to the negative values of the force (drawing force). The value of tack is expressed in N.s.

The tacky wax which may be used, generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, notably ranging from 0.05 MPa to 3 MPa, or even further ranging from 0.1 MPa to 2.5 MPa.

Hardness is measured according to the procedure described earlier.

As a tacky wax, a C2o-C₄o alkyl (hydroxystearyloxy)stearate may be used, the alkyl group comprising from 20 to 40 carbon atoms, alone or as a mixture, in particular a C2o-C₄o alkyl 12-(12'-hydroxystearyloxy)stearate. Such a wax is notably sold under the names of "Kester Wax K 82 P®" and "Kester

Wax K 80 P®" by KOSTER KEUNEN. The waxes mentioned above generally have a onset melting point of less than 45°C.

It is also possible to use the microcrystalline wax marketed under reference SP18 by STRAHL and PITSCH which has a hardness of about 0.46 MPa and a tack value of about 1 N.s.

The wax(es) may be present as an aqueous wax microdispersion. By aqueous wax dispersion is meant an aqueous dispersion of wax particles, in which the size of said wax particles is less than or equal to about 1 pm.

The wax microdispersions are stable dispersions of colloidal wax particles, and are notably described in "Microemulsions Theory and Practice", L.M. Prince Ed. Academic Press (1977) pages 21 -32.

In particular, these wax microdispersions may be obtained by melting the wax in the presence of a surfactant, and optionally of a portion of water, and then by gradually adding hot water with stirring. The intermediate formation of an emulsion of the water-in-oil type is observed, followed by phase inversion with a micro-emulsion of the oil-in-water type being finally obtained. Upon cooling, a stable micro-dispersion of solid colloidal wax particles is obtained. The wax microdispersions may also be obtained by stirring a mixture of wax, of surfactant and of water by a stirring means such as ultrasonic waves, high pressure homogenizer, turbines.

The wax microdispersion particles preferably have average dimensions of less than 1 pm (notably ranging from 0.02 pm to 0.99 pm), preferably less than 0.5 pm (notably ranging from 0.06 pm to 0.5 pm).

These particles essentially consist of wax or of a mixture of waxes.

However they may comprise as a minority proportion, oily and/or pasty fatty additives, a surfactant and/or a customary oil-soluble active/additive. According to a preferred embodiment, the waxes which may be dispersed in the compositions according to the invention, may be selected from hydrocarbon waxes such as beeswax, and notably white beeswax, rice waxes and notably rice bran wax, carnauba wax, and a premix of waxes comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax such as for example the copolymer premix in waxes comprising 80% by weight of ethylene/vinyl acetate copolymer marketed as Cerylene B72^® by Baerlocher, in which the percentage of vinyl acetate is 13% by weight based on the total weight of the copolymer, the copolymer being pre-dispersed in a mixture of waxes comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax. The selection of these waxes not only gives the possibility of imparting to the composition, excellent stability over time of its texture, but also of providing a particularly loading and volumizing make-up result on the eyelashes.

The wax may be present in a content ranging from 0.1 % to 50% by weight, preferably from 1 % to 40% by weight, and more preferentially from 5% to 30% by weight based on the total weight of the composition.

According to a particular embodiment, the composition may comprise a wax content greater than or equal to 15% by weight, notably ranging from 15% to 50% by weight, preferably greater than or equal to 18% by weight, notably ranging from 18% to 40% by weight, and more preferentially greater than or equal to 20% by weight, notably from 20% to 30% by weight, based on the total weight of the composition. Film-forming polymer

The compositions according to the present application may also contain at least one hydrophilic or lipophilic film-forming polymer.

In the present application, by "film-forming polymer", is meant a polymer capable of forming by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous adherent film on the eyelashes, and preferably a cohesive film, and even better a film, for which the cohesion and the mechanical properties are such that said film may be isolated and handled individually, for example when said film is made by casting on an anti-adhesive surface such as a Teflon or silicone surface. Generally, the film-forming polymer content of the compositions according to the present application may range from 0.1 % to 40% by weight, preferably from 0.5% to 30% by weight, and more preferentially from 1 % to 20% by weight, based on the total weight of the composition.

The hydrophilic film-forming polymer may be a water-soluble polymer or appear as a dispersion in an aqueous medium. Among the film-forming polymers which may be used in the composition of the present invention, mention may be made of synthetic polymers, of the radical type or of the polycondensate type, of polymers of natural origin, and mixtures thereof.

As examples of water-soluble film-forming polymers, mention may be made of: - proteins such as proteins of vegetable origin such as wheat, soya bean proteins; proteins of animal origin such as keratins, for example keratin hydrolyzates and sulfonic keratins;

- cellulose polymers such as hydroxyethylcellulose, hydroxylpropylcellulose, methylcellulose, ethylhydroxyetheylcellulose, carboxymethylcellulose, and quarternized derivatives of cellulose;

- acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;

- vinyl polymers such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, the copolymer of vinyl acetate and crotonic acid, the copolymers of vinylpyrrolidone and vinyl acetate, the copolymers of vinylpyrrolidone and caprolactam, polyvinyl alcohol;

- anionic, cationic, amphoteric or non-ionic chitin or chitosan polymers; - arabic gums, guar gum, xanthan derivatives, karaya gum;

- alginates and carrageenans;

- glycoaminoglycans, hyaluronic acid and derivatives;

- shellac resin, sandarac gum, dammars, elemis, copals; - deoxyribonucleic acid;

- mucopolysaccharides such as chrondoitin sulfate, and mixtures thereof;

- natural polysaccharides such as those produced from starch by fermentation using natural yeast such as pullulan® marketed by Hayashibara International, or galactoarabinan marketed as Laracare A200® by Larex; - mixtures of oligosaccharides such as inulin sold under the reference Inutec

H25P® by Naturochim.

The film-forming polymer may also be present in the composition as particles dispersed in an aqueous phase, generally known as a latex or pseudo-latex. The techniques for preparing these dispersions are well-known to one skilled in the art. As an aqueous dispersion of film-forming polymer, it is possible to use:

- acrylic dispersions sold under the names of Neocryl XK-90 ® , Neocryl A-1070 ® Neocryl A-1 090 ®, Neocryl BT-62 ®, Neocryl A-1079 ® and Neocryl A-523 ® by VECIA-NEORESINS, Dow Latex 432 ® by DOW CHEMICAL, Daitosol 5000 AD ® or Daitosol 5000 SJ ® by DAITO KASEY KOGYO; Syntran 5760 ® by Interpolymer Allianz Opt ® by Rohm & Haas;

- aqueous dispersions of polyurethane sold under the names of Neorez R-981 ® and Neorez R-974 ® by AVECIA-NEORESINS, Avalure UR-405 ® , Avalure UR-410 ® , Avalure UR-425®, Avalure UR-450®, Sancure 875®, Avalure UR-445 ® and Sancure 2060 ® by NOVEON, Impranil 85 ®, BaycusanC1001®, BaycusanC1004® by BAYER, Aquamere H-151 1 ® by HYDROMER;

- sulfopolyesters sold under the trade name of Eastman AQ ® by Eastman Chemical Products;

- vinyl dispersions such as Mexomer PAM ®;

- aqueous dispersions of polyvinyl acetate like "Vinybran ®" from Nisshin Chemical or those marketed by UNION CARBIDE, aqueous dispersions of vinylpyrrolidone/ dimethylaminopropyl methacrylamide/lauryl dimethylpropyl methacrylamido-ammonium chloride terpolymer such as Styleze W- from ISP;

- aqueous dispersions of hybrid polyurethane/polyacrylic polymers such as those marketed under references "Hybridur ®" by AIR PRODUCTS or "Duromer ®" from NATIONAL STARCH;

- core/shell type dispersions; for example those marketed by ATOFINA under reference Kynar (core: fluorinated, shell: acrylic) or further those described in document US 5,188,899 (core: silica, shell: silicone) and mixtures thereof. The lipophilic polymer may be in solution or as a dispersion in a non-aqueous solvent phase or else dispersed in a mixture of waxes.

The lipophilic polymer may in particular be an ethylene/vinyl acetate copolymer.

It is generally present in a sufficient amount in the composition in order to avoid the formation of clumps upon applying the formulation on the eyelashes.

The amount of ethylene/vinyl acetate copolymer may thus be adjusted depending on the level of waxes present in the composition of the invention.

The weight ratio of the ethylene/vinyl acetate copolymer to the wax or to the mixture of waxes in the composition of the invention is preferably comprised between 1 :55 and 1 :99.

Preferably, the weight ratio of the ethylene/vinyl acetate copolymer to the wax or to the mixture of waxes in the composition of the invention is comprised between 1 :55 and 1 :15.

Even more preferentially, the weight ratio of the ethylene/vinyl acetate copolymer to the wax or to the mixture of waxes in the composition of the invention is comprised between 1 :50 and 1 :20. In a preferred embodiment of the invention, an ethylene/vinyl acetate copolymer dispersed beforehand in a mixture of waxes is used.

This has the advantage of reducing the melting point of the copolymer, which allows reduction in the heating temperature for preparing the composition of the invention. The waxes used for the pre-dispersion of the copolymer of the invention may be selected from those which are mentioned hereinbefore. Preferably, the waxes used for pre-dispersing the polymer are selected from synthetic wax, microcrystalline wax or their mixture.

In particular, it is possible to use a copolymer premix in waxes comprising 80% by weight of ethylene/vinyl acetate copolymer, in which the vinyl acetate percentage is 13% by weight based on the total weight of the copolymer, the copolymer being pre- dispersed in a mixture of waxes comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax marketed under the name of Cerylene B72^® by Baerlocher.

Gelling agents The compositions according to the present application may also contain at least one hydrophilic gelling agent, which may be selected from:

- homo- or co-polymers of acrylic or methacrylic acids or their salts and esters and in particular the products sold under the names of VERSICOL F ® or VERSICOL K ® by ALLIED COLLOID, ULTRAHOLD 8® by CIBA-GEIGY, polyacrylic acids of the SYNTHALEN K type,

- copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names of RETEN® by HERCULES, sodium salts of polyhydroxycarboxylic acids sold as HYDAGEN F ® by HENKEL,

- polyacrylic acid/alkyl acrylate copolymers of the PEMULEN type, - AMPS (polyacrylamidomethyl propane sulfonic acid partly neutralized with ammonia and highly cross-linked) marketed by CLARIANT,

- AMPS/acrylamide copolymers of the SEPIGEL® or SIMULGEL® type marketed by SEPPIC,

- AMPS/polyoxyethylene alkyl methacrylate (either cross-linked or not) and mixtures thereof and

- associative polyurethanes such as C16-EO 120-C1 6 polymer from SERVO DELDEN (marketed as SER AD FX1 100, a molecule with a urethane function and a weight average molecular weight of 1 ,300), EO being an oxyethylene unit, Rheolate 205 with a urea function sold by RHEOX or further Rheolate 208 or 204 (these polymers being sold in a pure form) or DW 1206B from ROHM & HAAS with a C₂o alkyl chain and a urethane bond, sold with 20% of active material in water. It is also possible to use solutions or dispersions of these associative polyurethanes notably in water or in a water-alcohol medium. As an example, of such polymers, mention may be made of SER AD fx1010, SER AD FX1035 and SER AD 1070 from SERVO DELDEN, Rheolate 255, Rheolate 278 and Rheolate 244 by RHEOX. It is also possible to use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from ROHM & HAAS, or else further Borchigel LW 44 from BORCH ERS, and mixtures thereof.

Certain water-soluble film-forming polymers mentioned above may also play the role of a water-soluble gelling agent. Hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 40% by weight, preferably from 0.1 % to 20% by weight, and more preferentially from 0.5% to 15% by weight, based on the total weight of the composition.

Oils

The compositions according to the present application may also contain at least one or several oils or an organic solvent.

By oil or organic solvent, is meant a non-aqueous body which is liquid at room temperature and at atmospheric pressure. The oil may be volatile or non-volatile.

By "volatile organic solvent or oil", is meant in the sense of the invention any non-aqueous medium which may evaporate in contact with keratinous materials in less than hour, at room temperature and at atmospheric pressure. The volatile organic solvent(s) and the volatile oils of the invention are organic solvents and volatile cosmetic oils, which are liquid at room temperature, having a non-zero vapor pressure, at room temperature and at atmospheric pressure, ranging from 0.13 Pa to 40,000 Pa (0.001 to 300 mm of Hg), in particular ranging from 1 .3 Pa to 13,000 Pa (0.01 to 100 mm of Hg) and more particularly ranging from 1 .3 Pa to 13,000 Pa (0.01 to 10 mm of Hg).

By "non-volatile oil", is meant an oil remaining on the keratinous materials at room temperature and at atmospheric pressure for at least several hours and notably having a vapor pressure of less than 10^"3 mm of Hg (0.13Pa).

The composition according to the invention may comprise volatile oils and/or non-volatile oils, and mixtures thereof. The volatile oils (or organic solvents) may be hydrocarbon oils, silicone oils, fluorinated oils or mixtures thereof.

By "hydrocarbon oil", is meant an oil mainly containing hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur, phosphorus atoms. Volatile hydrocarbon oils may be selected from hydrocarbon oils having from 8 to 16 carbon atoms, and notably branched Cs-Ci6 alkanes such as Cs-Ci6 isoalkanes derived from petroleum (also called isoparaffins) such as isododecane (further called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example oils sold under the trade names of « isopars® » or « Permetyls® », branched Cs-Ci6 esters, isohexyl neopentanoate and mixtures thereof.

Other volatile hydrocarbon oils such as petroleum distillates, notably those sold under the name of "Shell Solt ®" by SHELL may also be used.

As volatile oils, it is also possible to use volatile silicones, such as for example volatile linear or cyclic silicone oils, notably those having a viscosity of 6 centistokes (6.10^"6 m²/s), and notably having from 3 to 6 silicon atoms, these silicones optionally including one or several alkyl or alkoxy groups having 1 or 2 carbon atoms. As a volatile silicone oil which may be used in the invention, mention may notably be made of octometh yl cycl otetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

It is also possible to use volatile organic solvents notably fluorinated solvents such as nonafluoromethoxy butane or perfluoromethyl cyclopentane.

Each of the compositions according to the invention may also comprise at least one non-volatile organic oil or solvent, which may in particular be selected from non-volatile hydrocarbon and/or silicone and/or fluorinated oils.

As a non-volatile hydrocarbon oil, mention may notably be made of:

- hydrocarbon oils of vegetable origin such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have various lengths of chains from C₄ to C2₄, the latter may be linear or branched, saturated or unsaturated; these oils are notably wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, sheah, avocado, olive, soya bean oils, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, gourd, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passiflora, rosehip oils; or further triglycerides of caprylic/capric acids like those sold by Stearineries Dubois or those sold under the names of Miglyol 810 ® , 812 ® and 818 ® by Dynamit Nobel,

- synthetic ethers having from 10 to 40 carbon atoms;

- linear or branched hydrocarbons of mineral or synthetic origin such as vaseline, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof; - synthetic esters like the oils of formula R1 -COOR2 wherein R1 represents the remainder of a linear or branched fatty acid including 1 to 40 carbon atoms and R2 represents a notably branched hydrocarbon chain containing from 1 to 40 carbon atoms, provided that R1 + R2 has 10 carbon atoms, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propyleneglycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and esters of pentaerythritol;

- branched and/or unsaturated carbon chain fatty alcohols, liquid at room temperature, having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecyl-pentadecanol;

- higher fatty acids such as oleic acid, linoleic acid, linolenic acid; and mixtures thereof.

Non-volatile silicone oils which may be used in either one of the compositions (i) or (ii) according to the invention may be non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes including alkyl or alkoxy groups, either pendant and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicat.es; The fluorinated oils which may be used in the compositions according to the invention are notably fluorosilicone oils, fluorinated polyethers, fluorinated silicones as described in document EP-A-847752.

The non-volatile organic solvent or oil content in the composition according to the invention ranges from 0.01 to 30% by weight, in particular from 0.1 to 25% by weight, and better from 0.1 to 20% by weight based on the total weight of the composition.

Coloring material

The compositions according to the invention may also comprise at least one coloring material such as powdery materials, oil-soluble coloring agents, water-soluble coloring agents.

Powdery coloring materials may be selected from pigments and pearlescent agents.

The pigments may be white or colored, mineral and/or organic, either coated or not. Among mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among organic pigments, mention may be made of carbon black, pigments of the D & C type, and of lacquers based on cochineal carmine, barium, strontium, calcium, aluminium.

The pearlescent agents may be selected from white pearly pigments such as mica covered with titanium or bismuth oxychloride, colored pearly pigments such as titanium mica with iron oxides, titanium mica with notably ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearly pigments based on bismuth oxychloride.

Oil-soluble coloring agents are for example Sudan Red, D&C Red 17, D&C Green 6, 13-carotene, soya bean oil, Sudan brown, D&C Yellow 1 1 , D&C Violet 2, D&C Orange 5, quinoline yellow, achiote.

These coloring materials may be present in a content ranging from 0.01 to 30% by weight based on the total weight of the composition.

Fillers The compositions according to the invention may also comprise one filler. Fillers may be selected from those well-known to one skilled in the art and commonly used in cosmetic compositions. The fillers may be mineral or organic, lamellar or spherical. Mention may be made of talcum, mica, silica, kaolin, powders of polyamide such as Nylon® marketed under the name of Orgasol® by Atochem, of poly-13-alanine and polyethylene, powders of tetrafluoroethylene polymers such as Teflon®, lauroyl-lysine, starch, boron nitride, expansed hollow polymeric microspheres such as those of polyvinylidene chloride/acrylonitrile like those marketed under the name of Expancel® by Nobel Industrie, acrylic powders such as those marketed under the name of Polytrap® by Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (Tospearls® from Toshiba for example), precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from carboxylic organic acids having from 8 to 22 carbon atoms and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

It is also possible to use a compound which may swell with heat and notably thermoexpandable particles such as non-expansed microspheres of vinylidene chloride/acrylonitrile/methylmethacryalte copolymer or acrylonitrile homopolymer copolymer such as for example those respectively marketed under the references of Expancel® 820 DU 40 and Expancel® 007WU by AKZO NOBEL. Mention may also be made of Advancell® marketed by Sekuisi Plastic or Thermoexpandable Microspheres® from Matsumoto.

The fillers may represent from 0.1 % to 25% by weight, in particular from 0.2% to 20% by weight, based on the total weight of the composition. Fibers

The compositions according to the invention may also comprise at least one fiber which allows an improvement in the lengthening effect.

By "fiber", an object of length L and of diameter D should be understood such that L is much larger than D, D being the diameter of the circle in which the section of the fiber is included. In particular, the L/D ratio (or form factor) is selected from the range from 3.5 to 2,500, in particular from 5 to 500, and more particularly from 5 to 150. The fibers which may be used in the composition of the invention may be fibers of mineral or organic, synthetic or natural origin. They may be short or long, unitary or organized, for example braided, hollow or solid. Their section may be any section and notably a circular or polygonal (square, hexagonal or octagonal) section depending on the contemplated specific application. Their shape may be linear, curved, sinusoidal or crinkled. In particular, their ends are blunted and/or polished to avoid any injury.

In particular, the fibers have a length ranging from 1 m to 10 mm, in particular from 0.1 mm to 5 mm and more particularly from 0.3 mm to 3.5 mm. Their section may be comprised in a circle with a diameter ranging from 2 nm to 500 μιτι, in particular ranging from 100 nm to 100 μιτι and more particularly from 1 μιτι to 50 μιτι. The weight or the titer of the fibers is often given in denier or decitex and represents the weight in grams for 9 kilometers of yarn. The fiber according to the invention may in particular have a titer selected from the range from 0.15 to 30 deniers and notably from 0.18 to 18 deniers. The fibers which may be used in the composition of the invention may be selected from rigid or non-rigid fibers, they may be of mineral or organic, synthetic or natural origins.

Moreover, the fibers may either be treated at the surface or not, either coated or not, either colored or not. As fibers which may be used in the composition according to the invention, mention may be made of non-rigid fibers such as polyamide fibers (Nylon()) or rigid fibers such as polyimide-amide fibers like those sold under the names of KERMEL®, KERMEL TECH® by RHODIA or poly-(phenylene-terephthalamide fibers) (or aramide fibers) notably sold under the name of Kevlar® by DUPONT DE NEMOURS. The fibers may be present in the composition according to the invention in a content ranging from 0.01 % to 10% by weight, in particular from 0.1 % to 5% by weight, and more particularly from 0.3% to 3% by weight, based on the total weight of the composition.

Actives The compositions according to the invention may also comprise at least one cosmetic active. As cosmetic actives which may be used in the compositions according to the invention, mention may notably be made of antioxidants, preservatives, perfumes, neutralizing agents, emollients, coalescence agents, plasticizers, moisturizers, vitamins and in particular solar screens, and mixtures thereof.

Of course, one skilled in the art will ensure that the optional additional additives and/or their amounts be selected so that the advantageous properties of the composition according to the invention are not or substantially not altered by the contemplated addition. Preferably the composition according to the invention is a non-rinsed composition.

The composition according to the invention may be packaded in a container delimiting at least one compartment which comprises said composition, said container being closed by a closure member.

The container is preferably associated with an applicator, notably as a brush including an arrangement of bristles held by a twisted wire. Such a twisted brush is notably described in US patent 4,887,622. It may also be in the form of a comb including a plurality of application members, notably obtained from molding. Such combs are for example described in patent FR 2 796 529. The applicator may be secured to the container, as described for example in patent FR 2 761 959. Advantageously, the applicator is secured to a rod which itself is secured to the closing member.

The closure member may be coupled with the container by screwing. Alternatively, the coupling between the closure member and the container is accomplished in another way than by screwing, notably via a bayonet mechanism, by snap-on fastening, or by clamping. By "snap-on fastening" is meant in particular any system involving the crossing of a bulge or of a bead of material by elastic deformation of a portion, notably of the closure member, and then its return to an elastically non-stressed position of said portion after crossing of the bulge or of the bead.

The container may at least partly be made in thermoplastic material. As examples of thermoplastic materials, mention may be made of polypropylene or polyethylene.

Alternatively, the container is made in a non-thermoplastic material, notably in glass or in metal (or alloy). The container is preferably equipped with the wiper positioned in the vicinity of the aperture of the container. With such a wiper, it is possible to wipe the applicator and optionally the rod to which it may be secured. Such a wiper is for example described in patent FR 2 792 618. The compositions according to the invention have a particularly stable viscosity over time and produce a loading make-up, notably of the eyelashes. By changing the amount of waxes, gelling agents, film-forming polymers and fillers, it is possible to additionally obtain lengthening, curving and volumizing eyelash properties.

The following examples are given as an illustration of the present invention and cannot limit the scope thereof.

Examples

The following compositions were made. The indicated amounts are expressed as a weight percentage, based on the total weight of the composition.

Example A 3 mascara formulations according to the invention were prepared comprising an ester of behen ic acid and of g lycerol contained in the product Emulium®22 of Gattefosse, and having the following compositions:

Composition Composition Composition

Phase Chemical name 1 2 3

(%) (%) (%)

1 Paraffin wax (WAX JH 140) 12.00 12.00 12.00

Emulium 22 marketed by Gattefosse

comprising the ester of behenic acid and of 6.00 3.00 9.00 glycerol according to the invention

Beeswax - white beeswax 3.50 3.50 3.50

Carnauba wax 2.25 2.25 2.25

Rice bran wax - Rice Wax No.1 1.00 1.00 1.00 Pre-mix comprising 80% by weight of

ethylene/vinyl acetate copolymer in which the

percentage of vinyl acetate is 13% by weight

based on the total weight of the copolymer, the

copolymer being pre-dispersed in a mixture of 0.75 0.75 0.75 waxes comprising 15% by weight of

monocrystalline wax and 5% by weight of

synthetic wax marketed under the name of

Cerylene B72® by Baerlocher

Anti-foam emulsion comprising 10% of

dimethicone sold under reference Dow 0.25 0.25 0.25 Corning 1510

2 Black iron oxides 8.00 8.00 8.00

Water 29.92 32.60 26.6

Hydroxyethylcellulose gel comprising:

3.35% Cellulosize HEC QP-440H

25.00 25.00 25.00 96.15% water, and

0.5% de phenoxyethanol

Arabic gum gel comprising:

50.3% of quick gum type 8287

49.3% of water

3

6.00 6.00 6.00

0.25% de methyl paraben

0.15% anti-foam emulsion comprising 10% of

dimethicone, sold under reference Dow

Corning 1510

Polyquaternium-10 gel sold under the

reference Ucare Polymer JR-400 at 5% in 2 2 2 water

Preservatives qsp qsp qsp

25% sodium hydroxide solution 0.08 0.40 0.40

Total 100.00 100.00 100.00

The ingredients of phase 1 were heated to 90°C in a water bath, under stirring with the Moritz for about 30 mins until the waxes were properly melted. The pigment (phase 2) was milled in phase 1 in the Mo tz for 30 mins at 2,500rpm, always in the water bath at 90°C.

The gel of polymer Ucare JR-400 was prepared; by heating water to 50°C and dispersing therein 5% by weight of the polymer Ucare JR-400. Mixing and homogenizing was carried out with a Rayneri deflocculator.

The aqueous phase was heated to 90°C (phase 3) in the water bath while stirring with the Rayner deflocculator (100rpm) so as to generate a slight vortex.

The fatty phase (phases 1 + 2) was added to the homogenized aqueous phase (phase 3) and emulsifying was carried out for 20 minutes under strong stirring with the Rayneri deflocculator (270 rpm).

The mixture was withdrawn from the water bath and left to cool at room temperature always under stirring with the deflocculator (V: 200rpm) down to a temperature of about 45°C and by "detaching" the emulsion which gradually sets on the walls of the beaker during the cooling. Around 50°C, the product takes up viscosity. In order to homogenize the product, the stirring rate is then adjusted to 450 rpm. The cooling time required for attaining 45°C is of about 1 h.

Once the temperature of 45°C is reached, cooling was continued with a basin of cold water by proceeding in the same way but while reducing the stirring rate (V: 400 rpm). Once the temperature of 35°C is reached, stirring and cooling was stopped.

The product was placed in vacuo in order to remove the air bubbles for 5 to 10 minutes.

The product was stored in twist-off pots for stability measurements of the formulation at 5°C, 40°C and 45°C. The viscosities of the compositions 1 to 3 were then measured at T=7 days, at

T=1 month and at T=2 months for samples stored at 20°C.

These measurements were conducted at 20°C. The apparatus used is a Brookfield DV-ll+Pro. A mobile D is used, the measurement is conducted in a 210ml_ twist-off pot, with a diameter of about 6 cm, filled up to the neck. The value is read after 1 minute. The results are shown in Table 1 hereafter: Composition 1 Composition 2 Composition 3

D7 1 month 2months D7 D1 month D2months D7 D1 month D2months

Viscosity in 77.10³ 74.10³ 75.2.10³ 37.4.10³ 37.4.10³ 39.4.10³ 98.9.10³ 102.4.10³ 107.10³ cPs

Comments

Stable viscosity Stable viscosity Stable viscosity on the

viscosity

stability

Stability of

Nothing to report, stable Nothing to report, stable Nothing to report, stable the

formulation

(at 5°C,

20°C, 40°C,

45°C) for 2

month

Table 1: viscosity measurements of the compositions 1 to 3 according to the invention.

The mascara compositions 1 , 2 and 3 according to the invention have stable consistency over time, notably after two months of storage and good dispersion of the waxes and pigments which ensures an intense and uniform black shade, which is sought for this type of product. These mascaras are easily applied on eyelashes and form a loading, smooth and homogeneous coating.

A stable emulsion is obtained at different contents of the ester of behenic acid and glycerol according to the invention (between 3% and 9%), with optimal results at 6% of ester of behenic acid and glycerol.

Example B

A mascara composition 4 according to the invention was prepared, corresponding to composition 1 in which the ester of behenic acid and glycerol is introduced as a mixture of glyceryl mono-, d i and tri-behenate in the product Compritol 888® from Gattefosse. The composition 4 comprises 6% of Compritol 888® from Gattefosse.

A mascara was prepared according to the preparation method described in Example A.

The viscosities of the composition 4 were then measured with a Malvern (CVO or Gemini) rheometer equipped with a mobile: plane-striated plane (PP40S), air gap 1 ,ΟΟΌμηη. The value indicated here is G' at 0.1 Hz.

The results are shown in Table 2 hereafter: Composition 4

D7 1 month 2months

Rheology in Pa G'=49Pa G'=48.31 Pa G' = 49.81

Comments on the stability of Stable rheology

the rheology

Stability (at 5°C, 20°C, 40°C, Nothing to report, stable

45°C) for 2 months

Table 2: Viscosity measurements of the composition of 4 of the invention

The composition 4 according to the invention has a very stable viscosity over time, since the values of G' measured at D7, 1 month and 2 months have not changed. This composition also has good dispersion of the waxes and pigments which ensures an intense and uniform black shade, which is sought for this type of product. The mascara is easily applied on eyelashes and forms a loading, smooth and homogeneous coating.

Comparative Example C

A mascara formulation was prepared, not according to the invention (comparative composition 1 ) corresponding to composition 1 in which the ester of behenic acid and glycerol was replaced with another non-ionic surfactant: Glycereth-26 which is an ester of polyethylene glycol and of glycerol.

The mascara of comparative composition 1 was prepared according to the preparation method described in Example A.

The viscosities were then measured according to the method used in Example A. The results are shown in Table 3 hereafter:

Composition 1 according to the Comparative composition 1

invention

D7 1 month 2 months D7 D1 month D2months

Viscosity in cPs

77.10³ 74.10³ 75.2.10³ / / /

Comments on Stable viscosity Not measured because of phase the stability of separation in the product viscosity

Stability (at 5°C, Nothing to report, stable Phase separation from D+1 20°C, 40°C,

45°C) for two

months Table 3: comparison of the viscosities of composition 1 according to the invention and of the comparative composition 1.

With 6% Glycereth-26, it is not possible to obtain a stable mascara emulsion. Comparative Example D

2 other mascara formulations outside the invention were prepared corresponding to the composition 1 in which:

- Comparative composition 2: the ester of behenic acid and of glycerol according to the invention was replaced with 3% of a non-ionic emulsifier comprising a behenic chain and a PEG chain, Eumulgin BA 25® (INCI: BEHENETH-25) from Cognis, the balance being made with water;

- Comparative composition 3: the ester of behenic acid and of glycerol according to the invention was replaced with 6% of non-ionic emulsifier comprising a behenic chain and a PEG chain, Eumulgin BA 25® (INCI: BEHENETH-25) from Cognis.

The mascaras of comparative compositions 2 and 3 were prepared according to the preparation method described in Example A.

The viscosities of the composition were then measured according to the method used in Example A.

The results are shown in Table 4 hereafter:

Composition 1 Comparative composition Comparative composition

2 3

D7 1 month 2months D7 D1 month D2months D7 D1 month D2months

Viscosity in 77.10³ 74.10³ 75.2.10³ / / / / / / cPs

Comments Stable viscosity Not measured, because Not measured because on the

phase-separated product phase-separated product stability of

the

rheology

and

viscosity

Stability (at Nothing to report, stable Phase separation from D+1 Phase separation from D+1 5°C, 20°C,

40°C,

45°C) for 2

months Table 4: comparison of the viscosities of composition 1 according to the invention and of comparative compositions 2 and 3.

The emulsion with Eumulgin BA25® is not stable at the different tested percentages, while Emulium 22® comprising the ester of behenic acid and of glycerol according to the invention, gives the possibility of obtaining a stable emulsion when it is introduced at a content comprised between 3 and 9% by weight.

Comparative Example E

A mascara formulation outside the invention was prepared (comparative composition 4) corresponding to composition 1 in which the ester of behenic acid and glycerol according to the invention was replaced by another non-ionic emulsifier: glyceryl stearate sold under the commercial reference TEGIN M by EVONIK (formerly GOLDSCHMIDT).

The mascara of the comparative composition 4 was prepared according to the preparation method described in Example A.

The mascara prepared with the comparative composition 4 is very hard and friable. It is not possible to apply it on eyelashes or to measure its rheology.

Comparative Example F

A mascara formulation outside of the invention was prepared (comparative composition 5) corresponding to composition 1 in which the ester of behenic acid and of glycerol according to the invention was replaced by another non-ionic emulsifier: polyethoxylated glyceryl stearate with 30 ethylene oxide groups sold under the commercial reference TAGAT S by EVONIK (formerly GOLDSCHMIDT).

The mascara of the comparative composition 5 was prepared according to the preparation method described in Example A. The prepared emulsion with the comparative composition 5 is unstable and completely phase-separated. It is not possible to apply it on eyelashes or to measure its rheology.

Comparative Example G

A mascara formulation outside the invention was prepared (comparative composition 6) corresponding to composition 1 in which the 6% of the ester of behenic acid and glycerol according to the invention was replaced by 7.5% of another emulsifier: a triethanolamine stearate sold under the commercial stearic acid reference TP Ref 1200 by Stearinerie Dubois. The balance was completed with water and with preservatives.

The ingredients of phase 1 were heated to 95°C in the water bath, stirred with the Moritz for about 30 mins until the waxes were properly melted.

The pigment (phase 2) was milled in phase 1 with the Moritz for 30 mins at 2,200 rpm, always in the water bath at 95°C.

The aqueous phase was heated to 85°C (phase 3) with the Stephan while stirring (300 rpm) with the bottom scraper and (300 rpm) with the emulsifying device, the vacuum being 30-40 bars. Once 85°C were attained, stirring was continued for 2mins.

The fatty phase (phases 1 + 2) was added to the aqueous phase (phase 3) in the Stephan and was emulsified for 20 mins at 85°C with intense stirring (300 rpm) with the bottom scraper and (300 rpm) with the emulsifying device, the vacuum being a maximum (around 40 bars). The vacuum was monitored for 20 mins, it should remain at 40 bars at least.

The jacket of the Stephan was slowly cooled by means of a stream of water down to about 31 °C at about a rate of 1 °C per minute (cooling is accomplished in about 50 mins).

During the cooling, the vacuum was monitored, and it was increased from time to time up to a maximum possible vacuum for the machine (between 60 and 90 bars).

Once the temperature of 31 °C was reached, the vacuum application was stopped as well as the cooling system.

The product was stored in twist-off pots and small mascara flasks were filled therewith. The viscosities of the composition were then measured according to the method used in Example B. The results are shown in Table 5 hereafter:

Table 5: comparison of the viscosities of the composition 1 according to the invention and of the comparative composition 6

The comparative composition 6 containing triethanolamine stearate has a viscosity which changes over time unlike the compositions according to the invention for which viscosity is stable over time.

Thus, the compositions according to the invention give the possibility of improving the stability of the viscosity of mascaras, as compared with the compositions of the prior art comprising another surfactant, notably triethanolamine stearate. The eyelashes made up by the compositions according to the invention are clad over their whole length and the coating is particularly loading.

Claims

1 . A cosmetic composition for coating keratinous fibers, in particular eyelashes, in the form of a wax-in-water emulsion characterized in that it comprises at least one ester of behenic acid and of glycerol, said ester of behenic ester and of glycerol forming the main surfactant system of the composition.

2. The composition according to the preceding claim, characterized in that the ester of behenic acid and of glycerol represents from 90% to 100% by weight, preferably from 95% to 99.5% by weight, more preferentially from 98% to 99% by weight of the surfactant system.

3. The composition according to the preceding claim, characterized in that the ester of behenic acid and of glycerol forms the single surfactant system of the composition.

4. The cosmetic composition according to one of the preceding claims, characterized in that it comprises less than 1 % by weight, preferably less than 0.5% by weight of triethanolamine, based on the total weight of the composition, and better, is free of triethanolamine.

5. The cosmetic composition according to one of the preceding claims, characterized in that it comprises less than 1 % by weight, preferably less than 0.5% by weight of triethanolamine stearate, based on the total weight of the composition, and better, is free of triethanolamine stearate.

6. The composition according to one of the preceding claims, characterized in that the ester of behenic acid and of glycerol is selected from glyceryl mono-behenate, glyceryl di-behenate, glyceryl tri-behenate, and mixtures thereof.

7. The composition according to one of the preceding claims, characterized in that the ester of behenic acid and of glycerol is present in a content ranging from 1 % to 12% by weight, preferably from 3 to 9% by weight and better around 6% by weight based on the total weight of the composition.

8. The cosmetic composition according to one of the preceding claims, characterized in that it comprises an aqueous phase comprising water and optionally at least one water-soluble solvent.

9. The cosmetic composition according to the preceding claim, characterized in that the aqueous phase is present in a content ranging from 1 % to 95% by weight, preferably ranging from 3% to 80% by weight, and preferentially ranging from 5% to 60% by weight, based on the total weight of the composition.

10. The cosmetic composition according to one of the preceding claims, characterized in that it comprises at least one wax, notably selected from hydrocarbon waxes such as beeswax, and notably white beeswax, rice waxes and notably rice bran wax, carnauba wax, and a premix of waxes comprising 15% by weight of microcrystalline wax and 5% by weight of synthetic wax.

1 1 . The composition according to one of the preceding claims, characterized in that the wax is present in a content ranging from 0.1 % to 50% by weight, preferably from 1 % to 40% by weight and preferentially ranging from 5% to 30% by weight based on the total weight of the composition.

12. The cosmetic composition according to one of the preceding claims characterized in that it comprises at least one hydrophilic or lipophilic film-forming polymer and/or at least one hydrophilic gelling agent.

13. The cosmetic composition according to one of the preceding claims, characterized in that it further comprises at least one compound selected from oils, coloring materials, fillers, fibers, cosmetic actives such as antioxidants, preservatives, perfumes, neutralizing agents, emollients, coalescence agents, plasticizers, moisturizers, vitamins and screens, in particular solar screens, and mixtures thereof.

14. A non-therapeutic make-up and/or care method for keratinous fibers, notably eyelashes, comprising the application on said keratinous fibers of a composition according to one of the preceding claims.

15. The use of a composition according to one of claims 1 to 14 in order to obtain a homogeneous and/or loading make-up on keratinous fibers, in particular eyelashes.

16. The use of at least one ester of behenic acid and of glycerol for stabilizing the viscosity of a wax-in-water emulsion.