Cosmetic composition in inverse emulsion comprising an oil, a surfactant, a film-forming polymer and a hydroxy acid

Abstract

Cosmetic composition in reverse emulsion comprising an oil, a surfactant, a film-forming polymer, and a hydroxy acid. The present invention relates to a cosmetic composition in the form of a water-in-oil (W / O) emulsion, comprising: a) a continuous oil phase comprising at least one hydrocarbon oil with a refractive index n greater than or equal to 1.4, b) an aqueous phase dispersed in the continuous oil phase, c) at least one emulsifying surfactant with an HLB less than or equal to 8, d) at least one lipophilic film-forming polymer, e) at least one hydroxy acid, and f) at least one colorant. Figure for abstract: None

Description

Title of the invention: Cosmetic composition in inverse emulsion comprising an oil, a surfactant, a film-forming polymer and a hydroxy acid

[0001] The present invention relates to a cosmetic composition in the form of a water-in-oil (W / O) emulsion, comprising a continuous oily phase including at least one hydrocarbon oil with a refractive index greater than or equal to 1.4, an aqueous phase dispersed in the continuous oily phase, at least one emulsifying surfactant with an HLB less than or equal to 8, at least one lipophilic film-forming polymer, at least one hydroxy acid, and at least one coloring material.

[0002] In the field of makeup products, the range of compositions is very broad. It extends from very fluid liquid compositions to compositions in the form of molded solids, not forgetting pressed or loose powders. Furthermore, these compositions may be anhydrous or include an aqueous phase and be found, for example, in emulsified form.

[0003] Despite this great diversity of galenics, each area of ​​makeup has developed characteristics that are more particular to it, due to the constraints to which the compositions are subjected once applied and the performance expected for the compositions.

[0004] Thus, in the field of complexion makeup, formulas can be in the form of liquid emulsions, either direct (oil-in-water) or inverse (water-in-oil). These compositions have made it easier to deliver active ingredients, particularly for enhanced skincare and hydration performance.

[0005] However, there is still a need for complexion makeup compositions, which are presented in the form of an inverse emulsion, and which provide a luminous, or even very luminous, effect to the complexion, while maintaining good hold.

[0006] The present invention aims to provide a solution to the problems mentioned above.

[0007] The Applicant has indeed developed water-in-oil (W / O) emulsions comprising at least one hydrocarbon oil with a refractive index greater than or equal to 1.4, at least one emulsifying surfactant with an HLB less than or equal to 8, at least one lipophilic film-forming polymer, at least one hydroxy acid, and at least one colorant. Such emulsions make it possible to obtain foundations whose luminous effect can be maximized, while maintaining good wear.

[0008] Accordingly, the present invention relates, according to a first aspect, to a cosmetic composition in the form of a water-in-oil (W / O) emulsion, comprising:

[0009] a) a continuous fatty phase comprising at least one hydrocarbon oil with a refractive index n greater than or equal to 1.4,

[0010] b) an aqueous phase dispersed in the continuous oily phase,

[0011] c) at least one emulsifying surfactant with an HLB of less than or equal to 8,

[0012] d) at least one lipophilic film-forming polymer,

[0013] e) at least one hydroxy acid, and

[0014] f) at least one coloring matter.

[0015] Preferably, the composition according to the invention is substantially free of silicone oil. By "substantially free of silicone oil," we mean a composition comprising less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.3% by weight relative to the total weight of the composition, of silicone oil. Preferably, the composition according to the invention is completely free of silicone oil.

[0016] Despite the very low content, or even the total absence of silicone oil, the compositions according to the invention exhibit very good performance.

[0017] Although the composition is more particularly intended for complexion makeup, it is not excluded to apply the composition according to the invention to the skin, for example on the lips or cheekbones, as one would do with a blush.

[0018] Moreover, the composition according to the invention is typically a makeup composition of keratinous materials, in particular of the complexion (therefore of the skin of the face); it can also have a skincare valence.

[0019] The present invention also relates to a method of makeup or care for keratinous materials, and in particular for the complexion, in which a composition according to the invention is applied to the keratinous materials, and in particular to the skin of the face. CONTINUOUS FAT PHASE

[0020] The continuous fatty phase of the composition according to the invention comprises at least one hydrocarbon oil with a refractive index greater than or equal to 1.4 (compound a).

[0021] Hydrocarbon oil with a refractive index n greater than or equal to 1.4

[0022] The continuous oily phase of the composition according to the invention comprises at least one hydrocarbon oil with a refractive index n greater than or equal to 1.40, preferably greater than or equal to 1.45. Preferably, this hydrocarbon oil is non-volatile.

[0023] By "oil" is meant a non-aqueous compound, liquid at 25°C and atmospheric pressure (1.013.105 Pa), immiscible with water.

[0024] By "immiscible" is meant that the mixture of the same quantity of water and oil, after stirring, does not lead to a stable solution comprising only one phase, under the aforementioned temperature and pressure conditions. The observation is made at by eye or by means of a phase contrast microscope if necessary, on 100g of mixture obtained after sufficient Rayneri shaking to cause a vortex to appear within the mixture (for guidance 200 to 1000 rpm); the resulting mixture being left to stand, in a closed bottle, for 24 hours at room temperature before observation.

[0025] By "non-volatile oil" is meant an oil whose vapor pressure at 25°C and atmospheric pressure is non-zero and less than 2.66 Pa, more particularly less than or equal to 0.13 Pa. By way of example, the vapor pressure can be measured according to the static method or by the isothermal thermogravimetric effusion method, according to the vapor pressure (OECD standard 104).

[0026] The term “hydrocarbon oil” means an oil formed essentially, or even composed, of carbon and hydrogen atoms, and possibly of oxygen and nitrogen atoms, and not containing silicon or fluorine atoms. Hydrocarbon oil is therefore distinct from silicone oil and fluorinated oil.

[0027] It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

[0028] Preferably, the hydrocarbon oil is free from heteroatoms such as nitrogen, sulfur and phosphorus.

[0029] In particular, this hydrocarbon oil comprises at least one alcohol function (it is then an "alcohol oil") or at least one ester function (it is then an "ester oil").

[0030] The ester oils that can be used in the compositions according to the invention can in particular be hydroxylated.

[0031] Preferably, the oily phase of the composition according to the invention comprises at least one non-volatile hydrocarbon oil having a refractive index n greater than or equal to 1.45. The refractive index is measured at ambient temperature (20°C) and atmospheric pressure.

[0032] Said hydrocarbon oil is in particular chosen from non-volatile hydrocarbon oils having a refractive index n greater than or equal to 1.45 and their mixtures.

[0033] Examples of hydrocarbon oils with a refractive index n greater than or equal to 1.4, preferably greater than or equal to 1.45, include:

[0034] - linear or branched hydrocarbons, of mineral or synthetic origin, in in particular polybutenes such as the commercial products INDOPOL H 100 (n= 1,49), INDOPOL H 1500® (n = 1,5) from INEOS, hydrogenated polyisobutenes such as the commercial products PARLEAM HV® (n = 1,456), PARLEAM SV® (n= 1,458) from NOF CORPORATION;

[0035] - synthetic fatty acid esters such as isostearyl lactate, palmitate isostearyl, octyldodecyl neodecanoate, isocetyl stearate, the propylene glycol monoisostearate, ethyl-2-hexyl isostearate, octyldodecyl stearate, octyldodecyl myristate, diisostearyl adipate, octyl hydroxystearate, glyceryl triisostearate, octyldodecyl stearoylstearate, diisocetyl dodecane dioate, dipentaerythrityl hexacaprylate / hexacaprate, octyl-2-dodecyl hydroxystearate, pentaerythrityl tetra-octyldodecanoate, triisostearyl citrate, pentaerythrityl tetra-2-hexyldecanoate, propylene glycol diisostearate, tridecyltetradecanoine, isostearate isostearyl, isofol 24 isostearate, triisocetyl citrate, diisopropyl dimer dilinoleate, pentaerythrityl tetradecyltetradecanoate, diisostearyl malate (n= 1.46) as the commercial product SCHERCEMOL DISM ESTER® from LUBRIZOL, di-iso-arachidyl dodecane dioate, octyldodecyl erucate, triisoarachidyl citrate, hexyldecyl myristoyl methylaminopropionate,pentaerythrityl tetraisostearate, trimethylolpropane triisostearate, oleyl erucate, ditrymethylolpropane tetraisostearate, dioctyldodecyl dimer dilinoleate, ethyl panthenol, sucrose 6-8 soybean fatty acids, triisostearyl trilinoleate, octyl-2-dodecyl benzoate, ethyl-2-hexyl benzoate, isofol 12 trimellitate, C12-C15 alkylbenzoate, hydrogenated dimer dilinoleyl / dimethylcarbonate copolymer, triiso-decyl trimellitate, tri-decyl trimellitate, triethyl-2-hexyl trimellitate, castor oil benzoate, dipropylene glycol dibenzoate, the ethyl-2-hexyl glyceryl ether palmitate;

[0036] - hydrocarbon oils of vegetable origin, such as triglycerides of acids fats in C5-36 (especially C6-12) and glycerol (n= 1.45-1.46) such as caprylic / capric triglycerides, such as the commercial product DUB MCT 7030 / MB by STEARINERIE DUBOIS, arara oil, jojoba oil, pracaxi oil, virgin olive oil, meadowfoam oil, sesame oil, ximenia oil, soybean oil, macadamia oil, castor oil;

[0037] - oils obtained by dimerization of fatty acids, in particular fatty acids unsaturated in C8-C20, such as dilinoleic acid (C36) marketed by Croda under the name Pripol 1013-LQ-(GD);

[0038] - oils comprising polyoxypropylene (POP) groups or polyoxyethylenated (POEs), such as oxypropylene myristyl diadipate (3 OP), oxyethylenated glyceryl triacetate (7 OE), PEG-4 (40E), PEG-6 (60E), PEG (8 OE), octyldodecyl PPG-3 myristyl ether dimer dilinoleate; or

[0039] - their mixtures.

[0040] Preferably, as hydrocarbon oils with a refractive index n greater than or equal to 1.4, a mixture of C5-C36 fatty acid triglycerides (in particular C6-C12) and glycerol (preferably caprylic / capric triglycerides), diisostearyl malate and dilinoleic acid are used.

[0041] The hydrocarbon oil(s) with a refractive index n greater than or equal to 1.4 is / are preferably present in a concentration ranging from 5 to 50% by weight and more preferably from 8 to 40% by weight, and particularly from 10 to 30% by weight relative to the total weight of the composition.

[0042] The continuous fatty phase may also include at least one hydrocarbon volatile oil, preferably nonpolar. Nonpolar volatile hydrocarbon oils

[0043] For the purposes of this invention, "volatile oil" means an oil capable of evaporating upon contact with the skin or keratin fiber in less than one hour at room temperature (20-25°C) and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils, liquid at room temperature, having a non-zero vapor pressure at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40,000 Pa (103 to 300 mm Hg), in particular from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg).

[0044] Nonpolar hydrocarbon volatile oils are preferably chosen from among nonpolar hydrocarbon oils and in particular can be chosen from among hydrocarbon volatile oils having 8 to 16 carbon atoms and mixtures thereof, and in particular: - C8-Ci6 branched alkanes such as C8-Ci6 isoalkanes (also called isoparaffins), isododecane, isodecane, isohexadecane, and for example oils sold under the trade names Isopars or Permetyls, - linear alkanes, for example such as n-decane (C10) and n-dodecane (C12) sold by Biosynthis under the reference Vegelight Silk, n-dodecane (C12) sold by Sasol under the reference PARAFOL 12-97, as well as their mixtures, the undecane-tridecane mixture (Cétiol UT), the mixtures of n-undecane (Cl1) and n-tridecane (Cl3) obtained in examples 1 and 2 of application WO2008 / 155059 from Société Cognis, or the mixture of C9-C12 alkanes, and - their mixtures.

[0045] Among volatile hydrocarbon oils, C8-Ci6 isoalkanes, in particular isododecane, and mixtures of alkanes, are preferred.

[0046] The oil or volatile hydrocarbon oils according to the invention are present, preferably, in concentrations ranging from 5 to 30% by weight and more particularly ranging from 8 to 20% by weight relative to the total weight of the composition. DISTRESSED AQUEOUS PHASE

[0047] The composition according to the invention comprises an aqueous medium, constituting an aqueous phase, which forms the dispersed phase of the composition (compound b). The composition according to the invention is in fact an inverse emulsion (water-in-oil or W / O).

[0048] The aqueous phase may consist essentially of water; it may also comprise a mixture of water and water-miscible solvent (miscibility in water greater than 50% by weight at 25°C).

[0049] The water-miscible solvent can be chosen from lower monoalcohols having 1 to 5 carbon atoms such as ethanol, isopropanol and their mixtures.

[0050] The water-miscible solvent can be selected from polyols, more particularly C2-C8, preferably C3-C6, liquid polyols at room temperature, saturated or unsaturated, linear or branched, comprising 2 to 6 hydroxyl groups. Preferably, the polyol is selected from glycerin, diglycerin, pentanediol, C3-C8, linear or branched, saturated glycols, in particular propylene glycol, ethylene glycol, 1,3-butylene glycol, pentylene glycol, caprylyl glycol, dipropylene glycol, and mixtures thereof, and preferably glycerin, propylene glycol, 1,3-butylene glycol, and mixtures thereof.

[0051] The composition preferably comprises a water content representing at least 10% by weight, preferably at least 20% by weight, preferably a content ranging from 20% to 40% by weight relative to the total weight of the composition.

[0052] Preferably, the composition according to the invention comprises at least one water-miscible solvent selected from lower monoalcohols having 1 to 5 carbon atoms, polyols and mixtures thereof.

[0053] The composition according to the invention may include a water-miscible solvent(s) content of between 2 and 15% by weight, preferably from 4 to 10% by weight, relative to the weight of the composition. Surfactants with an HLB value of less than or equal to 8

[0054] The compositions of the invention comprise at least one emulsifying surfactant having an HLB (hydrophilic / lipophilic balance) less than or equal to 8, more particularly less than or equal to 7, preferably between 1 and 6 (compound c). The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.

[0055] Preferably, it is non-ionic.

[0056] Preferably, the surfactant(s) are chosen from hydrocarbon non-ionic surfactants and their mixtures.

[0057] Non-ionic surfactants may be selected in particular from polyoxyethylenated C8-C30 alcohols, alkyl(C8-C30)- and polyalkyl(C8-C30)- esters (Poly)oxyethylenated and / or (poly)oxypropylenated; fatty acid polyesters, preferably polyhydroxylated, in the form of Ci2-C2o, polyoxyethylenated, having from 4 to 50 moles of ethylene oxide; alkyl- and polyalkyl- esters of sorbitan; alkyl- and polyalkyl- esters of (poly)glycerol; hydrocarbon surfactants resulting from the esterification of a mixture of polyglycerol with (i) a polyhydroxystearic acid, (ii) aliphatic dicarboxylic acids, linear or branched, having from 4 to 14 carbon atoms, or (iii) saturated or unsaturated fatty acids, linear or branched, having from 16 to 20 carbon atoms; and mixtures thereof.

[0058] As C8-C30 poly(oxyethylenated) alcohols, those with a number of ethylene oxide (EO) motifs ranging from 2 to 4 are preferred. Examples include laureth-2; steareth-2; oleth-2; oleth-3; ceteth-2; ceteareth-3.

[0059] As alkyl(C8-C30)- and polyalkyl(C8-C30)- esters (poly)oxyethylenated and / or (poly)oxypropylenated, those with a number of ethylene oxide (EO) motifs ranging from 1 to 5 are preferably used, with for example glycol distearate, glycol stearate, PEG-2 oleate; PEG-3 oleate; PEG-4 dilaurate, propylene glycol isostearate; PEG-2.5 castor oil; PEG-3 castor oil.

[0060] Other usable surfactants include fatty acid polyesters, preferably polyhydroxylated, in the form Ci2-C20, polyoxyethylenated, having from 4 to 50 moles of ethylene oxide, and possessing water-in-oil emulsifying properties. In particular, these polymers are sequenced polymers, preferably of ABA structure, comprising poly(hydroxylated ester) sequences and polyoxyethylenated sequences. The fatty acid of said emulsifying polymer, as defined above, preferably has from 14 to 18 carbon atoms. The esters may, in particular, be selected from oleates, palmitates, or stearates. The polyoxyethylenated sequences of said emulsifying polymer, as defined above, preferably comprise from 20 to 40 moles of ethylene oxide.A polymer surfactant particularly suitable for the preparation of the compositions of the invention is polyethylene glycol di-polyhydroxystearate 30 OE (PEG-30 DIPOLYHYDROXYSTEARATE) sold under the trade name Cithrol DPHS-SO-(MV) by the company Croda.

[0061] As alkyl(C8-C30)- and polyalkyl(C8-C30)- esters of sorbitan, particular examples include sorbitan trioleate, sorbitan sesquioleate, sorbitan oleate, sorbitan palmitate; sorbitan stearate, sorbitan isostearate, mixtures of sorbitan stearate and sucrose cocoate or sorbitan isostearate and glycerol (Arlacel 986 marketed by Croda), and mixtures thereof.

[0062] As alkyl(C8-C30)- and polyalkyl(C8-C30)- esters of (poly)glycerol, those with a number of glycerol motifs ranging from 1 to 4 are preferably used. Examples include polyglyceryl-4 isostearate (Isolan GI 34 marketed by Evonik Goldschmidt); polyglyceryl-3 diisostearate (Lameform TGI marketed by Cognis), glyceryl stearate, glyceryl laurate, alone or in mixtures.

[0063] Finally, as hydrocarbon surfactants resulting from the esterification of a mixture of polyglycerol with (i), (ii) or (iii), we may mention hydrocarbon surfactants resulting from the esterification (i) of a polyhydroxystearic acid with 2 to 5 units of polyglycerol, preferably 4 units, (ii) of a mixture of polyglycerol with aliphatic dicarboxylic acids, linear or branched having 4 to 14 carbon atoms, preferably sebacic acid, and (iii) of a mixture of polyglycerol with saturated or unsaturated fatty acids, linear or branched having 16 to 20 carbon atoms, preferably isostearic acid. A preferred example of a polyhydroxystearic acid and polyglycerol ester is polyglyceryl-4 diisostearate polyhydroxystearate sebacate (INCI name: POLYGLYCERYL-4 DIISOSTEARATE / POLYHYDROXYSTEARATE / SEBACATE) with the formula:

[0064] [Chem.l]

[0065] where PHS denotes polyhydroxystearic acid and IS denotes isostearic acid.

[0066] Such a compound is prepared according to US application 2005 / 0031580 and marketed under the name ISOLAN GPS by the company Evonik Goldschmidt.

[0067] Preferably, the composition comprises a mixture of a polyhydroxylated fatty acid polyester, in Ci2-C2o, polyoxyethylenated having 4 to 50 moles of ethylene oxide, and polyglyceryl-4 diisostearate polyhydroxystearate sebacate.

[0068] According to the invention, the surfactant(s) having an HLB of 8 or less are present in a concentration ranging from 0.1 to 15%, preferably from 1 to 12%, and even more preferably from 2 to 10% by weight relative to the total weight of the composition. Lipophilic film-forming polymer

[0069] The composition according to the invention comprises at least one lipophilic film-forming polymer, preferably at least one silicone film-forming polymer, and more particularly at least one silicone resin (compound d).

[0070] Advantageously, the lipophilic film-forming polymer is present in a content of at least 5% by weight, preferably in a content ranging from 5 to 20% by weight relative to the total weight of the composition, or better from 6 to 15% by weight, relative to the total weight of the composition.

[0071] Preferably, the composition according to the invention comprises at least one silicone resin.

[0072] More generally, the term "resin" refers to a compound with a three-dimensional structure. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

[0073] The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known as "MDTQ", the resin being described according to the different siloxane monomeric units it comprises, each of the letters "MDTQ" characterizing a type of unit.

[0074] The letter “M” represents the Monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being bonded to a single oxygen atom in the polymer comprising this unit.

[0075] The letter “D” signifies a Difunctional unit R1 R2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.

[0076] The letter “T” represents a Trifunctional unit of formula RlSiO3 / 2.

[0077] In the motifs M, D, T defined above, Ri, namely RI, R2 and R3, identical or different, represent a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0078] Finally, the letter “Q” signifies a Tetrafunctional SiO4 / 2 unit in which the silicon atom is bonded to four oxygen atoms which are themselves bonded to the rest of the polymer.

[0079] Such resins are described for example in "Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or even US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

[0080] Various silicone resins of different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical(s) Ri, the length of the polymer chain, the degree of branching and the size of the dangling chains.

[0081] As examples of silicone resins that can be used in the compositions according to the invention, silicone resins of type MQ, type T or type MQT can be used.

[0082] MQ Resins:

[0083] By way of example of MQ type silicone resins, siloxysilicate type resins such as alkylsiloxysilicates, aryl siloxysilicate or alkylaryl siloxysilicates, of formula [(Rl)3SiOi / 2]x(SiO4 / 2)y (MQ units) in which x and y are integers from 50 to 80, and such that the RI group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group,

[0084] Examples of solid silicone resins of type MQ of type Trimethylsiloxysilicate (INCI name) include those marketed under the reference SR1000 by General Electric, under the reference TMS 803 by Wacker, or mixtures including it such as the product marketed under the name Silsoft 74 Fluid (in isododecane) by Momentive.

[0085] Examples of silicone resins comprising siloxysilicate MQ motifs include phenylalkylsiloxysilicate resins, such as Phenylpropyl dimethylsiloxysilicate (INCI name), like Silshine 151 marketed by General Electric. The preparation of such resins is described in particular in US patent 5817302. Resins T#:

[0086] Examples of T-type silicone resins include polysilsesquioxanes comprising predominantly units of the formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes possibly also comprising Si-OH terminal groups. Thus, these resins comprise, for example, at least 80 mole percent of T units.

[0087] We can also mention polymethylsilsesquioxanes, which are polysilsesquioxanes in which none of the methyl groups is substituted by another group. Such polymethylsilsesquioxanes are described, for example, in US patent 5,246,694.

[0088] Preferably, Polymethylsilsesquioxane resins (INCI name) can be used in which R represents a methyl group, such as those marketed by Wacker under the reference Resin MK such as Belsil PMS MK, by SHIN-ETSU under the references KR-220L, KR-242A or KR-251.

[0089] Among the silsesquioxane resins that can be used in the present invention, mention may also be made of those corresponding to homopolymers and / or copolymers of silsesquioxane having an average siloxane unit of general formula Rln SiO(4- n) / 2, wherein each RI is a propyl group, in which more than 80 mole percent of the RIs represent a C3 to C10 alkyl group, n is a value of 1.0 to 1.4, and more than 60 mole percent of the copolymer comprises R1SiO3 / 2 units. Since each RI is a propyl group, these polymers are called Polypropylsilsesquioxane resins (INCI name) or "t-propyl" silsesquioxane resins. These resins and their manufacturing processes are described, for example, in documents US8586013, US2012 / 0301415, and US2006 / 0292096.

[0090] Among the Polypropylsilsesquioxane resins, we can mention those marketed by Dow Corning under the name Dowsil 680 ID Fluid, which are mixtures of Polypropylsilsesquioxane with isosodecane.

[0091] MQT Resins:

[0092] As examples of resins comprising MQT motifs, those cited in US document 5,110,890 are known.

[0093] A preferred form of MQT-type resins is MQT-propyl resin (also called MQTPr). Such resins usable in compositions according to the invention include, in particular, those described and prepared in application WO 2005 / 075542, the contents of which are incorporated herein by reference.

[0094] The MQ-T-propyl resin preferably comprises the following units: (i) (Rl3SiO1 / 2)a (ii) (R22SiO2 / 2)b (üi) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d

[0095] with - RI, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, - a, b, c and d being mole fractions, - a being between 0.05 and 0.5, - b being between zero and 0.3, - c being greater than zero, - d being between 0.05 and 0.6, - a + b + c + d = l, - provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0096] Preferably, the siloxane resin comprises the following units: (i) (Rl3SiO1 / 2)a (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d

[0097] with - RI and R3 independently represent an alkyl group having from 1 to 8 carbon atoms, RI preferably being a methyl group and R3 preferably being a propyl group, - a being between 0.05 and 0.5, preferably between 0.15 and 0.4, - c being greater than zero, preferably between 0.15 and 0.4, - d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or even between 0.2 and 0.55, - a + b + c + d = 1, and a, b, c and d are mole fractions, - provided that more than 40% by moles of the R3 groups of the resin siloxane are propyl groups.

[0098] The siloxane resins usable according to the invention can be obtained by a process comprising the reaction of:

[0099] A) an MQ resin comprising at least 80 mole percent of (Rl3SiO1 / 2)a and (SiO4 / 2)d units - RI representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, - a and d being greater than zero, - the ratio a / d being between 0.5 and 1.5;

[0100] and of

[0101] B) a propyl resin T comprising at least 80 mole percent of (R3SiO3 / 2)c units, - R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, - c being greater than zero, - provided that at least 40 mole percent of the R3 groups are propyl groups, - where the mass ratio A / B is between 95:5 and 15:85, preferably the mass ratio A / B is 30:70.

[0102] Advantageously, the mass ratio A / B is between 95:5 and 15:85. Preferably, the A / B ratio is less than or equal to 70:30. These preferred ratios have been shown to allow comfortable deposition.

[0103] Preferably, the composition according to the invention comprises, as a silicone resin, at least one MQ type resin as described above.

[0104] In particular, the silicone resin is a siloxysilicate resin, preferably an alkylsiloxysilicate resin, preferably Trimethylsiloxysilicate.

[0105] Advantageously, the silicone resin is present in a content of at least 5% by weight, preferably in a content ranging from 5 to 20% by weight relative to the total weight of the composition, or better from 6 to 15% by weight, relative to the total weight of the composition. Hydroxyacid

[0106] The composition according to the invention comprises at least one hydroxy acid (compound e)).

[0107] The hydroxy acid can be selected from α-hydroxy acids (AHAs) and their derivatives, γ-hydroxy acids (BHAs) and their derivatives, polyhydroxy acids (PHAs), and mixtures thereof.

[0108] Preferably, the composition comprises:

[0109] - at least one α-hydroxy acid and at least one γ-hydroxy acid, or

[0110] - at least one α-hydroxy acid and at least one polyhydroxy acid, or

[0111] - at least one [3-hydroxy acid and at least one polyhydroxy acid, or

[0112] - at least one α-hydroxy acid, at least one γ-hydroxy acid and at least one polyhydroxyacid.

[0113] The α-hydroxy acid(s), the |3-hydroxy acid(s) and the polyhydroxy acid(s) of each of these embodiments may be as defined below.

[0114] Preferably the composition comprises at least one [3-hydroxy acid, preferably in a mixture with at least one α-hydroxy acid and / or at least one polyhydroxy acid, each being as defined below according to any embodiment.

[0115] The term "alpha-hydroxy acid", "a-hydroxy acid", or "AHA" here means a compound comprising at least one carboxylic acid (COOH) function and at least one hydroxyl (OH) group on the carbon (alpha) atom adjacent to one of the CCOH functions, preferably comprising one or two, preferably only one, OH groups (independently of the OH group(s) of the COOH function(s)).

[0116] The α-hydroxy acid may be selected from: glycolic acid, citric acid, lactic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxynonanoic acid, 2-hydroxydecanoic acid, 2-hydroxyundecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxytetracosanoic acid, 2-hydroxyeicosanoic acid; 1-hydroxy-1-cyclopropanecarboxylic acid; 2-hydroxy-3-butenoic acid; 2-Hydroxyisobutyric acid; 2-Hydroxy-n-butyric acid; isoserine; 2-Hydroxy-2-methylbutyric acid; 4-Amino-2-hydroxybutyric acid; 1-Hydroxycyclohexanecarboxylic acid; dihydroxyfumaric acid; 2-Trifluoromethyl-2-hydroxypropionic acid; 3-Hydroxymandelic acid; 4-Hydroxymandelic acid; 3-Methoxymandelic acid; 4-Methoxymandelic acid; 2-Hydroxy-4-(methylthio)butyric acid; 2-Hydroxy-3-methylvaleric acid; 3-Imidazolelactic acid; Glyceric acid; 2-Hydroxy-3-methylbutyric acid; 3-(4-Hydroxyphenyl)lactic acid; 1,2-Dihydroxycyclobutanecarboxylic acid; 2-Ethyl-2-hydroxybutyric acid; α-Hydroxyisocaproic acid; α-Hydroxycaproic acid; 2-Hydroxy-3,3-Dimethylbutyric acid; Mandelic acid; Phenyllactic acid; Tartronic acid; Tartaric acid; malic acid; their salts and mixtures;

[0117] and among the derivatives of α-hydroxy acids, which are preferably esters, preferably formed from one or more COOH groups of the α-hydroxy acid. Preferably, the ester group(s) is / are formed from one or more COOH groups of the α-hydroxy acid and an OH-Rc compound, with Rc being a saturated or unsaturated, straight-chain, branched-chain, or cyclic alkyl, aralkyl, or aryl group having 1 to 19 carbon atoms. When the α-hydroxy acid contains two or more COOH groups, the ester may exist as a partial or complete ester, for example (without limitation), monoethyl tartrate and diethyl tartrate, monoethyl citrate, diethyl citrate, and triethyl citrate.

[0118] Preferably, the α-hydroxy acid is chosen from glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, mandelic acid and their salts; more preferably, the α-hydroxy acid is chosen from glycolic acid, citric acid, lactic acid, their salts and mixtures thereof, and even more preferably, the α-hydroxy acid is lactic acid.

[0119] The term “beta-hydroxy acid”, “[3-hydroxy acid], or “BHA” means here a compound comprising at least one carboxylic acid (COOH) function and at least one hydroxyl (OH) group on the beta carbon atom to one of the carboxylic acid functions, preferably includes one or two hydroxyl groups (independently of the OH group(s) of the COOH function(s)).

[0120] The [3-hydroxy acid may be selected from salicylic acid and its derivatives, preferably selected from salicylic acid, 5-(n-decanoyl)salicylic acid, 5-(n-dodecanoyl)salicylic acid and 5-(n-heptyloxy)salicylic acid; 5-(n-octanoyl)salicylic acid (CTFA name: Capryloyl Salicylic Acid), 5-n-decanoylsalicylic, 5-n-dodecanoylsalicylic, 5-n-octylsalicylic, 5-n-heptyloxysalicylic, 5-tert-octylsalicylic, 5-butoxysalicylic, 5-ethoxysalicylic, 5-methoxysalicylic, 5-propoxysalicylic, 5-methylsalicylic, 5-ethylsalicylic and 5-propylsalicylic acids, and mixtures thereof.

[0121] More preferably, the [3-hydroxyacid is a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid.

[0122] The term "polyhydroxy acid" designates an organic compound that has at least one carboxyl group and a plurality of hydroxyl groups. The number of hydroxyl groups in the polyhydroxy acid preferably ranges from 2 to 10, more preferably from 3 to 10, or from 2 to 6, or from 3 to 6.

[0123] Polyhydroxy acids may be selected from a dihydroxypropanoic acid such as glyceric acid; a trihydroxybutanoic acid such as erythronic acid and threonic acid; a tetrahydroxypentanoic acid such as ribonic acid, arabinonic acid, xylonic acid and lyxonic acid; a pentahydroxyhexanoic acid such as allonic acid, altronic acid, gluconic acid, mannic acid, gulonic acid, idonic acid, galactonic acid and talonic acid; a hexahydroxyheptanoic acid such as glucoheptanoic acid and galactoheptonic acid; lactobionic acid; maltobionic acid; their derivatives such as their salts or their lactone forms such as gluconolactone or ribonolactone; and mixtures thereof.

[0124] Preferably, the polyhydroxy acid is chosen from lactobionic acid, gluconic acid, gluconolactone, ribonolactone and mixtures thereof, and more preferably, the polyhydroxy acid is gluconolactone.

[0125] The type of salt is not limited. Examples of salts include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; zinc salts; iron salts; ammonium salts; amine salts such as monoethanolamine salt, diethanolamine salt, and triethanolamine salt; and mixtures thereof. Sodium salt is preferred. If two or more salts are used, they may be the same or different.

[0126] More preferably, the composition according to the invention comprises a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid, preferably mixed with at least one α-hydroxy acid selected from glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, mandelic acid and their salts, and / or mixed with at least one polyhydroxy acid selected from lactobionic acid, gluconic acid, gluconolactone, ribonolactone and mixtures thereof. Advantageously, the composition comprises a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid, preferably mixed with lactic acid and / or gluconolactone.

[0127] The hydroxyacid(s) may be present in the composition according to the invention in an active matter content ranging from 0.1 to 15%, preferably from 0.3 to 10% by weight, preferably from 0.5 to 8% by weight, preferably from 1 to 6% by weight relative to the total weight of said composition.

[0128] If the composition comprises several (at least two) hydroxy acids, the above amounts refer to the total hydroxy acid content of the composition. Colouring agents

[0129] The composition according to the invention further comprises at least one colouring material (compound f) which is preferably chosen from colourants, pigments, mother-of-pearls and mixtures thereof.

[0130] The colouring material(s) may be present in the composition in a content ranging from 0.1% to 25% by weight, relative to the weight of the composition, preferably from 0.5% to 20% by weight, in particular from 1% to 20% by weight.

[0131] By "colorants", we should understand compounds generally organic soluble in fats such as oils or in an aqueous or hydroalcoholic phase.

[0132] The composition according to the invention may comprise at least one water-soluble colorant and / or at least one fat-soluble colorant.

[0133] For the purposes of this invention, "water-soluble colorant" means any compound, generally organic, natural or synthetic, soluble in an aqueous phase or in water-miscible solvents and capable of coloring. In particular, the term "water-soluble" characterizes the ability of a compound to dissolve in water, measured at 25 °C, at a concentration of at least 0.1 g / L (obtaining a macroscopically isotropic and transparent solution, colored or not). This solubility is, in particular, greater than or equal to 1 g / L.

[0134] Suitable water-soluble colorants for the invention include, in particular, synthetic or natural water-soluble colorants such as, for example, DC Red 6 (Lithol Rubine Na; CI: 15850), DC Red 22 (CI: 45380), DC Red 28 (CI: 45410, Na salt), DC Red 30 (CI: 73360), DC Red 33 (CI: 17200), DC Red 40 (CI: 16035), FDC Yellow 5 (CI: 19140), FDC Yellow 6 (CI: 15985), DC Yellow 8 (CI: 45350 Na salt), FDC Green 3 (CI: 42053), DC Green 5 (CI: 61570), FDC Blue 1 (CI: 42090).

[0135] By way of illustration and not limitation of sources of water-soluble colouring material(s) which may be used in the context of the present invention, we may in particular mention those of natural origin, such as extracts of carmine, cochineal, beetroot, grape, carrot, tomato, annatto, paprika, henna, caramel and curcumin.

[0136] Thus, the water-soluble coloring materials suitable for the invention include, in particular, carminic acid, betanin, anthocyanins, enocyanins, lycopene, bixin, norbixin, capsanthin, capsorubin, flovoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, riboflavin, roudoxanthin, cantaxanthin, chlorophyll, and mixtures thereof.

[0137] It may also be copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamine, betaine, methylene blue, disodium salt of tartrazine and disodium salt of fuchsin.

[0138] Some of these water-soluble coloring materials are specifically approved for use in food. Representative examples of these colorings include carotenoid colorings, referenced under food codes E120, E162, E163, E160a-g, E150a, E101, E100, E140 and E141.

[0139] According to a particularly preferred embodiment, the water-soluble colouring material(s) are chosen from among the sodium salts of Yellow 6, Yellow 5, Red 6, Red 33, Red 40.

[0140] By "liposoluble colorant", in the sense of the invention, means any compound generally organic, natural or synthetic, soluble in an oily phase or solvents miscible with the oily phase and capable of coloring.

[0141] As suitable liposoluble colorants for the invention, the following may be cited in particular: liposoluble colorants such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, Sudan brown.

[0142] By way of illustration, natural fat-soluble colorants, one can particularly mention carotenes such as [3-carotene, α-carotene, lycopene; quinoline yellow; xanthophylls such as astaxanthin, antheraxanthin, citranaxanthin, cryptoxanthin, canthaxanthin, diatomoxanthin, flavoxanthin, fucoxanthin, lutein, rhodoxanthin, rubixanthin, siphonaxanthin, violaxanthin, zeaxanthin; annatto; curcumin; quinizarin (Ceres Green BB, D&C Green No. 6, CI 61565, 1,4-Di-p-Toluidinoanthraquinone, Green No. 202, Quinzaine Green SS) and chlorophylls.

[0143] By pigments, we mean white or colored particles, mineral or organic, insoluble in an aqueous solution, intended to color and / or opacify the resulting deposit.

[0144] The pigments can be selected from mineral pigments, organic pigments, and composite pigments (i.e., pigments based on mineral and / or organic materials). The pigments can be selected from monochrome pigments, lacquers, mother-of-pearl pigments, pigments with optical effects, such as reflective pigments and goniochromatic pigments.

[0145] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0146] By "mineral pigment" is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include zirconium oxides or cerium, as well as zinc, iron (black, yellow, or red) or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metallic powders such as aluminum and copper powder. The following mineral pigments can also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂ mixed with TiO₂, ZrO₂, Nb₂O₅, CeO₂, and ZnS.

[0147] The size of the pigment used in the present invention is generally greater than 100 nm and can be up to 10 µm, preferably from 200 nm to 5 µm, and more preferably from 300 nm to 1 µm. According to a particular embodiment of the invention, the pigments have a size characterized by a D

[50] greater than 100 nm and can be up to 10 µm, preferably from 200 nm to 5 µm, and more preferably from 300 nm to 1 µm. The sizes are measured by laser diffraction using a commercial particle size analyzer such as the Malvern MasterSizer 3000®, which allows for the determination of the particle size distribution of all the particles over a wide range from 0.01 µm to 1000 µm. The data are processed based on the classical Mie scattering theory. This theory is best suited for size distributions ranging from submicron to multi-micron, it allows us to determine an "effective" particle diameter.This theory is notably described in the work of Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. D

[50] represents the maximum size that 50% of the particles have by volume.

[0148] In the context of the present invention, the mineral pigments are more particularly iron oxide and / or titanium dioxide.

[0149] As mineral pigments usable in the invention, nacres may also be mentioned. "Nacres" should be understood to mean colored particles of any shape, iridescent or not, in particular, produced by certain mollusks in their shells or synthesized, and which exhibit a color effect through optical interference. Nacres may be chosen from among pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. They may also consist of mica particles on the surface of which at least two successive layers of metal oxides and / or organic coloring materials are superimposed.

[0150] We can also cite, as an example of nacres, natural mica covered with titanium oxide, iron oxide, natural pigment or bismuth oxychloride.

[0151] Mother-of-pearl may in particular have a yellow, pink, red, bronze, orange, brown, gold and / or copper colour or reflection.

[0152] Among the pigments usable according to the invention, one can also mention those with an optical effect different from a simple conventional hue effect, that is to say, unified and stabilized such as that produced by conventional coloring materials, such as, for example, monochromatic pigments. For the purposes of the invention, "stabilized" means devoid of any color variability effect with the angle of observation or in response to a change in temperature. For example, this material can be chosen from metallic-reflecting particles, goniochromatic coloring agents, diffracting pigments, thermochromic agents, optical brightening agents, as well as fibers, in particular, interference fibers. Of course, these different materials can be combined in such a way as to provide the simultaneous manifestation of two effects, or even a new effect according to the invention.

[0153] According to a particular mode, the composition according to the invention comprises at least one uncoated pigment.

[0154] According to another particular embodiment, the composition according to the invention comprises at least one pigment coated with at least one lipophilic or hydrophobic compound. This type of pigment is particularly advantageous. Insofar as they are treated with a hydrophobic compound, they exhibit a predominant affinity for an oily phase, which can then carry them. The coating may also comprise at least one additional non-lipophilic compound.

[0155] For the purposes of the invention, "coating" of a pigment according to the invention generally means the total or partial surface treatment of the pigment by a surfactant, absorbed, adsorbed or grafted onto said pigment.

[0156] Surface-treated pigments can be prepared using surface treatment techniques of a chemical, electronic, mechano-chemical or mechanical nature well known to those skilled in the art. Commercial products can also be used.

[0157] The surfactant can be absorbed, adsorbed, or grafted onto the pigments by solvent evaporation, chemical reaction, and the formation of a covalent bond. In one embodiment, the surface treatment consists of coating the pigments. The coating can represent from 0.1% to 20% by weight, and in particular from 0.5% to 5% by weight, of the total weight of the coated pigment.

[0158] The coating can be achieved for example by adsorption of a liquid surfactant to the surface of the solid particles by simple mixing under agitation of the particles and said surfactant, possibly hot, prior to the incorporation of the particles into the other ingredients of the makeup or skincare composition.

[0159] The coating can be achieved, for example, by a chemical reaction of a surfactant with the surface of the solid pigment particles and the creation of a covalent bond. between the surfactant and the particles. This method is described in particular in US patent 4,578,266.

[0160] Chemical surface treatment may consist of diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, and then slowly evaporating the volatile solvent so that the surfactant is deposited on the surface of the pigments.

[0161] According to a particular embodiment of the invention, the pigments can be coated according to the invention by at least one compound selected from silicone surfactants; fluorinated surfactants; fluoro-siliconized surfactants; metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

[0162] According to a particular mode, the colouring material is an organic, synthetic, natural or naturally derived pigment.

[0163] By "organic pigment" is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on organic pigment. The organic pigment may in particular be chosen from among the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0164] The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the Color Index under references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments coded in the Color Index under references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under references CI 61565, 61570, 74260, the orange pigments coded in the Color Index under the references CI 11725, 15510, 45370, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and pigments obtained by oxidative polymerization of indole derivatives,phenolic compounds as described in French patent FR 2 679 771.

[0165] The pigments can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed, in particular, of particles having an inorganic core coated with less partially of an organic pigment and at least one binder ensuring the fixation of the organic pigments to the core.

[0166] The pigment can also be a lacquer. By lacquer, we mean insolubilized dyes adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0167] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0168] Among the organic dyes, we can mention cochineal carmine. We can also mention the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090). Examples of lacquers include the product known as D&C Red 7 (CI 15 850 :1). ADDITIONAL COMMON COSMETIC INGREDIENTS

[0169] The composition according to the invention may further include any common cosmetic ingredient which may be chosen in particular from hydrophobic thickeners, fillers of organic or mineral nature, antioxidants, perfumes, preservatives, neutralizers, sequestrants, active ingredients and mixtures thereof.

[0170] Of course, a person skilled in the art will take care to choose any additional ingredients and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not or substantially not altered by the envisaged addition.

[0171] The hydrophobic thickener may be selected from alkylated guar gums (with alkyl group in C1-C6), such as those described in EP-A-708114; polyamide resins comprising alkyl groups having from 12 to 22 carbon atoms, such as those described in US-A-5783657; alkyl ethers of polysaccharides, in particular having the alkyl group comprising from 1 to 24 carbon atoms, preferably from 1 to 10, better from 1 to 6, and more especially from 1 to 3, such as those described in EP-A-898958; organophilic clays; hydrophobic fumed silicas; hydrophobic silica aerogels; elastomeric organopolysiloxanes and mixtures thereof.

[0172] Clays are silicates containing a cation that can be selected from among the cations of calcium, magnesium, aluminum, sodium, potassium, lithium and mixtures thereof. Examples of such products include clays of the smectite family such as montmorillonite, hectorite, bentonite, Beidellites, saponites, as well as members of the vermiculite family, stevensite, and chlorites. These clays can be of natural or synthetic origin. Organophilic clays are clays modified with a chemical compound chosen from among quaternary amines, tertiary amines, amino acetates, imidazolines, amino soaps, fatty sulfates, alkyl aryl sulfonates, amine oxides, and mixtures thereof.

[0173] We can thus mention hectorites modified by a quaternary amine, more precisely by a halide, such as a chloride, of ammonium of fatty acid in C10 to C22, such as hectorite modified by distearyl dimethyl ammonium chloride (CTFA name: Disteardimonium hectorite), such as, for example, that marketed under the name Bentone 38V®, Bentone 38V CG, Bentone EW CE, by the company Elementis; stearalkonium Hectorites such as Bentone 27 V.

[0174] Other examples include quatemium-18 bentonites such as those sold under the names Bentone 34 marketed by Elementis, Claytone 40, Tixogel VP by United Catalyst and Southern Clay; stearalkonium bentonites such as those sold under the names Tixogel LG by United Catalyst, Claytone AF, Claytone APA by Southern Clay; and quatemium-18 / benzalkonium bentonite such as those sold under the name Claytone HT by Southern Clay.

[0175] According to a preferred embodiment, the thickening agent is chosen from organophilic modified clays, in particular organophilic modified hectorites, in particular by halides, preferably benzyldimethylammonium stearate chlorides, or by distearyl dimethyl ammonium chloride.

[0176] Hydrophobic pyrolyzed silicas can be obtained by modifying the silica surface through a chemical reaction that reduces the number of silanol groups, these groups being able to be replaced by hydrophobic groups. The hydrophobic groups can be:

[0177] - trimethylsiloxyl groups, which are obtained in particular by treatment of pyrogenated silica in the presence of hexamethyldisilazane. Silicas treated in this way are called "Silica silylate" according to the CTFA (6th edition, 1995). They are marketed for example under the references "Aerosil R812®" by the company Degussa, "CAB-O-SIL TS-530®" by the company Cabot;

[0178] - dimethylsilyloxyl or polydimethylsiloxane groups, which are in particular obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas treated in this way are called "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are marketed, for example, under the references "Aerosil R972®", "Aerosil R974®" by the company Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" by the company Cabot.

[0179] - Silica aerogels are porous materials obtained by replacing (with The liquid component of a silica gel is dried by air. These gels are generally synthesized by the sol-gel process in a liquid medium and then dried, usually by extraction from a supercritical fluid, most commonly supercritical CO2. This type of drying prevents pore and material contraction. The sol-gel process and the various drying methods are described in detail in Brinker CL, and Scherer GW, Sol-Gel Science: New York: Academie Press, 1990.

[0180] Preferably, hydrophobic silica aerogel particles modified on the surface by trimethylsilyl groups will be used.

[0181] - As an example of hydrophobic silica aerogels, aerogel may be cited Marketed under the name VM-2260 (INCI name Silica silylate) by Dow Corning, its particles have an average size of approximately 1000 microns and a specific surface area per unit mass ranging from 600 to 800 m² / g. Other examples include aerogels marketed by Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, Enova® Aerogel MT 1100, and ENOVA Aerogel MT 1200.

[0182] Elastomeric organopolysiloxanes are generally partially or fully crosslinked and may have a three-dimensional structure. Organopolysiloxane elastomerics associated with an oil phase are generally in the form of a gel consisting of an organopolysiloxane elastomeric combined with an oil phase, embedded in at least one hydrocarbon oil. They may be selected, in particular, from among the crosslinked polymers described in application EP-A-0295886. According to this application, organopolysiloxane elastomerics are obtained by the addition and crosslinking reaction of at least:

[0183] (a) an organopolysiloxane having at least two lower alkenyl groups per molecule;

[0184] (b) an organopolysiloxane having at least two hydrogen atoms bonded to one atom of silicon per molecule;

[0185] (c) and a platinum-type catalyst.

[0186] The thickening agent may be present in a content ranging from 0.1% to 20% by weight, relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight.

[0187] By "charge" is meant colorless or white solid particles of all shapes, which are insoluble and dispersed in the medium of the composition. They are distinct from coloring materials.

[0188] Among the fillers that can be used in the compositions according to the invention, mention may be made of silica, kaolin, starch, lauroyl-lysine, fumed silica particles, optionally hydrophilically treated, mica, talc, sericite, perlite, powders polyamide (Nylon®), poly-palanine and polyethylene, tetrafluoroethylene polymer powders (Teflon®), hollow polymeric microspheres such as those of polyvinylidene chloride / acrylonitrile like Expacel® (Nobel Industrie), acrylic acid copolymers, silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydroxyapatite, barium sulfate, aluminum oxides, polyurethane powders, composite fillers, hollow silica microspheres, glass or ceramic microcapsules, metallic soaps derived from carboxylic organic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example stearate of zinc, magnesium or lithium, zinc laurate and magnesium myristate and mixtures thereof.

[0189] A composition implemented according to the invention may comprise one or more fillers in a content ranging from 0.1% to 15% by weight, in particular from 0.2% to 10% by weight, relative to the weight of the composition.

[0190] The composition according to the invention may further comprise at least one active ingredient.

[0191] The term "active ingredient" means a compound having a cosmetic and / or dermatological effect, particularly on the lips. This active ingredient may be hydrophilic or hydrophobic. The active ingredient may be water-soluble.

[0192] Thus, the active ingredient present in the composition according to the invention can be independently chosen from among agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation, anti-irritant agents, anti-pollution or anti-radical agents, UV filters, moisturizing agents other than the aforementioned polyols such as, for example, hyaluronic acid and its salts, vitamins A, E, C, B3, provitamins such as D-panthenol, soothing agents such as a-bisabolol, aloe vera, allantoin, plant extracts or essential oils, agents acting on microcirculation, agents acting on the energy metabolism of cells, healing agents, freshness actives such as menthol and its derivatives, and mixtures thereof.

[0193] The quantity of active ingredient(s) ranges for example from 0.0001 to 10% by weight and preferably from 0.01 to 8% by weight of active ingredient relative to the total weight of the composition.

[0194] The composition according to the invention may further comprise a phosphonic derivative of the following formula (I): RJO-PfOMOHU, ®

[0195] where R represents a saturated linear cyclic alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, preferably between 5 and 7 carbon atoms, and n represents an integer between 1 and 10, preferably between 4 and 8, preferably between 5 and 7 such that 6.

[0196] Preferably, the alkyl radical is not substituted.

[0197] According to a particularly preferred embodiment of the invention, the alkyl radical is the cyclohexyl radical.

[0198] Preferably, the phosphonic derivative of formula (I) is phytic acid.

[0199] The quantity of phosphonic derivative(s) ranges, for example, from 0.01 to 5% by weight and preferably 0.1 to 1% by weight of active material relative to the total weight of the composition.

[0200] The product according to the invention can advantageously be used for skin and / or lip makeup depending on the nature of the ingredients used. In particular, the product of the invention can be in the form of foundation, lipstick, concealer or eye contour product, eyeliner, eyeshadow, or body makeup product.

[0201] Preferably, the composition of the invention may be in the form of a coloured complexion makeup product such as a foundation, possibly having care or treatment properties.

[0202] The composition according to the invention can be manufactured by known processes, generally used in the cosmetic or dermatological field.

[0203] The present invention also relates to a method of makeup or care for keratinous materials and in particular for the complexion, in which a composition according to the invention is applied to the keratinous materials, and in particular to the skin of the face.

[0204] The invention is now illustrated by the following example. In what follows, unless otherwise stated, quantities are expressed as a percentage by weight relative to the total weight of composition (% w / w).

[0205] Example: preparation of a composition according to the invention and of a composition comparative and evaluation

[0206] The Cl to C4 compositions according to the invention and comparative CCI are prepared as follows: Preparation of the oil phase:

[0207] Combine all the ingredients of phase A in a beaker, stirring using the Moritz method, and heat to 55°C. Once the mixture is homogeneous, add phase C. Let it stir for 15 minutes.

[0208] Lower the temperature to room temperature and add phase D then E. Preparation of the aqueous phase:

[0209] Stir phase B in a beaker. Heat to 55°C to facilitate homogenization of the mixture, then cool to room temperature. Adjust the pH if necessary. Emulsification:

[0210] Pour the aqueous phase onto the oily phase while stirring Mortiz.

[0211] Let it shake for 10 to 15 minutes.

[0212] Add phase F and let it stir for 10 minutes.

[0213] Condition the white formula. Tinting:

[0214] Place the white formula under Rayneri stirring and disperse the pigments until a homogeneous and fine dispersion is obtained. Package.

[0215] [Tables 1] Ingredients CCI (not in invention) Cl (invention) C2 (invention) C3 (invention) C4 (invention) Phase Polyhydroxy acid(s) 5.00 5.00 B Alpha hydroxy acid(s) 3.00 B Beta hydroxy acid(s) 0.49 0.19 0.49 B PHYTIC ACID 0.21 0.21 B Antioxidant 0.15 0.15 0.15 B GLYCERIN 1.00 1.00 1.00 1.00 1.00 B NaOH 0.78 0.78 0.78 B Other active ingredients 0.09 0.09 0.09 0.09 0.09 B CAPRYLYL GLYCOL 0.15 0.15 0.15 0.15 0.15 B ETHANOL 5.00 5.00 5.00 5.00 5.00 F Water Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 B CAPRYLIC / CAPRIC TRIGL YCERIDE 8.39 8.39 8.39 8.39 8.39 A DIISOSTEARYL MALATE 8.38 8.38 8.38 8.38 8.38 A DILINOLEIC ACID 1.55 1.55 1.55 1.55 1.55 A PEG-30 DIPOLYHYDROXY STEARATE 3.00 3.00 3.00 3.00 3.00 A (CITHROL DPHS-SO-(MV) from CRODA) POLYGLYCERYL-4 DIISOS TEARATE / POLYHYDROX YSTEARATE / SEBACATE (ISOLAN GPS from EVONIK G OLDSCHMIDT) 2.25 2.25 2.25 2.25 2.25 A TRIMETHYLSILOXYSILIC ATE (SILSOFT 74 FLUID from MO MENTIVE PERFORMANCE MATERIALS) 9.33 9.33 9.33 9.33 9.33 D DISTEARDIMONIUM HEC TORITE 1.00 1.00 1.00 1.00 1.00 C PERLITE 0.08 0.08 0.08 0.08 0.08 E SILICA SILYLATE 0.41 0.41 0.41 0.41 0.41 E ISODODECANE 7.21 7.21 7.21 7.21 7.21 D C9-12 ALKANE 4.32 4.32 4.32 4.32 4.32 D IRON OXIDES (and) TRIET HOXYCAPRYLYLSILANE 0.12 0.12 0.12 0.12 0.12 IRON OXIDES (and) TRIET HOXYCAPRYLYLSILANE 2.42 2.42 2.42 2.42 2.42 IRON OXIDES (and) TRIET HOXYCAPRYLYLSILANE (and) IRON OXIDES 0.45 0.45 0.45 0.45 0.45 TITANIUM DIOXIDE (and) TRIETHOXYCAPRYLYLSI LANE 12.51 12.51 12.51 12.51 12.51

[0216] The CCI and Cl to C4 compositions are evaluated for various parameters (see Table 2), including transfer resistance and gloss.

[0217] The suitability for transfer is assessed as follows:

[0218] - Spreading the composition on a contrast card at a thickness of 30 pm;

[0219] - Allow to dry at room temperature for a minimum of 6 hours;

[0220] - Apply a piece of white Whypall-type fabric to the deposit and place a weight on it 300g on top;

[0221] - Leave to stand for 10 seconds;

[0222] - Remove the weight and then gently remove the piece of fabric;

[0223] - Evaluate the transfer of the deposit onto the tissue.

[0224] Results: Rate between 0 and 5 with:

[0225] 0 = an absence of transfer, and

[0226] 5 = all the deposit has left and transferred onto the tissue (total transfer).

[0227] CONFORMITY: to be compliant, the composition must have a score between 0 and 3.5.

[0228] Gloss is evaluated as follows:

[0229] Use of the glossmeter (RHOPOINT Q 20 / 60 / 85° Glossmeter):

[0230] - Spreading the composition on a contrast card to a thickness of 120 pm;

[0231] - Allow to dry at room temperature for a minimum of 12 hours;

[0232] Measure the gloss at different angles (20°, 60° and 85°) using the glossmeter.

[0233] Results: The higher the values, the better the brightness. Always compare from the same angle.

[0234] The results are below:

[0235] [Tables2] ICC (outside invention) Cl (invention) C2 (invention) C3 (invention) C4 (invention) Macroscopic appearance: Conformity: Bulk appearance, homogeneity Beautiful homogeneous cream Beautiful homogeneous cream Beautiful homogeneous cream Beautiful homogeneous cream Beautiful homogeneous cream Microscopic appearance *10: Conformity: Fineness of the emulsion, good pigment dispersion Fine and homogeneous emulsion Fine and homogeneous emulsion Fine and homogeneous emulsion Fine and homogeneous emulsion Fine and homogeneous emulsion 24h stability: OK OK OK OK OK Compliance: Little or no change in bulk between the end of manufacturing and 24 hours at ambient temperature. Transfer resistance results (0: no transfer / 5: total transfer): 1.5 2.5 2.5 2.5 2.5 2.5 20°C brightening results (standard deviation): 21.73 (0.40) 31.57 (1.96) 24.77 (0.61) 61.73 (0.55) 51.87 (3.01) 60°C brightening results (standard deviation): 57.73 (0.38) 66.37 (1.86) 61.43 (0.55) 77.1 (0.44) 75.77 (0.95) 85°C brightening results (standard deviation): 77.7 (0.78) 86.73 (1.04) 81.27 (0.65) 97.13 (1.88) 96.5 (0.46) Conclusion The presence of at least one hydroxy acid improves the brilliance of the composition, while maintaining good transfer resistance.

Claims

Demands

1. Cosmetic composition in the form of a water-in-oil (W / O) emulsion, comprising: a) a continuous oil phase comprising at least one hydrocarbon oil with a refractive index n greater than or equal to 1.4, b) an aqueous phase dispersed in the continuous oil phase, c) at least one emulsifying surfactant with an HLB less than or equal to 8, d) at least one lipophilic film-forming polymer, e) at least one hydroxy acid, and f) at least one colorant.

2. Composition according to claim 1, which is substantially free of silicone oil, preferably comprising less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.3% by weight relative to the total weight of the composition, of silicone oil; preferably the composition according to the invention is totally free of silicone oil.

3. Composition according to claim 1 or 2, wherein the hydrocarbon oil of refractive index n greater than or equal to 1.4 is selected from: - linear or branched hydrocarbons, of mineral or synthetic origin, in particular hydrogenated polybutenes or polyisobutenes;- synthetic fatty acid esters such as isostearyl lactate, isostearyl palmitate, octyldodecyl neodecanoate, isocetyl stearate, propylene glycol monoisostearate, ethyl-2-hexyl isostearate, octyldodecyl stearate, octyldodecyl myristate, diisostearyl adipate, octyl hydroxystearate, glyceryl triisostearate, octyldodecyl stearoyl stearate, diisocetyl dodecane dioate, dipentaerythrityl hexacaprylate / hexacaprate, octyl-2-dodecyl hydroxystearate, tetra-octyldodecanoate pentaerythrityl, tri-isostearyl citrate, pentaerythrityl tetra-2-hexyldecanoate, propylene glycol diisostearate, tridecyltetradecanoine, isostearyl isostearate, isofol 24 isostearate, triisocetyl citrate, diisopropyl dimer dilinoleate, pentaerythrityl tetradecyltetradecanoate;

4. diisostearyl malate (n= 1.46), diisoarachidyl dodecane di-oate, octyldodecyl erucate, triisoarachidyl citrate, hexyldecyl myristoyl methylaminopropionate, pentaerythrityl tetraisostearate, trimethylolpropane triisostearate, oleyl erucate, ditrymethylolpropane tetraisostearate, dioctyldodecyl dimer dilinoleate, ethyl panthenol, sucrose 6-8 soybean fatty chains, triisostearyl trilinoleate, octyl-2-dodecyl benzoate, ethyl-2-hexyl benzoate, isofol 12 trimellitate, C12-C15 alkylbenzoate, hydrogenated dimer dilinoleyl / dimethylcarbonate copolymer, tri-iso-decyl trimellitate, tri-decyl trimellitate, tri-ethyl-2-hexyl trimellitate, castor oil benzoate, dipropylene glycol dibenzoate, ethyl-2 hexyl glyceryl ether palmitate; - vegetable hydrocarbon oils, such as C5-36 fatty acid triglycerides (especially C6-12) and glycerol (n= 1.45-1.46) such as caprylic / capric triglycerides, arara oil, jojoba oil, pracaxi oil, virgin olive oil, meadowfoam oil, sesame oil, ximenia oil, soybean oil, macadamia oil, castor oil; - oils obtained by dimerization of fatty acids, in particular unsaturated fatty acids in C8-C20, such as dilinoleic acid (C36); - oils comprising polyoxypropylene (POP) or polyoxyethylenate (POE) groups, such as oxypropylene myristyl diadipate (3 OP), oxyethylenated glyceryl triacetate (7 OE), PEG-4 (40E), PEG-6 (60E), PEG (8 OE), octyldodecyl PPG-3 myristyl ether dimer dilinoleate; and - their mixtures, preferably the hydrocarbon oil with a refractive index n greater than or equal to 1.4 is a mixture: - of C5-C36 fatty acid triglycerides, particularly C6-C12, and glycerol, - diisostearyl malate and - dilinoleic acid. Composition according to any one of the preceding claims, wherein the hydrocarbon oil having a refractive index n greater than or equal to 1.4 is present in a concentration ranging from 5 to 50% by weight and more preferably from 8 to 40% by weight, and particularly 10 to 30% by weight relative to the total weight of the composition.

5. Composition according to any one of the preceding claims, wherein the aqueous phase consists essentially of water or comprises a mixture of water and a water-miscible solvent, preferably the water-miscible solvent is selected from lower monoalcohols having 1 to 5 carbon atoms, polyols and mixtures thereof.

6. Composition according to any one of the preceding claims, comprising a water content of at least 10% by weight, preferably at least 20% by weight, preferably a content of 20% to 40% by weight relative to the total weight of the composition; and / or a water-miscible solvent(s) content of between 2 and 15% by weight, preferably from 4 to 10% by weight, relative to the weight of the composition.

7. Composition according to any one of the preceding claims, wherein the emulsifying surfactant of HLB less than or equal to 8 is non-ionic, preferably selected from hydrocarbon non-ionic surfactants and mixtures thereof.

8. Composition according to any one of the preceding claims, wherein the emulsifying surfactant of HLB less than or equal to 8 is selected from polyoxyethylenated C8-C30 alcohols, (poly)oxyethylenated and / or (poly)oxypropylenated alkyl(C8-C30)- and polyalkyl(C8-C30)- esters; polyoxyethylenated fatty acid polyesters, preferably polyhydroxylated, in Ci2-C2o, having from 4 to 50 moles of ethylene oxide; alkyl- and polyalkyl- esters of sorbitan; alkyl- and polyalkyl- esters of (poly)glycerol; hydrocarbon surfactants resulting from the esterification of a mixture of polyglycerol with (i) a polyhydroxystearic acid, (ii) aliphatic dicarboxylic acids, linear or branched having 4 to 14 carbon atoms, or (iii) saturated or unsaturated fatty acids, linear or branched having 16 to 20 carbon atoms; and mixtures thereof;preferably the composition comprises a mixture of a polyhydroxylated fatty acid polyester, in Ci2-C20, polyoxyethylenated having 4 to 50 moles of ethylene oxide, and polyglyceryl-4 diisostearate polyhydroxystearate sebacate.;

9. Composition according to any one of the preceding claims, wherein the emulsifying surfactant of HLB is less than or equal to 8 is present in a content ranging from 0.1 to 15%, preferably from 1 to 12% and even more preferably from 2 to 10% by weight relative to the total weight of the composition.

10. Composition according to any one of the preceding claims, wherein the lipophilic film-forming polymer is a silicone resin.

11. Composition according to any one of the preceding claims, wherein the lipophilic film-forming polymer is present in a content of at least 5% by weight, preferably in a content of 5 to 20% by weight relative to the total weight of the composition, or better yet 6 to 15% by weight, relative to the total weight of the composition.

12. Composition according to any one of the preceding claims, wherein the lipophilic film-forming polymer is a silicone resin of type MQ, preferably a siloxysilicate resin, preferably an alkylsiloxysilicate resin, preferably Trimethylsiloxysilicate.

13. A composition according to any one of the preceding claims, wherein the hydroxy acid is selected from α-hydroxy acids and their derivatives, γ-hydroxy acids and their derivatives, polyhydroxy acids, and mixtures thereof; preferably the α-hydroxy acid is selected from glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, mandelic acid and their salts; more preferably, the α-hydroxy acid is selected from glycolic acid, citric acid, lactic acid, their salts and mixtures thereof, and even more preferably, the α-hydroxy acid is lactic acid; the γ-hydroxy acid is a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid; and the polyhydroxy acid is selected from lactobionic acid, gluconic acid, gluconolactone, ribonolactone and mixtures thereof.

14. A composition according to any one of the preceding claims, comprising at least one 3-hydroxy acid, preferably in a mixture with at least one α-hydroxy acid and / or at least one polyhydroxy acid; preferably comprising a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid, preferably in a mixture with at least one α-hydroxy acid selected from glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, mandelic acid and their salts and / or in a mixture with at least one polyhydroxy acid selected from lactobionic acid, gluconic acid, gluconolactone, ribonolactone and mixtures thereof; advantageously comprising a mixture of salicylic acid and 5-(n-octanoyl)salicylic acid, preferably in mixture with lactic acid and / or gluconolactone.

15. Composition according to any one of the preceding claims, wherein the hydroxy acid(s) is / are present in the composition in an active substance content of 0.1 to 15%, preferably 0.3 to 10% by weight, preferably 0.5 to 8% by weight, preferably 1 to 6% by weight relative to the total weight of said composition.

16. Composition according to any one of the preceding claims, wherein the colouring material is selected from colourants, pigments, mother-of-pearls and mixtures thereof; preferably it is present in a content from 0.1% to 25% by weight, relative to the weight of the composition, preferably from 0.5% to 20% by weight, preferably from 1% to 20% by weight.

17. Composition according to any one of the preceding claims, further comprising at least one additional cosmetic ingredient selected from hydrophobic thickeners, fillers of organic or mineral nature, antioxidants, perfumes, preservatives, neutralizers, sequestrants, active ingredients and mixtures thereof.

18. A composition according to any one of the preceding claims, further comprising a phosphonic derivative of the following formula (I): where R represents a saturated linear cyclic alkyl radical, comprising from 1 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, preferably from 5 to 7 carbon atoms, and n represents an integer from 1 to 10, preferably from 4 to 8, preferably from 5 to 7 such that 6, the phosphonic derivative of formula (I) advantageously being phytic acid; preferably, the amount of phosphonic derivative(s) ranges, for example, from 0.01 to 5% by weight and preferably from 0.1 to 1% by weight of active material relative to the total weight of the composition.

19. A method for making up or caring for keratinous materials, and in particular for the complexion, in which a composition as defined in one of the preceding claims is applied to the keratinous materials, and in particular to the skin of the face.