INVERSE EMULSION COMPRISING PULLULAN, AN APOLAR HYDROCARBON OIL, A SILICONE FILMLOGEN POLYMER, A COLORING MATERIAL AND MAKE-UP PROCESS

Abstract

Title: INVERSE EMULSION COMPRISING PULLULAN, AN APOLAR HYDROCARBON OIL, A SILICONE FILMLOGENE POLYMER, A COLOURING MATERIAL AND MAKE-UP METHOD USING IT The present invention relates to a cosmetic composition for making up human keratin materials, in particular the skin and / or the lips, preferably the lips, in the form of a water-in-oil emulsion, comprising: - at least 3% by weight of pullulan; - at least 12% by weight of at least one first apolar hydrocarbon oil comprising from 8 to 16 carbon atoms, - at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone acrylamide copolymers, and mixtures thereof, - at least one colouring material. It also relates to a makeup process, in which this composition is applied to said keratin materials.

Description

Title of the invention: INVERSE EMULSION COMPRISING PULLULAN, AN APOLAR HYDROCARBON OIL, A SILICONE FILMLOGEN POLYMER, A COLORING MATERIAL AND MAKE-UP PROCESS

[0001] The present invention relates to a cosmetic composition for makeup, in particular for the skin and / or the lips, preferably the lips, in the form of an inverse emulsion (therefore a water-in-oil emulsion) comprising at least 3% by weight of pullulan, at least one particular hydrocarbon oil, at least one silicone film-forming polymer and at least one coloring matter. The invention also relates to a makeup process using such a composition.

[0002] Compositions intended to be applied to the skin or to the lips, and providing a matte finish after application, are well known in the cosmetic field and most of the time have the characteristic of comprising high contents of volatile oils and / or fillers. The high content of volatile oil(s) makes it possible to further increase the content of solid particles in the deposit, such as fillers and pigments, once the composition has been applied and dried. As regards the fillers used in compositions providing a matte finish, organic particles are often found, in particular polymeric particles such as nylon, polytetrafluoroethylene, polyethylene, silicone resins or elastomers, or even mineral particles, such as kaolin, silica for example. These fillers make it possible, among other things, to partially absorb the remaining oily compounds, whether they come from the composition or from the support on which it is applied (sebum).With the high content of volatile oils and solid particles in compositions with a matte finish, the content of non-volatile oils is consequently greatly reduced in the deposit after application and drying of the composition. This is why matte compositions are generally considered by users to be little or not at all comfortable, once put in place, also leading to a more or less marked sensation of dryness.

[0003] In addition to the color effect provided on the skin and / or lips, we also seek to improve the hold and non-transfer properties of the compositions. Indeed, poor hold causes visible premature removal of the deposit (for example, a fading of the color), thus forcing the user to reapply makeup more often than desired to maintain an appropriate coloring. We also seek to limit the transfer of the composition to another support (clothing, cups, etc.), which limits staining problems and contributes in the majority of cases to maintaining good holding the deposit.

[0004] Improving the hold of the compositions is achieved by compositions forming a film after application. Such compositions generally contain volatile solvents which evaporate on contact with the skin or lips, leaving a layer comprising waxes and / or film-forming polymers, pigments and fillers. The film-forming polymers are synthetic polymers, often silicone or acrylic. Thus, mention may be made of the use of silicone resins, such as, for example, resins of the trimethylsiloxysilicate type (INCI name) or polypropylsilsesquioxane type (INCI name) or even comprising silicone polymers such as silicone acrylate dendrimer copolymers (acrylates / polytrimethylsiloxy-methacrylate copolymer (INCI name). Acrylic polymers of the Acrylic Acid / Isobutyl Acrylate / Isobutyl Acrylate Copolymer type are also used.However, these compositions are also very often considered less comfortable, or even uncomfortable, from a sensory point of view for consumers.

[0005] We are therefore always looking for makeup compositions which are more comfortable, without loss of hold performance, and this despite quantities of silicone film-forming polymers which could be reduced compared to those found in long-lasting makeup products on the market.

[0006] These and other problems are solved by the present invention which relates to a cosmetic composition for making up human keratin materials, in particular the skin and / or the lips, preferably the lips, in the form of a water-in-oil emulsion, comprising: - at least 3% by weight, relative to the total weight of the composition, of pullulan; - at least 12% by weight, relative to the total weight of the composition, of at least one first apolar hydrocarbon oil comprising from 8 to 16 carbon atoms, - at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone polyamides, and mixtures thereof, - at least one coloring matter.

[0007] The present invention also relates to a makeup process in which the aforementioned cosmetic composition is applied to human keratin materials, in particular the skin and / or the lips, preferably the lips.

[0008] The composition according to the invention has the advantage of being stable over time, easy to apply, without dewetting during application or blotting. The deposit obtained is also precise, homogeneous, non-stringy, with little or no stickiness.

[0009] The deposit also does not migrate into wrinkles and fine lines, especially around the lips.

[0010] The resulting deposit is finally matte to satin, with good hold. It is also comfortable, without leaving a feeling of dryness or tightness.

[0011] The composition according to the invention is therefore in the form of a water-in-oil emulsion, or inverse emulsion. In other words, the composition comprises an aqueous phase which is dispersed within the lipophilic phase, which constitutes the continuous phase of the emulsion.

[0012] The composition according to the invention is advantageously in the form of a liquid composition.

[0013] By “liquid composition” is meant any composition which has one or more of the following characteristics:

[0014] i) flows under its own weight at room temperature (20°C) and atmospheric pressure (1.013 .105 Pa);

[0015] ii) is not solid at room temperature and atmospheric pressure and of which it is possible to measure a viscosity or its consistency characterized by its hardness;

[0016] iii) does not have any particular shape such as that which can be obtained by hot casting in a mold or container of a given shape.

[0017] Such compositions can therefore be found in particular in fluid, creamy, pasty or gel form. Viscosity measurement protocol

[0018] The viscosity measurement is carried out with a sample of composition at 25°C, at least 24 hours after its manufacture (storage at room temperature), using a RHEOMAT RM 180 viscometer equipped with a spindle no. 2, 3 or 4, the measurement being carried out after 10 minutes of rotation of the spindle within the composition (time at the end of which a stabilization of the viscosity and the rotation speed of the spindle is observed), at a shear of 200 revolutions / min (rpm).

[0019] According to one embodiment, the composition according to the invention may have at 25°C a viscosity of between 2 and 20 Pa.s, preferably of between 3 and 15 Pa.s. PULLULANE

[0020] As previously indicated, the composition comprises pullulan.

[0021] Pullulan is a polysaccharide consisting of maltotriose units, known as α-(1,4)-α(1,6)-glucan. Three glucose units in maltotriose are connected by an α-(1,4) glycosidic bond, while consecutive maltotriose units are connected to each other by an α-(1,6) glycosidic bond. It is produced from starch by the fungus Aureobasidium pullulans.

[0022] Pullulan is for example produced under the commercial reference Pullulan PF 20® by the Hayashibara group in Japan or under the reference Aqua Beta® by the company Daiso, Co., Ltd like the product sold under the name Pullulan Cosmetic Grade® by the company Hayashibara.

[0023] The composition according to the invention comprises at least 3% by weight of pullulan, expressed as active ingredient, relative to the total weight of the composition. More particularly, the pullulan content is between 4 and 15% by weight, more particularly between 5 and 10% by weight, relative to the total weight of the composition. FIRST HYDROCARBON OIL

[0024] The composition further comprises at least one first apolar hydrocarbon oil comprising from 8 to 16 carbon atoms.

[0025] Oil is understood to mean any compound immiscible with water which is in liquid form at room temperature and atmospheric pressure.

[0026] By "immiscible in water" 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, at room temperature and atmospheric pressure. The observation is made by eye or by means of a phase contrast microscope if necessary, on 100g of mixture obtained after sufficient Rayneri stirring to cause a vortex to appear within the mixture (for information 200 to 1000 rpm); the resulting mixture being left to stand, in a closed bottle, for 24 hours at room temperature before observation.)

[0027] By "apolar hydrocarbon oil" is meant an oil chosen from hydrocarbons, that is to say from compounds comprising only carbon and hydrogen atoms.

[0028] The first apolar hydrocarbon oils which can be used in the context of the invention are more particularly chosen from oils having from 8 to 16 carbon atoms, linear or branched, preferably saturated, and their mixtures.

[0029] Advantageously, these oils are volatile.

[0030] By "volatile oil" is meant an oil having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 2.66 Pa to 40,000 Pa, in particular ranging to 13,000 Pa, and more particularly ranging to 1300 Pa (OECD standard 104).

[0031] The apolar hydrocarbon oils can thus be chosen from linear alkanes comprising from 8 to 14 carbon atoms.

[0032] Examples of linear alkanes, in particular C8-C14, that may be mentioned include n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), and mixtures thereof. Examples include n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references Parafol 12 97® and Parafol 14 97®, and mixtures thereof. According to another embodiment, a mixture of n-dodecane and n-tetradecane may be used, and in particular the dodecane / tetradecane mixture sold by the company Biosynthis under the reference Vegelight 1214®. According to yet another embodiment, also use a mixture of volatile linear C9-C12 alkanes with INCI name: C9-12 Alkane such as the product marketed by the company Biosynthis under the reference Vegelight SILK®. According to yet another embodiment, it is possible to use a mixture of n-undecane (C11) and n-tridecane (Cl3) such as those obtained in examples 1 and 2 of application WO2008 / 155059 (mixtures of distinct alkanes differing by at least one carbon) from the company Cognis and such as that sold under the trade name Cetiol Ultimate® by the company BASF.

[0033] Mention may also be made of the alkanes described in the patent applications of the company Cognis WO 2007 / 068371. These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

[0034] The hydrocarbon oils that can be used in the compositions according to the invention can be chosen from branched C8-C16 alkanes. Mention may in particular be made of C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopar® or Permetyl®.

[0035] According to a particularly preferred embodiment, the first is chosen from isododecane, the mixture of linear C9-C12 alkanes (INCI name: C9-12 Alkane), and the mixture of n-undecane (Cl 1) and n-tridecane (C13), and their mixtures.

[0036] Preferably, the content of first apolar hydrocarbon oil(s) represents from 12 to 40% by weight, preferably from 12 to 35% by weight, relative to the total weight of the composition. SILICONE FILM-FORMING POLYMER

[0037] As indicated previously, the composition according to the invention comprises at least one silicone film-forming polymer chosen from non-glycerolated silicone resins; glycerolated silicone resins; silicone vinyl copolymers, such as vinyl polymers grafted with a carbosiloxane dendrimer, silicone acrylate copolymers; silicone polyamides; as well as mixtures thereof. Non-glycerolated silicone resin

[0038] More generally, the term "resin" means a compound whose structure is three-dimensional. Thus, for the purposes of the present invention, a poly(ethylsiloxane) is not a silicone resin.

[0039] 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 that it comprises, each of the letters "MDTQ" characterizing a type of unit: The letter "M" represents the Monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being linked to a single oxygen atom in the polymer comprising this unit. The letter "D" stands for a difunctional unit RlR2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms. The letter "T" represents a Trifunctional unit of formula RlSiO3 / 2.

[0040] In the M, D, T units 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. 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.

[0041] Such resins are described for example in "Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), pp. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

[0042] Various silicone resins with 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 pendant chains.

[0043] As silicone resins which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of the MQ type, of the T type or of the MQT type. MQ Resins

[0044] As an example of silicone resins of MQ type, mention may be made of siloxysilicate type resins such as alkyl siloxysilicates, aryl siloxysilicate or alkylaryl siloxy-silicates, of formula [(Rl)3SiOi / 2]x(SiO4 / 2)y (MQ units) in which x and y are integers ranging for example from 50 to 80, and such that the group RI 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,

[0045] The silicone resin can be used alone or in the form of a mixture in an oil, which can in particular be chosen from the first and second oil(s) as well as their combinations.

[0046] Examples of MQ type silicone resins of Trimethylsiloxysilicate type (INCI name) include those marketed under the reference SR 1000 by the company General Electric, under the reference TMS 803 by the company Wacker, or even mixtures comprising it such as the products marketed under the names KF-7312J (in cyclopentasiloxane) by the company Shin-Etsu, “Silsoft 74 Fluid (in isododecane) by Momentive, Dowsil RSN-749 resin (in cyclopentasiloxane), Dowsil 593 Fluid (in dimethicone) by Dow Corning.

[0047] As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as Phenylpropyl-dimethylsiloxysilicate (INCI name; Silshine 151 marketed by the company General Electric). The preparation of such resins is described in particular in patent US5817302. T resins

[0048] As examples of T-type silicone resins, mention may be made of polysilsesquioxanes comprising mainly units of 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 being able to further comprise Si-OH end groups. Thus, these resins comprise, for example, at least 80 mol% of T units.

[0049] Mention may be made of polymethylsilsesquioxanes which are polysilsesquioxanes in which none of the methyl radicals is substituted by another group. Such polymethylsilsesquioxanes are described for example in document US 5,246,694.

[0050] Preferably, it is possible to use Polymethylsilsesquioxane resins (INCI name) in which R represents a methyl group, such as for example those marketed by the company Wacker under the reference Resin MK such as Belsil PMS MK by the company Shin-Etsu under the references KR-220L, or under the reference KR-251. Also suitable are Polymethylsilsesquioxane resins mixed with solvents, such as for example Granresin PMSQ-C9 (Polymethylsilsesquioxane (and) C9-12 Alkane), Granresin PMSQ-ID (Polymethylsilsesquioxane (and) isododecane), from the company Grant Industries.

[0051] Among the silsesquioxane resins which can be used in the present invention, mention may also be made of those corresponding to silsesquioxane homopolymers and / or copolymers having an average siloxane unit of general formula Rln SiO(4-n) / 2, in which each RI is a propyl group, in which more than 80 mol% of RI represents a C3 to C10 alkyl group, n is a value of 1.0 to 1.4, and more than 60 mol% of the copolymer comprises RlSiO3 / 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.

[0052] Among the polypropylsilsesquioxane resins suitable for use in the present invention, mention may be made of those marketed by Dow Corning under the names nominations Dowsil 670 Fluid or Dowsil 680 ID Fluid, which are mixtures of Poly-propylsilsesquioxane respectively with cyclopentasiloxane or with isosodecane, or the product Dowsil MQ-1640 Flake Resin, from Dow, comprising a mixture of Trimethylsiloxysilicate and Polypropylsilsesquioxane. MQT Resins

[0053] As a resin comprising MQT units, those cited in document US 5110890 are known in particular.

[0054] A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins which can be used in the compositions according to the invention are in particular those described and prepared in application WO 2005 / 075542.

[0055] The MQ-T-propyl resin preferably comprises the units: (i) (Rl3SiO1 / 2)a (ii) (R22SiO2 / 2)b (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d 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 molar 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 = 1; provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

[0056] Preferably, the siloxane resin comprises the units: (i) (Rl3SiO1 / 2)a (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)davec RI and R3 independently representing 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 between 0.2 and 0.55; a + b + c + d = 1, and a, b, c and d being mole fractions; provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups. Glycerolated silicone resin

[0057] The composition according to the invention may also comprise at least one glycerolated silicone resin.

[0058] The glycerolated silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol group(s).

[0059] In particular, the glycerolated silicone resin contains at least one organosiloxane unit of the type RR'R”SiOi / 2 in which R, R' and R'”, identical or different, denote hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerolated silicone resin contains at least one dimethylsiloxane unit R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

[0060] By “hydrocarbon radical” is meant a radical containing hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

[0061] The glycerolated silicone resin(s) according to the invention are preferably chosen from those of the following formula (1). (R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (1) in which - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - each R2 is a mono- or poly-glycerol group of the following general formula (2) -(CH2)2—CiH2i—O—(CH2CH(OH)CH2O);R4 (2), in which R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and the indices 1 and i are integers which satisfy the conditions 0 < 1 < 15 and 0 <i< 5, - each R3 is an identical or different group of general formula (3), (4), (5) or (6) below: —(CH2)2—CmH2m—(SiOR^j—SiR>3 (3) —(CH2)2—CmH2m—SiR'kl—(OSiR'3)3 kl) (4) —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (5) —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 kl (6) where - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - the indices m, j and ki to k3 are integers which satisfy the following conditions: 0 <m<5, 0<j<500, 0<kl<2, 0<k2<2 et 0<k3<2 ; - the indices a, b, c, d, e and f are numbers that satisfy the following conditions: 0 <a<400, 0<b<200, 0<c<400, 0<d<320, 0<e<320, 0<f<1000 et 0,5<(a+b+c) / f<l,5.

[0062] The glycerolated silicone resins according to the invention are described in the application of patent US20200332065 from Shin Etsu.

[0063] According to a particular embodiment, the glycerolated silicone resin(s) of formula (1) as defined above are chosen from those whose indices b and c satisfy the conditions 0 <b<30 et 0<c<30 ; et dont l'indice i dans la formule générale (2) du groupe monoglycérol ou polyglycérol R2, est un nombre entier qui satisfait à la condition 0<i<3.

[0064] According to a particular embodiment, the glycerolated silicone resin(s) of formula (1) are in solid form at 25°C when the index c satisfies the condition 0 <c<400 et R3 est un groupe de formule générale (3) où l'indice j satisfait à la condition 0<j< 10.

[0065] According to a particular embodiment, the glycerolated silicone resin(s) have a weight-average molecular weight ranging from 1000 to 100000.

[0066] The glycerolated silicone resin(s) are amphiphilic, i.e. they have two parts of different polarity. In general, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (Hydrophilic Lipophilicity Balance), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and is described for example in "The HLB System. A time-saving guide to Emulsifier Selection” published by ICI Americas Inc; 1984). The HLB value of the glycerolated silicone resins according to the invention preferably varies from 0.1 to 15 according to the GRIFFIN method.

[0067] The glycerolated silicone resin(s) may be obtained by a preparation process comprising the hydrosilylation step A) of a silicone resin containing a hydrosilyl group of formula (7) below. (R13SiO1 / 2)aHnR>3nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (7) in which: - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 <a<400, 0<b<200, 0<c<400, 0<d<320, 0<e<320, 0<f <1000 et 0,5<(a+b+c) / f<l,5 ; - n is an integer that satisfies condition l <n<3, avec B) one or more compounds which are selected from the compounds terminated by an alkenyl group of general formulas (8), (9), (10), (11) and (12) below. CH2=CH-CiH21-O-(CH2CH(OH)CH2O)iR4(8) CH2=CH-CmH2m-(SiOR12)j-SiR13 (9) CH2=CH—CmH2m—SiR'kl—(OSiR'3)3 kl (10) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (11) CH2=CH—CmH2m—SiR'k1—(OSiR1k2(OSiR1k3(OSiR13)3k3)3k2)3ki(12) where - R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, - the indices 1, and i are integers that satisfy the conditions 0 <l< 15, 0<i<5 ; - les indices m, j et ki à k3 sont des entiers qui satisfont aux conditions 0<m<5, 0<j<500, 0<ki<2, 0<k2<2 et 0<k3<2 ; ladite résine siliconée contenant un groupe hy-drosilyle de formule (7) réagissant avec au moins un composé de formule (8).

[0068] The hydrosilylation reaction is carried out in the presence of, for example, a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R4,1, m, i, j and ki to k3 are as defined above.

[0069] Silicone resin containing a hydrosilyl group used as starting material.

[0070] The silicone resin containing a hydrosilyl group of formula (7) may be in a solid or liquid form at 25°C, preferably solid. From the point of view of processing, the resin is preferably diluted with an organic solvent. The use of a solvent whose boiling point is higher than the reflux temperature during hydrolysis is preferred.

[0071] Examples of organic solvents used for dilution include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol.From the point of view of storage stability and lack of volatility, octamethylcyclotetrasiloxane and decamethylcyclopenta-siloxane are preferred.

[0072] The silicone resin containing a hydrosilyl group of formula (7) is prepared: i) by hydrolyzing, in the presence of an acid catalyst, a mixture of one or more compounds chosen from the organosilicon compounds of general formulas (13) and (14) below, one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) below and one or more compounds chosen from the hydrolyzable silanes of general formula (17) below, the partial hydrolytic condensates of these hydrolyzable silanes and the metal salts of these hydrolyzable silanes: RSSiOSiRS (13) RSSiX1 (14) HnR>(3 n)SiOSiR>(3 n)Hn (15) HnR'(3 n)SiX2 (16) where each R1, the same or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted group, an amino-substituted group or a carboxyl-substituted group thereof; X1 and X2 are hydrolyzable functional groups; and n satisfies condition l <n<3 ; SiX34 (17) where X3 is a hydrolyzable functional group); ii) by neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acid catalyst, and iii) by then carrying out a condensation.

[0073] In general formulas (13), (14), (15) and (16), the examples and preferred range for R1 are the same as those mentioned above.

[0074] In general formula (14), X1 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred.

[0075] In general formula (16), X2 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred.

[0076] In general formula (17), X3 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, an alkoxy group is preferred; from the viewpoints of availability and hydrolysis rate, a methoxy group or an ethoxy group is preferred. The hydrolyzable groups X3 on the molecule may be the same or different groups.

[0077] Examples of organosilicon compounds of general formula (13) include 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,1,3,3-pentavinylmethyldisiloxane, 1,1,1,3,3-n-octylpentamethyl-disiloxane, 1,1,1,3,3-chloromethylpentamethyldiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Of these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

[0078] Examples of organosilicon compounds of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane and triphenylethoxysilane. Of these, trimethylchlorosilane and trimethylethoxysilane are preferred.

[0079] Examples of organosilicon compounds containing a hydrosilyl group of general formula (15) include 1,1,3,3-tetramethyldisiloxane and 1,1,1,3,3-pentamethyldisiloxane. 1,1,3,3-Tetramethyldisiloxane is particularly preferred.

[0080] Furthermore, in general formulas (15) and (16), n satisfies the condition l <n<3. Dans la formule générale (15), le "n" associé à l'atome d’hydrogène et au R1 liés à un atome de silicone et le "n" associé à l'atome d’hydrogène et au R1 liés à l'autre atome de silicone peuvent être identiques ou différents.

[0081] Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0082] Examples of hydrolyzable silane of general formula (17) include tetrachlorosilane, tetramethoxysilane and tetraethoxysilane. Examples of partial hydrolysis condensates of hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silane include water glass, sodium silicate and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0083] In this invention, to a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes may be added. lysable before hydrolysis under an acid catalyst, or a mixture of one or more compounds selected from organosilicon compounds of general formula (18) or general formula (19) may be added after such hydrolysis and before the rehydrolysis described later: R'SiX43 (18); R^SiX^ (19) where each R1 is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted group, an amino-substituted group or a carboxyl-substituted group thereof; X4 and X5 are hydrolyzable functional groups.

[0084] In general formulas (18) and 19), the examples and preferred ranges for R1 are the same as those mentioned above.

[0085] In general formula (18), X4 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X4 on the same molecule may be the same or different.

[0086] In general formula (19), X5 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X5 on the same molecule may be the same or different.

[0087] Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane and methyltrichlorosilane. Among these, methyltrimethoxysilane, methyltriethoxysilane and methyltrichlorosilane are preferred.

[0088] Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropro-pyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane and dimethyldichlorosilane. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane are preferred.

[0089] A specific example of a method for preparing the hydrosilyl group-containing silicone resin serving as a raw material in the present invention is described. A solvent (particularly, an organic solvent) and a hydrolysis raw material (a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14), one or more compounds selected from hydrosilyl group-containing organosilicon compounds of general formulae (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes, and metal salts of these hydrolyzable silanes) are charged into a reactor, an acid is added as a catalyst, and water is added dropwise with stirring. It is also possible in this case to add the organic solvent after completing the dropwise addition of water.Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0090] The temperature during the dropwise addition of water is preferably between 0 and 80°C, and more preferably between 0 and 50°C. By maintaining the temperature in this range, the heat of reaction of the hydrolysis reaction on the starting product of hydrolysis in the system can be kept low. The amount of water added dropwise, expressed as a molar ratio per mole of hydrolyzable functional groups (alkoxy groups, etc.) is between 0.6 and 2, and preferably between 1.0 and 1.8. By maintaining the amount of water added in this range, it is possible to further suppress the deactivation of the hydrosilyl groups.

[0091] In order to suppress a decrease in the reaction rate due to retention and increase in viscosity of the uniform reaction system during the hydrolysis reaction, it is preferable to use an organic solvent as the solvent in the hydrolysis reaction. It is also desirable to use a solvent whose boiling point is higher than the reflux temperature during the hydrolysis.

[0092] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane.

[0093] In some cases, an alcoholic solvent of 1 to 10 carbon atoms may be used concomitantly. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. As solvents Since alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol and 2-propanol are particularly preferred.

[0094] The solvent used is included in an amount, relative to the overall reaction system, of 1 to 80% (here and below, "%" refers to the percentage by weight), and in particular of 5 to 50%. Within this range, the reaction system remains uniform and the reaction proceeds efficiently.

[0095] Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. The acid catalyst may be used in a small amount, with an amount in the range of 0.001 to 10% of the overall reaction system being preferred.

[0096] After adding the water dropwise as mentioned above, the hydrolysis reaction is carried out by heating the system at a temperature of 50 to 150°C, preferably 80 to 120°C, for about 2 to 8 hours. Meanwhile, by carrying out the reaction at a temperature lower than the boiling temperature of the hydrosilyl group-containing organic compound used, the deactivation of the hydrosilyl groups can be further suppressed.

[0097] After carrying out the hydrolysis in this manner on the starting product of the above hydrolysis in the presence of an acid catalyst, the system is cooled to a temperature of between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably to 25°C.

[0098] After the above hydrolysis, the system is neutralized at 10 to 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this time, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is suppressed, and the condensation reaction of the organosilicon resin is further promoted. Examples of such strongly basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate.Regarding the combinations of a strong basic catalyst with a weak basic catalyst, from the point of view of ease of obtaining a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, which makes it possible to more reliably obtain a high molecular weight organosilicon resin. lecular containing hydrosilyl groups.

[0099] The basic catalyst should be used in an amount greater than the molar equivalent of the acid catalyst. Carrying out the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, resulting in an increase in molecular weight and making it possible to obtain a high molecular weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the addition amount within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, making it possible to obtain a resin of target molecular weight.

[0100] After neutralization, the formed alcohols, the solvent and the excess water can be removed by heating between 95 and 120°C under normal or reduced pressure. Then, after confirming that the formed alcohols, the solvent and the excess water have been removed, the condensation reaction is carried out by heating between 120 and 150°C for about 2 to 5 hours. An organosilicon resin containing a hydrosilyl group is thus obtained.

[0101] In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio of the combined molar amount of the compounds of general formulas (13), (14), (15) and (16) to the molar amount of SiO4 / 2 units in the compound of general formula (17), expressed as the molar ratio ((13)+(14)+(15)+(16)):(19), is preferably 0.3:1 to 2:1, and more preferably 0.6:1 to 1.3:1.

[0102] Furthermore, the ratio of the combined molar amount of the compounds of general formulae (13) and (14) to the combined molar amount of the compounds of general formulae (15) and (16), expressed as the molar ratio ((13)+(14)):((15)+(16)), is preferably 0.3:1.0 to 2.0:1.0, and more preferably 0.6:1.0 to 1.3:1.0. By setting the values ​​within these ranges, the amount of hydrosilyl groups included in the hydrosilyl group-containing organosilicon resin can be quantitatively varied more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulae (15) and (16) are charged, it is possible to quantitatively vary the amount of hydrosilyl groups included on the organosilicon resin.

[0103] In the process described above for preparing a silicone resin containing hydrosilyl groups, after having carried out the hydrolysis, in the presence of an acid catalyst, of a mixture of one or more compounds chosen from organosilicon compounds of general formulas (13) and (14) with one or more compounds chosen from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, it is also possible to gradually add, drop by drop, one or more compounds chosen from organosilicon compounds containing a hydrosilyl group, of general formulas (15) and (16).

[0104] Next, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably carried out by heating at a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example at a temperature preferably between 40 and 150°C, and more preferably between 40 and 120°C, for about 2 to 8 hours. When the reaction is carried out in this temperature range, deactivation of the hydrosilyl groups can be further suppressed.

[0105] In the process of preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups become deactivated, may occur: SiOi / 2Hn R3-n' (M units) + -Si-OH -> -Si-O-SiOi / 2Hn iR3 n' (D units) (20) where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

[0106] However, by appropriately fixing the order in which the raw materials are added, i.e., by hydrolyzing a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14) with one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, and then adding one or more compounds selected from hydrosilyl group-containing organosilicon compounds of general formulae (15) and (16) and carrying out rehydrolysis, the above reaction (20) can be kept to a minimum. This reaction can be further suppressed by skillfully changing the amounts in which the raw materials are added and the type of catalyst used.

[0107] The amount of hydrosilyl groups included in the thus obtained hydrosilyl group-containing organosilicon resin is easily adjustable, and it is even possible to introduce a large amount of hydrosilyl groups, by varying the amount of the hydrosilyl group-containing organosilicon compound that is charged. Furthermore, by varying the amount of hydrolysis starting materials used, the type and amount of acid catalyst added, the reaction temperature and time, the amount of solvent added and the addition method, the molecular weight range, shape and other characteristics of the organosilicon resin can be adjusted, thereby preparing a hydrosilyl group-containing organosilicon resin for the intended application.

[0108] The silicone resin containing a hydrosilyl group obtained as described above has the average formula (7) above and is composed of Q units (SiO4 / 2) and M units ((RSSiOi / 2) and (HnRS nSiOi^)) as essential constituents, and also D units (R12SiO2 / 2) and T units (R1SiO3 / 2) as optional constituents. It can be in the form of a solid or a liquid at 25°C, although from the point of view of film formability it is preferably a solid. Examples include MQ resins, MTQ resins, MDQ resins and MDTQ resins. The weight average molecular weight is preferably between 2,000 and 30,000, although the range of 3,000 to 15,000 is more preferred from the point of view of performance and ease of carrying out operations such as filtration. The weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GC).

[0109] Process for the preparation of glycerol silicone resin

[0110] A specific example of a process for preparing the glycerolated silicone resin according to the invention is described below.

[0111] As mentioned above, the glycerolated silicone resin according to the invention can be obtained by the hydrosilylation step: (A) of a silicone resin containing a hydrosilyl group of average formula (7) below: (R13SiO1 / 2)a(HnR13nSiO1 / 2)b+c(R12SiO2 / 2)d(RiSiO3 / 2)e(SiO4 / 2)f (7) in which - each R1 is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 ​- n is an integer that satisfies the condition 1 < n < 3 with (B) one or more compounds which are selected from alkenyl-terminated compounds of general formulae (8), (9), (10), (11) and (12) below. CH2=CH-CiH2i-O-(CH2CH(OH)CH2O)iR4(8) CH2=CH-CmH2m-(SiOR12)j SiR>3 (9) CH2=CH—CmH2m—SiR'kl—(OSiR'3)3 kl (10) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 ki (11) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 ki (12) where - R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, - indices 1 and i are integers that satisfy the conditions 0 <l< 15 et 0<i<5 ; - les indices m, j et ki à k3sont des entiers qui satisfont aux conditions 0<m<5, 0<j<500, 0<ki<2, 0<k2<2 et 0<k3<2 ; ladite comprend un composé de formule générale (8).

[0112] The organosilicon resin containing hydrosilyl groups of average composition formula (7) and the compound having terminal alkenyl groups of general formula (8), (9), (10), (11) or (12) are mixed in a molar ratio, expressed as hydrosilyl groups / terminal unsaturated groups, which is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2.

[0113] The addition reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinyl siloxane complexes. When an excessive amount of the catalyst is included, discoloration of the sample occurs, and thus the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0114] Furthermore, if necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type solvents such as acetone, methylethylketone, diethylketone and methylisobutylketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol.From the point of view of reactivity, ethanol, 1-propanol and 2-propanol are preferred.

[0115] The amount of solvent used is preferably 1 to 80%, and more preferably 5 to 50%, of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0116] The conditions of the addition reaction are not particularly limited, although refluxing at a temperature of 50 to 150°C, particularly 80 to 120°C, for about 1 to 10 hours is preferred.

[0117] After the addition reaction, the step of removing the rhodium or platinum catalyst used with the activated carbon may be included. The amount of activated carbon used is preferably 0.001 to 5.0%, and especially 0.01 to 1.0%, of the overall system. By setting the amount of activated carbon in this range, the discoloration of the sample can be better removed.

[0118] After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups can be included. Especially in cases where use in applications such as cosmetic preparations is intended, there is a possibility that these hydrosilyl groups may deactivate over time due to dehydrogenation reactions, which is a problem from a safety point of view. It is therefore preferable to include a step of maintaining the hydrosilyl groups.

[0119] An example of a step for removing hydrosilyl groups is the method of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, and then neutralizing by adding an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of the basic catalyst include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the viewpoint of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being particularly preferred.Acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. In general, instead of using the acid or base alone, it is better to use them with water and heat them to a temperature not higher than the boiling point of water.

[0120] After the addition reaction, if necessary, a deodorization step to reduce the odor can be included. When use in applications such as cosmetic preparations in particular is intended, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common polyether-modified silicones can be explained as follows. When an addition reaction between an allyl-etherified polyether and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as side reactions, forming a propenyl-etherified polyether. This propenyl-etherified polyether has no reactivity with the polyorganosiloxane hydrogen, and therefore remains in the system as an impurity.It is believed that when water acts on this propenyl etherified polyether, the propenyl ether hydrolyzes, giving rise to propionaldehyde, which has an unpleasant odor. The reaction is known to . The above hydrolysis reaction is further promoted in the presence of an acid catalyst. Therefore, when polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and causing the appearance of an unpleasant odor.

[0121] Typical examples of the deodorization step include two approaches. The first is that, by adding an acid catalyst to the solution after the addition reaction, all the propenyl ether remaining in the system is hydrolyzed and the propionaldehyde that forms is removed by strip purification (JP No. 2137062).

[0122] Specific examples of the acid catalyst used in the first approach include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. These acids are used in combination with water. In cases where it is necessary to remove the acid that has been used, it is preferable to use a low-boiling acid, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Similarly, from the point of view of treatment efficiency, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

[0123] The treatment temperature is preferably set at 80°C or lower in order to avoid oxidation of hydrophilic groups. The amount of acidic aqueous solution added is preferably set at 0.1 to 100% relative to the organosilicon resin modified with organic groups. The use of 5 to 30% is more preferred.

[0124] From the productivity point of view, the method of adding to the post-reaction solution an aqueous solution so as to adjust the pH to 7 or less and performing strip purification after stirring under heating is preferred. The strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to effectively purify the strip under these temperature conditions, it is preferable to carry out this operation under reduced pressure; when carried out at normal pressure, the operation is preferably carried out under a flow of inert gas such as nitrogen or argon.

[0125] The second approach is that in which, by adding hydrogen to the solution after the addition reaction, the unsaturated double bonds are alkylated (subjected to a hydrogenation reaction) and the formation of propionaldehyde over time is stably controlled (US Pat. No. 5,225,509; JP-A H07-330907).

[0126] Hydrogenation reactions include methods involving the use hydrogen and methods involving the use of metal hydrides, and there are also homogeneous reactions and heterogeneous reactions. These methods can be used alone, but it is also possible to use them in combination. However, given the advantage that there is no trace of the catalyst used in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is preferred.

[0127] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron and the like, in uncombined form or in compound form. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support may be, for example, activated carbon, silica, silica-alumina, alumina or zeolite. These catalysts may be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. In addition, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0128] It is preferable to carry out the hydrogenation reaction at a pressure generally between 1 and 100 MPa and between 50 and 200°C. The hydrogenation reaction can be carried out batchwise or continuously. When it is a batch process, the reaction time depends, for example, on the amount of catalyst and the temperature, but is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to a suitable fixed pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing, and it can therefore be determined by carefully monitoring a pressure gauge.

[0129] The amount of aldehyde included in the glycerol silicone resin which has been purified by this acid treatment and this hydrogenation treatment can be set at 70 ppm or less, preferably at 20 ppm or less, and more preferably at 10 ppm or less.

[0130] It is also possible to combine the two types of deodorization steps mentioned above. In the approach that involves acid treatment, decomposition and removal of the aldehyde compound is possible, but since there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehyde from this cannot be completely suppressed. In the approach that involves a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound that is formed due to this. However, the aldehyde condensate that forms with the condensation of a portion of the aldehyde remains in the system even after such treatment has been carried out and Removal by strip purification is also difficult. Therefore, by alkylating the unsaturated double bonds remaining when the solution following the addition reaction is subjected to hydrogenation, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible (WO2002 / 05588).

[0131] The weight average molecular weight of the glycerolated silicone resin of average formula (1) preferably ranges from 1000 to 100000; from the viewpoint of performance and ease of operations such as filtration, the weight average molecular weight preferably ranges from 3000 to 50000. Here and below, the weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GPC).

[0132] The glycerolated silicone resin according to the invention is in a form at 25°C which can be solid or liquid, from the point of view of the formability of the film, it is preferably solid.

[0133] In particular, the glycerolated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b< 30 et 0<c<30, l'indice i dans la formule générale (2) est un nombre entier qui satisfait à la condition 0<i<3 et l'indice j dans la formule générale (3) satisfait à la condition 0<j< 10 est sous la forme d'un solide à 25°C et présente, de préférence une masse moléculaire moyenne en poids qui varie de préférence comprise de 1000 à 100000 et plus préférentiellement, de 3000 à 50000.

[0134] The glycerolated silicone resins according to the invention have a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, preferably from 0.1 to 15, and more preferably from 1.0 to 8.0.

[0135] According to a preferred form, the composition of the invention comprises at least one glycerolated silicone resin of formula (1) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type corresponding to the following formula (21):

[0136] [(CH3)3SiO1 / 2]a [R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) Or - R denotes the 3-glyceroxypropyl group of structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers which satisfy the conditions 0 <a<400, 0<b<30, 0<f<1000 et 0,5<(a+b) / f<l,5.

[0137] According to a particularly preferred form, the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil, chosen more particularly from hydrocarbon oils, silicone oils, and their mixtures.

[0138] Preferably, the composition according to the invention comprises, as silicone resin, at least one non-glycerolated silicone resin chosen from alkylsiloxysilicate, aryl- siloxysilicate, alkylarylsiloxysilicate, polysilsesquioxane, as well as mixtures thereof; more particularly among the non-glycerolated silicone resins with the following INCI names: Trimethylsiloxysilicate, Phenylpropyldimethylsiloxysilicate, Polymethylsil-sesquioxane, Polypropylsilsesquioxane, as well as mixtures thereof. Silicone vinyl copolymers

[0139] The term “vinyl polymer” means any polymer comprising a main chain (or skeleton) formed from at least one hydrocarbon monomer of the type RiR2C=CR3R4 comprising at least one ethylenic double bond, where Rh R2, R3, R4, identical or different, denote a hydrogen atom or a hydrocarbon group, in particular at least one monomer chosen from acrylic acid, methacrylic acid and its esters.

[0140] By "monomer or hydrocarbon group" is meant any molecule consisting of carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

[0141] Preferably, the film-forming silicone vinyl polymer(s) are chosen from vinyl polymers grafted with a carbosiloxane dendrimer, copolymers comprising (meth)acrylic groups and poly-dimethylsiloxane groups; mixtures thereof.

[0142] Vinyl polymers grafted with a carbosiloxane dendrimer

[0143] A vinyl polymer suitable for preparing a composition according to the invention comprises at least one carbosiloxane dendrimer-derived unit. The vinyl polymer has a vinyl (and therefore hydrocarbon) backbone and at least one side chain, which comprises a carbosiloxane dendrimer-derived unit having a carbosiloxane dendrimer structure.

[0144] The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular weights, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described as a highly branched siloxane-silylalkylene copolymer in Japanese patent application JPH11001530.

[0145] A vinyl polymer according to the invention may contain units derived from carbosiloxane den-drimers which may be represented by the following general formula (I):

[0146] [Chem.l] (I)

[0147] in which:

[0148] - R1 represents an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 with 10 carbon atoms;

[0149] - X' represents a silylalkyl group which, when i = 1, is represented by the formula (II):

[0150] [Chem.2] -R —Yes (II)

[0151] in which:

[0152] . R1 is as defined above in formula (I),

[0153] . R2 represents an alkylene radical of 2 to 10 carbon atoms,

[0154] . R3 represents an alkyl group of 1 to 10 carbon atoms,

[0155] . Xi+i is chosen from: a hydrogen atom, an alkyl group of 1 to 10 atoms of carbon, an aryl group of 5 to 10 carbon atoms and a silylalkyl group defined above of formula (II) with i = i + 1,

[0156] . i is an integer from 1 to 10 which represents the generation of said group if lylalkyl, and

[0157] . a' is an integer from 0 to 3;

[0158] - Y represents an organic group polymerizable by radical means chosen from:

[0159] . organic groups containing a methacrylic group or an acrylic group, said organic groups being represented by the formulas:

[0160] Or

[0161] [Chem.3] R4 OR* O

[0162] in which:

[0163] - R4 represents a hydrogen atom or an alkyl group of 1 to 10 atoms of carbon; and

[0164] - R5 represents an alkylene group of 1 to 10 carbon atoms, such as a group methylene, ethylene, propylene, or butylene, with methylene and propylene groups being preferred; and

[0165] . organic groups containing a styryl group of formula:

[0166] [Chem.4]

[0167] in which:

[0168] - R6 represents a hydrogen atom or an alkyl group of 1 to 10 atoms of carbon, such as a methyl group, an ethyl group, a propyl group, or a butyl group, with the methyl group being preferred;

[0169] - R7 represents an alkyl group of 1 to 10 carbon atoms;

[0170] - R8 represents an alkylene group of 1 to 10 carbon atoms, such as a group methylene, ethylene, propylene, butylene, the ethylene group being preferred;

[0171] - b is an integer from 0 to 4; and

[0172] - c is 0 or 1, so that if c is 0, -(R8)c- represents a bond.

[0173] According to one embodiment, R1 may represent an aryl group having from 5 to 10 carbon atoms or an alkyl group having from 1 to 10 carbon atoms. The alkyl group may preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group. The aryl group may preferably be represented by a phenyl group and a naphthyl group. Methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred.

[0174] According to one embodiment, R2 represents an alkylene group having from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene or 1,4-dimethylbutylene group. The ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are most preferred.

[0175] According to one embodiment, R3 is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.

[0176] In formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.

[0177] A vinyl polymer suitable for the present invention, having at least one carbosiloxane dendrimer-derived unit having a side molecular chain containing a carbosiloxane dendrimer structure, may be derived from the polymerization:

[0178] (A) from 0 to 99.9 parts by weight of a vinyl monomer; and

[0179] (B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a group organic polymerizable by radical route, represented by the general formula (I) as defined above.

[0180] The vinyl-type monomer which is component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-derived unit is a vinyl-type monomer which contains a radical-polymerizable vinyl group.

[0181] There is no particular limitation with respect to such a monomer. The following are examples of such a vinyl-type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower alkyl methacrylate analog; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher analogous methacrylate; vinyl acetate, vinyl propionate, or a lower analogous fatty acid vinyl ester;vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher fatty acid ester analog; styrene, vinyl toluene, benzyl methacrylate, phenoxyethyl methacrylate, vinyl pyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide, or analogous vinyl monomers that contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or analogous vinyl monomers that contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or similar vinyl-type monomers that contain a carboxylic acid group;tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, or a similar vinyl monomer with ether linkages; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a similar silicone compound having unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether;an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or; fumaric acid; a radically polymerizable unsaturated monomer having a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol having a tertiary amine group such as an ester of methacrylic acid and diethylamine.

[0182] Multifunctional vinyl monomers may also be used. The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on both ends, or analogous silicone compounds having unsaturated groups.

[0183] A carbosiloxane dendrimer, which is component (B), may be represented by formula (I) as defined above. Preferably, the Y group of formula (I) may be an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group, and a 5-hexenyl group.

[0184] According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:

[0185] [Chem.5]

[0186] in which:

[0187] . Y, R1, R2 and R3 are as defined in formulas (I) and (II) above;

[0188] . a1, a2 and a3 meet the definition of a' according to formula (II); and

[0189] . R12 is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.

[0190] According to one embodiment, a vinyl polymer having at least one carbosiloxane dendrimer-derived unit may comprise a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer-derived unit corresponding to one of the formulas:

[0191] [Chem.6]

[0192] Or

[0193] [Chem.7]

[0194] According to a preferred embodiment, a vinyl polymer having at least one carbosiloxane dendrimer-derived unit used in the invention comprises at least one butyl acrylate monomer.

[0195] The vinyl polymer comprising the carbosiloxane dendrimer can be obtained according to the method described for synthesizing a branched silalkylene siloxane described in Japanese patent application JPH111530, or else correspond to one of the polymers described in the examples of application EP963751.

[0196] According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group. Particularly preferred are structures in which the polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures as well as fluorinated organic groups are attached to side chains. The fluorinated organic groups may be obtained by substituting all or part of the hydrogen atoms of C1-C20 alkyl groups, as well as C6-C22 alkyloxyalkylene groups, with fluorine atoms.

[0197] A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO2003 / 045337. The carbosiloxane dendrimers may be prepared using the preparation method for branched siloxane / silakylene copolymers described in document EP1055674.

[0198] According to a preferred embodiment, a grafted vinyl polymer within the meaning of the The present invention can be carried in an oil or a mixture of oil(s), preferably volatile oil(s) in particular, chosen from silicone oils and hydrocarbon oils and their mixtures.

[0199] According to a particular embodiment, a silicone oil suitable for the invention may be cyclopentasiloxane.

[0200] According to another particular embodiment, a hydrocarbon oil suitable for the invention may be isododecane.

[0201] Preferably, the vinyl polymer grafted with at least one carbosiloxane dendrimer-derived unit is a copolymer with the INCI name: Acrylates / Polytrime-thylsiloxy-methacrylate Copolymer.

[0202] Such copolymers are for example marketed under the names Dowsil FA 4002 ID® Silicone Acrylate, Dowsil FA 4012 ID® Silicone Acrylate, Dowsil FA 4001 CM® Silicone Acrylate, Dowsil FA 4003 DM® Silicone Acrylate, Dowsil FA 4004 ID® Silicone Acrylate, by the company Dow Corning. Silicone acrylate copolymers

[0203] The silicone vinyl polymer can also be chosen from copolymers comprising (meth)acrylic groups and polydimethylsiloxane groups.

[0204] By "copolymer comprising (meth)acrylic groups and polydimethylsiloxane groups", is meant in the present application, a copolymer obtained from (a) one or more (meth)acrylic acid or meth)acrylic acid ester monomers and (b) one or more polydimethylsiloxane (PDMS) chains.

[0205] Thus, the monomer (a) may be chosen, for example, from acrylic acid, methacrylic acid, their esters and mixtures of these monomers. As esters, the following monomers may be mentioned: acrylate, methacrylate. According to a preferred embodiment of the invention, the monomers in the form of esters are more particularly chosen from linear or branched alkyl acrylates and methacrylates, preferably C1-C24 and better still C1-C22, the alkyl radical being preferentially chosen from methyl, ethyl, stearyl, butyl, ethyl-2-hexyl radicals, and mixtures thereof.

[0206] Thus, according to a particular embodiment of the invention, the copolymer comprises at least one group chosen from acrylic acid, methacrylic acid, methyl, ethyl, stearyl, butyl, ethyl-2-hexyl acrylates or methacrylates, and mixtures thereof.

[0207] In the present application, the term "polydimethylsiloxanes" (also abbreviated as PDMS) is intended to denote, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond =Si-O-Si=), comprising trimethyl radicals directly linked via a carbon atom to said silicon atoms. The PDMS chains which can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, that is to say that the PDMS can have for example a polymerizable radical group on both ends of the chain or have a polymerizable radical group on one end of the chain and a trimethylsilyl terminal group on the other end of the chain.The polymerizable radical group may be in particular an acrylic or methacrylic group, in particular a group CH2 = CRi-CO-O- R2, where Ri represents a hydrogen or a methyl group, and R2 represents -CH2-, -(CH2)n-with n = 3, 5, 8 or 10, -CH2-CH(CH3)-CH2-, -CH2-CH2-O-CH2-CH2-, -CH2-CH2-O-CH2-CH2-CH(CH3)-CH2 -. -ch2-ch2-o-ch2 ch2-o-ch2-ch2-ch2-,

[0208] These copolymers are generally obtained according to the usual polymerization and grafting methods, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of the ends of the chain or on both) and (B) of at least one carboxylic monomer, as described for example in documents US5061481 and US5219560.

[0209] The copolymers obtained generally have a molecular weight ranging from approximately 3000 to 200,000 and preferably from approximately 5000 to 100,000 g / mol.

[0210] Said copolymer can be presented as such or in dispersed form in a solvent such as lower alcohols containing from 2 to 8 carbon atoms, such as isopropyl alcohol, or oils such as volatile silicone oils (for example cyclopentasiloxane).

[0211] As copolymers which can be used, mention may be made, for example, of copolymers of acrylic acid and stearyl acrylate with polydimethylsiloxane grafts, copolymers of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of acrylic acid and stearyl methacrylate with polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Mention may in particular be made, as copolymers which can be used in the composition of the invention, of the copolymers marketed by the company SHIN-ETSU under the names KP-561® (INCI name: Acrylates / Stearyl Acrylate / Dimethicone Methacrylate Copolymer), KP-541® where the copolymer is dispersed at 60% by weight in isopropyl alcohol (INCI name: Acrylates / Dimethicone (and) Isopropyl Alcohol), KP-545® where the copolymer is dispersed at 30% in cyclopentasiloxane (INCI name: Acrylates / Dimethicone (and) Cyclopentasiloxane).

[0212] Mention may also be made of a copolymer of polydimethylsiloxane and one or more monomers chosen from acrylic acid, methacrylic acid and their esters and dissolved in isododecane marketed by the company Shin Etsu under the name KP-550® and the INCI name Acrylates / Dimethicone Copolymer (and) Iso-dodecane. Silicone Polyamide

[0213] The silicone polyamides of the composition are preferably solid at 20°C and atmospheric pressure (1,013.105Pa).

[0214] The silicone polyamides that can be used can be polymers of the polyorganosiloxane type, such as, for example, those described in documents US5874069, US5919441, US6051216 and US5981680.

[0215] According to the invention, the silicone polymers can belong to the following two families: (1) polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and / or (2) polyorganosiloxanes comprising at least two amide groups, these two groups being located on grafts or branches.

[0216] A) According to a first variant, the silicone polymers are polyorganosiloxanes whose amide units are arranged in the polymer chain.

[0217] The silicone polyamides may more particularly be polymers comprising at least one unit corresponding to the general formula (I):

[0218] [Chem. 8] 1) in which: G' represents C(O) when G represents -C(O)-NH-Y-NH- and G' represents -NH- when G represents -NH-C(O)-YC(O)- 2) R4, R5, R6 and R7, identical or different, represent a group chosen from: - linear, branched or cyclic hydrocarbon groups, C1 to C40, saturated or unsaturated, which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, and which may be substituted in part or completely by fluorine atoms, - C6 to C10 aryl groups, optionally substituted by one or more C1 to C4 alkyl groups, - polyorganosiloxane chains containing or not one or more oxygen, sulfur and / or nitrogen atoms, 3) the X, identical or different, represent a linear or branched C1 to C30 alkylene di-yl group, which may contain in its chain one or more oxygen and / or nitrogen atoms, 4) Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, saturated or unsaturated, C1 to C50, which may contain one or more oxygen, sulfur and / or nitrogen atoms, and / or may carry as a substituent one of the following atoms or groups of atoms: fluorine, hydroxy, C3 to C8 cycloalkyl, C4 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted by 1 to 3 C1 to C3 alkyl groups, C4 to C3 hydroxyalkyl and C6 to C6 amino alkyl, or 5) Y represents a group corresponding to the formula: R8-T<; in which - T represents a trivalent or tetravalent, linear or branched, saturated or unsaturated, C3 to C24 hydrocarbon group optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and - R8 represents a linear or branched C1-C50 alkyl group, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups which may or may not be linked to another chain of the polymer, 6) n is an integer ranging from 2 to 500, preferably from 2 to 200, and m is an integer ranging from 50 to 1000, preferably from 50 to 700 and more preferably from 50 to 200.

[0219] It will be noted that “m” corresponds to the average degree of polymerization of the silicone portion of the silicone polyamide.

[0220] According to one embodiment of the invention, 80% of R4, R5, R6 and R7 of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of R4, R5, R6 and R7 of the polymer are methyl groups.

[0221] B) According to the second variant, the silicone polyamides may be polymers comprising at least one unit corresponding to formula (II):

[0222] [Chem.9] (H) in which - R4 and R6, identical or different, are as defined above for formula (I), - R10represents a group as defined above for R4 and R6, or represents the group of formula -XG”-R12in which X are as defined above for formula (I) and R12 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated hydrocarbon group, C1 to C50, optionally comprising in its chain one or more atoms chosen from O, S and N, optionally substituted by one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more C1 to C4 alkyl groups, and G” represents —C(O)NH- and -HN-C(O)-. - R11 represents the group of formula -XG”-R12 in which X, G” and R12 are as defined above, - is an integer ranging from 50 to 998, and - m2 is an integer ranging from 2 to 500.

[0223] It will be noted that “mi” corresponds to the average degree of polymerization of the silicone portion of the silicone polyamide.

[0224] According to the invention, the silicone polymer may be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (I) or of formula (II).

[0225] According to the invention, it is also possible to use a polymer consisting of a copolymer comprising several different units of formula (I), i.e. a polymer in which at least one of R4, R5, R6, R7, X, G, Y, m and n is different in one of the units. The copolymer can also be formed from several units of formula (II), in which at least one of R4, R6, R10, R11, mi and m2 is different in at least one of the units.

[0226] It is also possible to use a polymer comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical or different from each other.

[0227] These copolymers can be block polymers, sequenced polymers or graft polymers.

[0228] In formulas (I) and (II), R4, R5, R6 and R7 preferably represent, independently, a linear or branched C1-C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups.

[0229] According to one variant, the polymer may be a polyamide containing several units of formula (I) or (II) of different lengths, or a polyamide corresponding to formula (III):

[0230] [Chem. 10] (IF) in which X, Y, n, R4 to R7 have the meanings given above, mi and m2 which are different, are chosen from the range from 1 to 1000, and p is an integer from 2 to 300.

[0231] In this formula, the units may be structured to form either a block copolymer, a random copolymer, or an alternating copolymer. In this copolymer, the units may be not only of different lengths but also of different chemical structures, for example having different Ys. In this case, the polymer may correspond to the formula (IV):

[0232] [Chem. 11] ZT'S 7's ; in which R4 to R7, X, Y, mb m2, n and p have the meanings given above and Y1 is different from Y but chosen from the groups defined for Y. As before, the different units can be structured to form either a block copolymer, a random copolymer, or an alternating copolymer.

[0233] In this first embodiment of the invention, the silicone polymer can also be constituted by a grafted copolymer. Thus, the polyamide with silicone units can be grafted and optionally crosslinked by silicone chains with amide groups. Such polymers can be synthesized with trifunctional amines.

[0234] According to the invention, as seen previously, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described above. In the pendant or grafted chains, the siloxane units may appear individually or in segments.

[0235] According to an alternative embodiment of the invention, a copolymer of silicone polyamide and hydrocarbon polyamide may be used, i.e. a copolymer comprising units of formula (I) or (II) and hydrocarbon polyamide units. In this case, the polyamide-silicone units may be arranged at the ends of the hy- polyamide carbon dioxide.

[0236] Advantageously, the composition comprises at least one polyamide / polydimethylsiloxane polymer, in particular a polymer of general formula (I) having an index m of value greater than 50, in particular greater than 75, in particular approximately 100.

[0237] Advantageously, the silicone polyamide of formula (I) has a weight-average molecular mass ranging from 10,000 to 500,000 g / mol.

[0238] More preferably, X and Y independently represent a group chosen from linear C1 to C20 alkylene groups, preferably C1 to C10.

[0239] As examples of silicone polyamide, mention may be made of one of the silicone polyamides obtained in accordance with examples 1 to 3 of document US5981680, as well as the product marketed under the reference DC 2-8179 by Dow Corning (INCI name: Nylon-611 / Dimethicone Copolymer).

[0240] The composition according to the invention preferably comprises at least one silicone polyamide, when the composition comprises at least one silicone resin, glycerolated or non-glycerolated, preferably non-glycerolated.

[0241] More particularly, the content of silicone film-forming polymer represents from 2 to 25% by weight, preferably from 3 to 20% by weight, relative to the total weight of the composition.

[0242] Preferably, the composition according to the invention comprises, as film-forming silicone polymer, at least one silicone resin, preferably non-glycerolated. Preferably, the silicone resin is chosen from the silicone resins with the following INCI names: Trimethylsiloxysilicate, Phenylpropyldimethylsiloxysilicate, Polymethylsil-sesquioxane, Polypropylsilsesquioxane, as well as mixtures thereof, and even more preferably Trimethylsiloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, as well as mixtures thereof. MINERAL LIPOPHILIC THICKENER

[0243] The composition according to the invention comprises at least one mineral lipophilic thickener, in particular chosen from lipophilic clays.

[0244] The term “lipophilic clay” means any clay that is liposoluble or lipodispersible in the oily phase of the composition.

[0245] Clay designates a material based on hydrated silicates and / or aluminosilicates with a lamellar structure.

[0246] The clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as a C10 to C22 ammonium chloride, particularly steralkonium chloride or di-stearyl di-methyl ammonium chloride.

[0247] They can be chosen from bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

[0248] Preferably, they are chosen from hectorites and bentonites.

[0249] For example, one can use a lipophilic clay chosen from bentonites hydrophobically modified and hydrophobically modified hectorites, in particular by a quaternary ammonium chloride in CIO to C22, such as: - a bentonite modified by stearalkonium chloride such as the commercial products sold under the name Claytone AF®, Garamite VT®, Tixogel® LG-M, Tixogel® MP 250 Tixogel® VZ, Tixogel® VZ-V XR, by the company BYK Additives Inc; the commercial products sold under the name Viscogel® B3, Viscogel® B4, Viscogel® B7, Viscogel® B8, Viscogel® ED, Viscogel® GM, Viscogel® S4, Viscogel® SD by the company Bentec SPA; - a bentonite modified by stearalkonium chloride in the presence of at least propylene carbonate and at least one oil such as the commercial products Dub Velvet Gum® from the company Stearinerie Dubois Fils, Myglyol Gel T® from the company Cremer Oleo, Tixogel® CGT 6030, Tixogel® DBA 6060, Tixogel® FTN, Tixogel® FTN 1564, Tixogel® IPM, Tixogel® LAN, Tixogel® LAN 1563 by the company BYK Additives Inc; - a hectorite modified with distearyl dimethyl ammonium chloride (INCI name: Disteardimonium Hectorite) such as, for example, that marketed under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialities; - a hectorite modified with distearyl dimethyl ammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil such as the commercial products sold under the name Bentone® GEL DOA V, Bentone® GEL EUG V, Bentone® GEL IHD V, Bentone® GEL ISD V, Bentone® GEL MIO V® Bentone® GEL PTM V® Bentone® SS-71 V, Bentone® VS-5 PC V, Bentone® VS-5 by the company Elementis Specialities; the commercial products sold under the name Creagel Bentone CPS / Hectone CPS, Creagel Bentone ID / Hectone ID by the company Créations Couleurs; the commercial products sold under the name NS GEL DM1®, NS GEL PTIS®, NS MGEL 1152® by the company Next Step Laboratories Stop.

[0250] More particularly, if the composition comprises it, the content of lipophilic thickening agent represents from 0.2 to 4% by weight, preferably from 0.3 to 3% by weight, relative to the total weight of the composition. SECOND OIL

[0251] The composition according to the invention may optionally comprise at least one second oil, different from the first oil(s), chosen from non- volatile hydrocarbons, polar or non-polar, among volatile or non-volatile silicone oils, as well as their mixtures.

[0252] The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. These oils are therefore distinct from silicone oils.

[0253] By "polar hydrocarbon oil" is meant that said oils comprise, in addition to carbon and hydrogen atoms, at least one oxygen atom. Thus said hydrocarbon oil comprises at least one hydroxyl, ester, ether and / or carboxylic function.

[0254] By “silicone oil” is meant an oil comprising at least one silicon atom, and in particular at least one Si-O group, and more particularly an organo-polysiloxane.

[0255] By "non-volatile oil" is meant an oil whose vapor pressure at 20°C and atmospheric pressure is non-zero and less than 2.66 Pa, preferably less than or equal to 0.13 Pa. For example, the vapor pressure can be measured using the static method or by the isothermal thermogravimetry effusion method, depending on the vapor pressure of the oil (OECD standard 104). Polar non-volatile hydrocarbon oils

[0256] The composition according to the invention can therefore comprise at least one non-volatile polar hydrocarbon oil, more particularly chosen from: * Fatty alcohols, preferably monoalcohols, saturated, unsaturated, linear or branched, C10-C26, preferably branched when they comprise at least 16 carbon atoms. More particularly, the fatty alcohol comprises from 10 to 24 carbon atoms, and more preferably from 12 to 22 carbon atoms; * Ethers of formula ROR', carbonates of formula RO(CO)OR', formulas in which, identical or not, the groups R, R' represent a hydrocarbon group comprising at most 16 carbon atoms, saturated or not, branched or not, preferably C3-Ci6; * hydroxylated or non-hydroxylated vegetable oils; * ester oils, comprising 1 or more ester functions, preferably 1 to 4 ester functions, and comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon group, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil may optionally comprise one or more ether or hydroxyl functions; * liquid polyesters resulting from the reaction of a mono- or polyunsaturated acid dimer, the fatty acid comprising 16 to 22 carbon atoms; * as well as their mixtures.

[0257] Preferably, the second oil is chosen from: - lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecyl pentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof; preferably octyldodecanol; - dicaprylyl ether; - dipropyl carbonate, diethylhexyl carbonate, dicaprylyl carbonate, C14-15 dialkyl carbonate; - castor oil, olive oil, jojoba oil, ximenia oil, pracaxi oil, wheat germ oil, corn oil, sunflower oil, sweet almond oil, macadamia oil, apricot kernel oil, soybean oil, rapeseed oil, peanut oil, cottonseed oil, alfalfa oil, poppy seed oil, pothnarron oil, sesame oil, pumpkin oil, avocado oil, hazelnut oil, grapeseed oil, blackcurrant oil, argan oil, evening primrose oil, millet oil, barley oil, linseed oil, quinoa oil, rye, safflower oil, candlenut oil, passionflower oil, rosehip oil, the liquid fraction of shea butter, and the liquid fraction of cocoa butter and mixtures thereof; - 2-ethylhexyl palmitate, 2-octyl-decyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, butyl stearate, 2-octyldodecyl erucate, C12-15 alcohol benzoates, 2-octyldodecyl benzoate, isocetyl isostearate, isostearyl isostearate, isononyl isononanoate, isopropyl palmitate, hexyl laurate, 2-hexyl-decyl laurate, isopropyl myristate, 2-octyldodecyl myristate, diisostearyl malate, neopentyl glycol dicaprate, tri glyceryl decyl-2 tetradecanoate, capric acid triglyceride alone or in mixture such as capric / caprylic acid triglycerides, C18-36 acid triglycerides, glyceryl triheptanoate, glyceryl trioctanoate, glyceryl tri decyl-2 tetradecanoate, triisostearyl citrate, tridecyl stearate, tridecyl trimellitate, pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate,Pentaerythrityl tetraisononanoate, Pentaerythrityl tetradecyl-2 tetradecanoate; Polyglycerol-2 tetraisostearate; Pentaerythrityl Isostearate / Caprate / Caprylate / Adipate (INCI name, e.g. Supermol L products from Croda); Isostearyl lactate, Octylhydroxystearate, Octyldodecyl hydroxystearate; ,

[0258] - the polyesters with the following INCI names: Dilinoleic Acid / Butanediol Copolymer, Di- linoleic Acid / Propanediol Copolymer, marketed for example under the name Viscoplast, by the company Biosynthis; Dimer Dilinoleyl Dilinoleate, marketed in particular under the name Lusplan by the company Nippon Fine Chemical; - as well as their mixtures. Non-volatile non-polar hydrocarbon oils

[0259] The non-volatile apolar hydrocarbon oil may be chosen from linear or branched hydrocarbons, of mineral, vegetable or synthetic origin such as for example: - paraffin oil, - squalane, particularly of plant origin, - isoeicosane, - mixtures of linear, saturated hydrocarbons, more particularly C15-C28, such as mixtures whose INCI names are, for example, the following: C15-19 Alkane Cl8-21 Alkane, C21-28 Alkane, such as, for example, the products Gemseal 40, Gemseal 60, Gemseal 120 marketed by Total, Emogreen L15 and L19 marketed by SEPPIC, - polybutenes, hydrogenated or not, such as, for example, products from the Indopol range marketed by the company Ineos Oligomers, - polyisobutenes, hydrogenated or not, such as for example the non-volatile compounds of the Parléam® range marketed by the company Nippon Oil & Fat, - polydecenes, hydrogenated or not, such as for example non-volatile compounds from the Silkflo range marketed by the company Ineos, Dekanex by the company IMCD, - and their mixtures. Non-volatile silicone oils

[0260] The composition according to the invention may comprise at least one non-volatile phenylated silicone oil, comprising or not at least one dimethicone fragment, or comprising at least one non-volatile non-phenylated silicone oil, or mixtures thereof.

[0261] The term “phenylated” specifies that said oil contains at least one phenyl radical in its structure.

[0262] The term "dimethicone fragment" designates a divalent siloxane group whose silicon atom carries two methyl radicals, this group not being found at one or both ends of the molecule. It can be represented by the following formula: -(Si(CH3)2-O)-.

[0263] Preferably, the silicones do not contain a C 2-C 3 alkylene oxide group, nor a glycerol group.

[0264] As non-volatile phenylated oil comprising at least one dimethicone fragment, mention may be made of the oils with the following INCI names: Trimethylsiloxyphenyl Dimethicone, Diphenyl Dimethicone, Tetramethyl Tetraphenyl Trisiloxane and their mixtures, preferably Trimethylsiloxyphenyl Dimethicone. Diphenyl Dimethicones are marketed in particular by the company Shin Etsu under the names KF-54, KF54HV, KF-50-300CS, KF-53 d, KF-50-100CS. Trimethylsiloxy Phenyl Dimethicones are marketed for example by the company Wacker Chemie under the names Belsil PDM 1000, Belsil PDM 20.

[0265] Among the non-volatile phenylated silicone oils devoid of dimethicone fragment, mention may be made of the compounds with the following INCI names: Phenyltrimethicone, Trimethyl Pentaphenyl Trisiloxane, alone or in mixtures. As non-volatile non-phenylated silicone oils suitable for carrying out the invention, mention may be made of those marketed by the company Wacker under the Belsil DM range, by the company Dow Corning with the Xiameter PMX 200 Silicone Fluid range, by the company Shin Etsu with the KF-96 A range.

[0266] Representative examples of non-volatile non-phenylated silicone oils include polydimethylsiloxanes, alkyldimethicones. Note that “Dimethicone” (INCI name) corresponds to a polydimethylsiloxane (chemical name). Preferably, these non-volatile non-phenylated silicone oils are chosen from polydimethylsiloxanes; alkyldimethicones comprising at least one C2-C24 alkyl group, as well as mixtures thereof. Thus, these oils can be chosen from Dimethicone, Cetyl Dimethicone, Stearyl Dimethicone, alone or in mixtures. Suitable non-volatile non-phenylated silicone oils include those marketed by Wacker under the Belsil DM range, by Dow Corning with the Xiameter PMX 200 Silicone Fluid range, and by Shin Etsu with the KF-96 A range.Alkyldimethicones can be marketed, for example, under the commercial references Abil Wax 9800, Abil Wax 9801 from Evonik Goldschmidt, or Dowsil 2502 Cosmetic Fluid, Dowsil 2503 Cosmetic Wax, from Dow Corning; and their mixtures. Volatile silicone oils

[0267] The volatile silicone oils can be chosen from linear, branched or cyclic silicone oils such as polydimethylsiloxanes having from 3 to 7 silicon atoms.

[0268] As an example of such oils, mention may be made of the oils with the following INCI names: Cyclopentasiloxane, Cyclotetrasiloxane, Cyclohexasiloxane, Caprylyl Methicone, Di-siloxane, Trisiloxane, Dimethicone in particular with a viscosity of less than 5 cSt, such as those marketed under the reference Xiameter PMX-200 silicone Fluid marketed by the company Dow Corning, with viscosities in particular of 1 cSt, 1.5 cSt, 3 cSt, or KF 96 L 2 es from Shin Etsu; alone or in mixtures.

[0269] Preferably, the second oil, if the composition according to the invention comprises it, is at least chosen from non-volatile hydrocarbon oils, preferably polar, alone or in mixtures.

[0270] Preferably, the second oil is chosen from polar non-volatile hydrocarbon oils.

[0271] Preferably, the second oil(s) is / are chosen from ether oils and ester oils. According to an even more preferred embodiment, if the composition comprises them, the second oil(s) is / are chosen from vegetable oils; ester oils, optionally hydroxylated, comprising 1 to 4 ester functions, comprising at least one linear or branched, saturated, unsaturated or aromatic group, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; ether oils of formula ROR' where R, R', identical or not, represent a hydrocarbon group comprising at most 16 carbon atoms, saturated or not, branched or not; as well as mixtures thereof.

[0272] According to a preferred embodiment, the second oil is chosen from fatty acid triglycerides containing from 8 to 24 carbon atoms, and more particularly a caprylic / capric acid triglyceride (INCI Name: Caprylic / Capric Triglyceride), vegetable oils, dicaprylyl ether, and mixtures thereof.

[0273] If the composition comprises it, the content of second oil(s) does not exceed 15% by weight, more particularly from 0.1 to 10% by weight, relative to the total weight of the composition.

[0274] Preferably, if the composition comprises at least one silicone oil, volatile or non-volatile, then their content does not exceed 5% by weight, more particularly does not exceed 3% by weight, even more preferably does not exceed 1% by weight, relative to the total weight of the composition. Preferably, the composition according to the invention is free of it. WATER

[0275] The composition according to the invention also comprises water.

[0276] A water suitable for the invention may be a demineralized water, a floral water such as cornflower water and / or a mineral water such as Vittel water, Lucas water or La Roche Posay water and / or a thermal water.

[0277] According to a particular embodiment of the invention, the water content is at least 20% by weight, preferably between 20 and 50% by weight, preferably between 20 and 40% by weight, relative to the total weight of the composition MONOALCOHOL C2-C6

[0278] The composition according to the invention may optionally comprise at least one C2-C6 monoalcohol, more particularly C2-C4, saturated or unsaturated, preferably saturated. The monoalcohol(s) may be represented for example by the formula RaOH, in which Ra represents a linear or branched alkyl group, comprising from 2 to 6 carbon atoms, preferably comprising from 2 to 4 carbon atoms. As mono-alcohol, mention may be made of ethanol, isopropanol, tert-butanol or butanol, or mixtures thereof. Preferably, said mono-alcohol comprises at least ethanol and even more preferably, the mono-alcohol is ethanol.

[0279] According to an advantageous embodiment of the invention, the monoalcohol content represents from 3 to 20% by weight, preferably from 5 to 15% by weight, relative to the total weight of the composition. LIQUID POLYOL

[0280] The composition according to the invention may optionally comprise at least one polyol which is liquid at room temperature, C2-C8, preferably C3-C6, saturated or unsaturated, linear or branched, comprising from 2 to 6 hydroxyl groups. More particularly, the liquid polyol is chosen from glycerin, diglycerin, glycols or alkanediols, C3-C8, linear or branched, saturated. Suitable in particular are propylene glycol, propanediol, butylene glycol, pentanediol, pentylene glycol, caprylyl glycol, dipropylene glycol, and mixtures thereof, and preferably glycerin.

[0281] According to an advantageous embodiment of the invention, the liquid polyol content varies from 3 to 20% by weight, in particular from 4 to 15% by weight, relative to the total weight of the composition. NON-IONIC SURFACTANT

[0282] The composition according to the invention comprises at least one non-ionic hydrocarbon or silicone surfactant with an HLB of less than or equal to 8.

[0283] For the purposes of the present invention, the term "surfactant" means an amphiphilic compound, i.e. one having two parts of different polarity. In general, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). Non-ionic surfactants are characterized by the value of their HLB (Hydrophilic Lipophilicity balance), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and is described for example in "The HLB System. A time-saving guide to Emulsifier Selection” (published by ICI Americas Inc; 1984). For the surfactants used in the context of the present invention, their HLB is more particularly less than or equal to 8 and more particularly ranging from 3 to 8. The HLB value can be determined by the GRIFFIN method or the DA VIES method.

[0284] More particularly, the non-ionic surfactant(s) are chosen from optionally (poly)oxyethylenated, (poly)oxypropylenated, (poly)glycerolated compounds. Non-ionic hydrocarbon surfactant

[0285] Among the non-ionic hydrocarbon surfactants that can be used in the context of the invention, mention may be made of (poly)oxyethylenated and / or (poly)oxypropylenated C8-C30 alcohols; (poly)oxyethylenated, (poly)oxypropylenated C8-C30 esters; polyoxyalkylenated, preferably polyhydroxylated, C12-C20 fatty acid polyesters, having from 4 to 50 ethylene oxide units; sorbitan alkyl(C8-C30)- and polyalkyl(C8-C30)-esters; (poly)glycerolated alkyl(C8-C30)- and polyalkyl(C8-C30)-esters; alone or in mixtures.

[0286] As examples of such surfactants, the following are particularly suitable: 1. (poly)oxyethylenated, (poly)oxypropylenated, preferably (poly)oxyethylenated C8-C30 alcohols, more particularly comprising a number of ethylene oxide (EO) units ranging from 2 to 4. Examples that may be mentioned include laureth-2; steareth-2, oleth-2; oleth-3; ceteth-2; ceteareth-3; 2. alkyl(C8-C30)- and polyalkyl(C8-C30)- (poly)oxyethylenated, (poly)oxypropylenated, preferably (poly)oxyethylenated esters, more particularly comprising a number of ethylene oxide (EO) units ranging from 1 to 5, with for example glycol distearate, glycol stearate, PEG-2 oleate; PEG-3 oleate; PEG-4 dilaurate (HLB 6), propylene glycol isostearate; PEG-2.5 castor oil; PEG-3 castor oil;

[0287] 3) fatty acid polyesters, preferably polyhydroxylated, C12-C20, polyoxy alkylenated, having from 4 to 50 ethylene oxide units. In particular, these polymers are block polymers, preferably of ABA structure, comprising poly(hydroxylated ester) blocks and polyethylene glycol blocks. The fatty acid of said surfactant polymer as defined above preferably has from 14 to 18 carbon atoms. The esters may in particular be chosen from oleates, palmitates or stearates. The polyethylene glycol blocks of said surfactant polymer as defined above preferably comprise from 20 to 40 ethylene oxide units. A polymer surfactant which is particularly suitable for producing the compositions of the invention is polyethylene glycol di-polyhydroxystearate with 30 EO sold under the trade name Arlacel P 135 by the company Croda.

[0288] 4) alkyl(C8-C30)- and polyalkyl(C8-C30)- sorbitan esters, such as for example sorbitan trioleate, sorbitan sesquioleate, sorbitan oleate, sorbitan palmitate; sorbitan stearate, sorbitan isostearate (Span 120 by Croda), sorbitan sesquiisostearate (Cosmol 182V by Nisshin Oillio), mixtures of sorbitan stearate and sucrose cocoate (Arlacel 2121 marketed by Croda); sorbitan isostearate mixed with hydrogenated castor oil, stearic acid and white wax (Arlacel 986 marketed by Croda), and mixtures thereof.

[0289] 5) alkyl(C8-C30)- and polyalkyl(C8-C30)- esters of (poly)glycerol, comprising more particularly a number of glycerol units ranging from 1 to 10. Examples include glyceryl isostearate, glyceryl stearate, glyceryl laurate, alone or in mixtures. Among the polyglycerolated non-ionic surfactants, we can cite in particular - esters of isostearic acid and polyglycerol having from 2 to 10 moles of glycerol units such as, for example, Polyglyceryl-4 Isostearate sold under the name Isolan GI34® by the company Evonik Nutrition & Care GmbH, polyglyceryl-2 sesquiisostearate sold under the name Hostacerin® DGI by the company Clariant, Polyglyceryl-3 Diisostearate sold under the name Lameform TGI® by the company Cognis; Polyglyceryl-2 Diisostearate sold under the name Emalex PGSA® by the company Nihon Emulsion; Polyglyceryl-10 Isostearate sold under the name Nikkol Decaglyn 1 -IS® by the company Nihon Surfactant; Polyglyceryl-4 Diisostearate / Polyhydroxystearate Sebacate sold under the name ISOLAN GPS® by Evonik Nutrition & Care GmbH, Polyglyceryl-2 Triisostearate sold under the name Cithrol PG23IS® by Croda Europe, Ltd; - esters of stearic acid and polyglycerol having 2 or 3 moles of glycerol units such as Polyglyceryl-2 Sesquistearate marketed by Taiyo Kagaku Company under the name SunSoft Q-18B®, Polyglyceryl-3 Distearate marketed by BASF under the name Cremophor GS 32®, Polyglyceryl-2 Stearate sold under the name Hostacerin DGMS® by Clariant International Ltd; - oleic acid and polyglycerol esters having 2 or 3 moles of glycerol units such as Polyglyceryl-2 Oleate sold under the name Nikkol DGMO-CV® by Nikko Chemicals, Polyglyceryl-3 Oleate sold under the name Isolan GO 33® by Evonik Nutrition & Care GmbH, Polyglyceryl-2 Dioleate; Polyglyceryl-3 Dioleate sold under the name Plurol Oleique CC 497® by Gattefosse; - polyglyceryl polyricinoleate(s) having 3 to 6 moles of glycerol units such as Polyglyceryl-3 Polyricinoleate, marketed in particular by the company Karlshamns under the name Akoline PGPR® or by the company Stéarinerie Dubois Fils under the name DUB PGPR or by the company Dr. Straetmans under the name DERMOFEEL®, or by the company Croda under the name CRESTER PR® or by the company Sasol under the name IMWITOR 600®; Polyglyceryl-5 Polyricinoleate marketed by the company Taiyo Kagaku Co. LTD under the name Sunsoft NO.818R®; Polyglyceryl-6 Polyricinoleate marketed by Nikko Chemicals Co. LTD under the name Hexaglyn PR-15® or by Sakamoto Yakuhin Kogyo Co. LTD under the name SY-Glyster CRS-75®. According to one embodiment, mixtures of these compounds can be used. More particularly, the non-ionic polyglycerol surfactant is chosen from polyglyceryl polyricinoleate(s) having from 3 to 6 moles of glycerol units, and more particularly Polyglyceryl-6 Polyricinoleate marketed by the company Nikko Chemicals Co. LTD under the name Hexaglyn PR-15® or by the company Sakamoto Yakuhin Kogyo Co. LTD under the name SY-Glyster CRS-75®. Non-ionic silicone surfactant

[0290] The non-ionic surfactant may also be chosen from silicone non-ionic surfactants, in particular linear oxyalkylenated (C3-C4) polydimethylmethylsiloxanes with an HLB of less than or equal to 8, preferably linear oxypropylenated and / or oxyethylenated, in particular of the following formula (I): [Chem 12] in which Rh R2, R3, independently of each other, represent a C1-C6 alkyl radical or a -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4 radical, at least one RB R2 or R3 radical not being an alkyl radical; R4 being a hydrogen, a C1-C3 alkyl radical or a C2-C4 acyl radical; A is an average integer ranging from 0 to 200; B is an average integer ranging from 0 to 50; provided that A and B are not equal to zero at the same time; x is an average integer ranging from 0 to 6; y is an average integer ranging from 1 to 30; z is an average integer ranging from 0 to 30.

[0291] According to a particular embodiment, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB < 8 is chosen from those of formula (I) where R1 and R3 denote methyl, R2 is -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4 and R4 is a hydrogen atom.

[0292] More particularly, among these compounds, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB < 8 is chosen from those of formula (I) where x is equal to 0.

[0293] More particularly, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB < 8 is chosen from those of formula (I) where R1 and R3 denote methyl, R2 is -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4> R4 is a hydrogen atom and z is equal to O.

[0294] According to a particular embodiment, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB < 8 is chosen from those of formula (I) where R 1 and R 3 denote -(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4, R2 is methyl and R4 is hydrogen.

[0295] As examples of silicone surfactants, mention may be made of the following surfactants with INCI names: PEG / PPG-8 / 8 Dimethicone, Bis-PEG / PPG-14 / 14 Dimethicone, PEG / PPG-18 / 18 Dimethicone, PEG / PPG-19 / 19 Dimethicone, PEG-3 Dimethicone, PEG-10 Dimethicone, as well as mixtures thereof.

[0296] The following products are particularly suitable: - PEG / PPG-8 / 8 dimethicone such as products sold under the trade names Silube J208-4I®, Silube J208-6I®, Silube J208-8I® and Silsurf J-1013-V-CG® by Siltech LLC; Andisil SP 1818® by AB Specialty Silicones; Jeesilc DMC 19® by Jeen International Corporation; Xiameter OFX-0190 Fluid® by Dow Chemical; - the mixture Bis-PEG / PPG-14 / 14 Dimethicone (and) Dimethicone sold under the trade name AB IL EM 97 S® by the company Evonik Goldschmidt; - the mixture of Cyclopentasiloxane and PEG / PPG-18 / 18 Dimethicone such as the products sold under the trade names Dowsil 5225C Formulation Aid® by Dow Chemical Company); Emusil WO-5115® by Innospec Performance Chemicals Company; Gransurf 10C® by Grant Industries, Inc.; Jeesilc DMC522® by Jeen International Corporation; Silsurf 400R® by Siltech LLC; - the mixture of Cyclotetrasiloxane and Cyclopentasiloxane and PEG / PPG-18 / 18 Dimethicone such as the commercial products sold under the name Dowsil 3225C Formulation Aid® by Dow Chemical; Emulsil WO-3115® by Innospec Performance Chemicals; Jeesilc DMC252® and Jeesilc DMC322® by Jeen International Corporation; - Dimethicone and PEG / PPG-18 / 18 Dimethicone mixture such as the commercial products Dowsil ES-5226 DM Formulation Aid® and Dowsil ES-5227 DM Formulations AID® from Dow Chemical; Gransurf 50C® and Gransurf 50C-HM® from Grant Industries, Inc. and X-22-6711D from Shin Etsu. - the mixture of PEG / PPG-19 / 19 Dimethicone and C13-C16 Isoparaffin and C10-C13 Iso-paraffin such as the commercial product Dow Corning® BY 25-337 from Dow Chemical; - PEG-3 Dimethicone such as the commercial product KF-6015® from Shin-Etsu Chemical Co., Ltd.; - PEG-10 Dimethicone such as commercial products KF-6017® from Shin-Etsu Chemical Co., Ltd.; Serasol SC 86® and Serasol SC 86A® from KCC Corporation); - their mixtures.

[0297] Preferably, the composition according to the invention comprises, as non-ionic surfactant(s), at least one hydrocarbon surfactant with an HLB of less than or equal to 8. and even more preferably, at least one polyglycerolated hydrocarbon surfactant as previously described.

[0298] A composition of the invention preferably comprises from 2 to 10% by weight of non-ionic hydrocarbon or silicone surfactant(s), in particular from 2 to 7% by weight, relative to the total weight of the composition. COLORING MATTER

[0299] The composition according to the invention comprises at least one coloring material.

[0300] According to a particular form of the invention, the coloring matter may be chosen from powdery coloring matters, liposoluble dyes, water-soluble dyes, and mixtures thereof. Powdered coloring matter

[0301] The powdery coloring materials can be chosen from mineral pigments, organic pigments, nacres and their mixtures.

[0302] The term “pigments” means white or colored particles, mineral or organic, insoluble in an aqueous medium, intended to color and / or opacify the composition and / or the resulting deposit. These pigments may be white or colored, mineral and / or organic.

[0303] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0304] By "mineral pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments may also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 in mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

[0305] The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can range up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1 μm.

[0306] According to a particular form of the invention, the pigments have a size characterized by a D

[50] greater than 100 nm and which can range up to 10 qm, preferably from 200 nm to 5 qm, and more preferably from 300 nm to 1 pm.

[0307] The sizes are measured by static light scattering using a commercial granulometer of the Master Sizer 3000® type from Malvern, making it possible to understand the granulometric distribution of all the particles over a wide range from 0.01 qm to 1000 qm. The data are processed on the basis of the classical Mie scattering theory. This theory is best suited for size distributions ranging from submicron to multimicron, and allows for the determination of 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.

[0308] D

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

[0309] According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, the latter being preferably present in the oily phase of the composition according to the invention.

[0310] According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from 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.

[0311] According to a preferred embodiment, the pigments may be coated according to the invention with an N-acylated amino acid or one of its salts which may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

[0312] The amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylated amino acid derivative which may in particular be a glutamic acid derivative and / or one of its salts, and more particularly a stearoyl glutamate, such as, for example, aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference NAI® by the company Miyoshi Kasei.

[0313] According to a preferred embodiment, the pigments may be coated according to the invention with isopropyl triisostearyl titanate. As examples of pigments treated with isopropyl titanium triisostearate (ITT), mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference BWB0-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWY0-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-12® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company Kobo.

[0314] The pigments that can be used according to the invention can also be organic pigments.

[0315] By "organic pigment" is meant any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone compounds.

[0316] 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 codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 1725, 15510, 45370, 71105, the red pigments codified 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 the pigments obtained by oxidative polymerization of indole derivatives,phenolics as described in patent FR2 679 771.,

[0317] These pigments can also be in the form of composite pigments as described in patent EPI 184426. These composite pigments can be composed in particular of particles comprising an inorganic core covered at least partially with an organic pigment and at least one binder ensuring the fixing of the organic pigments on the core.

[0318] The pigment may also be a lake. By lake is meant insolubilized dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

[0319] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

[0320] Among the organic dyes, we can cite cochineal carmine. Other products known under the following names include: 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 5 (CI 61 570), D&C Yellow 10 (CI 47 005), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0321] Examples of lacquers include the product known under the name D&CRed7 (CI 15850:1).

[0322] Preferably, the composition according to the invention comprises at least one pulverulent coloring material of mineral pigment type, in particular chosen from metal oxides, and more particularly chosen from titanium dioxides, iron oxides, coated or not, and their mixtures.

[0323] The nacres can be chosen from white nacreous pigments such as mica coated with titanium or bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as nacreous pigments based on bismuth oxychloride.

[0324] Preferably, the pulverulent coloring material(s) is (are) present, preferably, in the composition in a content ranging from 3 to 25% by weight, preferably from 5 to 20% by weight, more particularly from 5 to 15% by weight relative to the total weight of the composition. Water-soluble or fat-soluble coloring matter

[0325] A composition according to the invention may comprise at least one water-soluble or fat-soluble coloring matter and preferably in an amount of at least 0.01% by weight relative to the total weight of the composition.

[0326] For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the coloring materials considered and its adjustment clearly falls within the skills of those skilled in the art.

[0327] The additional coloring materials suitable for the invention may be liposoluble.

[0328] By "liposoluble coloring matter", within the meaning of the invention, is meant any generally organic, natural or synthetic compound, soluble in an oily phase or solvents miscible with a fatty substance and capable of coloring.

[0329] As liposoluble dyes suitable for the invention, mention may in particular be made of liposoluble dyes, synthetic or natural, 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, carotenes ([3-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto, curcumin.

[0330] The additional coloring materials suitable for the invention may be water-soluble.

[0331] By "water-soluble coloring matter", within the meaning of the invention, is meant any generally organic, natural or synthetic compound, soluble in an aqueous phase or water-miscible solvents and capable of coloring.

[0332] As water-soluble dyes suitable for the invention, mention may in particular be made of synthetic or natural water-soluble dyes such as, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocyanin, black carrot, hibiscus, elderberry), caramel, riboflavin.

[0333] The water-soluble or fat-soluble colorant(s), if the composition comprises them, are preferably present at contents of less than 4% by weight, or even less than 2% by weight, more preferably ranging from 0.01 to 2% by weight, and even better from 0.02 to 1.5% by weight relative to the total weight of the composition. CHARGE

[0334] The composition according to the invention preferably comprises at least one mineral filler, different from the mineral thickener described previously, or organic, as well as their mixtures.

[0335] By "filler" is meant a particle of organic or mineral nature, colorless or white, solid, of any shape, insoluble in the medium of the composition at room temperature and atmospheric pressure. These fillers are advantageously dispersed in the composition. Mineral charge

[0336] The term “mineral filler” means any compound whose chemical structure does not include a carbon atom, regardless of the presence of a coating of said filler.

[0337] The fillers are in the form of particles and are distinct from the coloring materials described above.

[0338] The fillers used in the compositions according to the present invention may be particles of lamellar, globular, spherical, fiber shapes or any other intermediate shape between these defined shapes. The fillers may be spherical, that is to say comprise at least one generally rounded portion, in particular defining at least one portion of a sphere, preferably internally defining a concavity or a hollow (sphere, globules, bowls, horseshoe, etc.) or lamellar.

[0339] According to a particular embodiment of the invention, the fillers more particularly have an average particle size (expressed as volume average diameter - D[0.5]) of at least 1 pm, preferably at least 2 pm, advantageously between 2 and 15 pm. The particle size can be measured by laser diffraction using a commercial granulometer of the Mastersizer 3000 type, from the company Malvern (see also standard ISO 13320).

[0340] The fillers used in the composition according to the invention may or may not be surface-coated, and in particular, they may be coated with a hydrophobic treatment agent, in particular promoting the dispersion and compatibility of the filler in the composition. The hydrophobic treatment agent may be chosen from silicones, in particular silanes; fluorinated derivatives, fatty acids such as stearic acid; metal soaps such as aluminum dimyristate, the aluminum salt of hydrogenated tallow glutamate; amino acids; N-acylated amino acids or their salts; lecithin, isopropyl trisostearyl titanate, and mixtures thereof. The N-acylated amino acids may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zinc, sodium, potassium salts. The amino acid may be, for example, lysine, glutamic acid, alanine. The term alkyl(e) mentioned in the compounds cited above designates in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.

[0341] Such charges are advantageously chosen from:

[0342] - Silica (INCI name: Silica), such as porous silica microspheres sold under the name Silica Beads SB-700 by Myoshi; Sunsphere H51, Sunsphere H33, SA Sunsphere H53, Sunsphere H121 by AGC SLTECH; MSS-500 / 20N and Silica Shells by Kobo; Perluccia 14M by JGC Catalysts & Chemicals; hollow silica microspheres, such as BA4 silicas, by JGC Catalysts & Chemicals; amorphous silica microspheres coated with polydimethylsiloxane. Also suitable are Resifa FB-82 by AGC SLTECH (INCI: Silica (and) Sodium Chloride); Aerova 5 Microns by JIOS Aerogel; Sunsil-Oleo 150H by Sunjin Beauty Science (INCI: Silica (and) Cetyl Alcohol); Sensibeads SI 175 by Sensient; Miyofeel SXLL by Myoshi (INCI: Mica (and) Silica (and) Hydrogenated Lecithin (and) Calcium Chloride).

[0343] - Perlite such as those marketed by the company World Minerais under the name commercial designation Perlite P1430, Perlite P2550, Perlite P2040, or OpTiMat 1430 OR or 2550 OR. Europerl EMP-2 and Europerl 1 by Imerys; Perlite-MSZ12 by Myoshi.

[0344] - Zeolites such as the products marketed by the company Zeochem under the names ZeoFlair 300, Zeoflair 200, Zeoflair 100, X-MOL and X-MOL MT.

[0345] - Particles of carbonate or hydrogen carbonate of alkaline earth metals, such as calcium, magnesium, hydroxyapatite. Examples include calcium magnesium carbonate particles such as those marketed by Imerys company under the name Calcidol. Calcium carbonate is also suitable, for example the products sold by Omya company under the names Omyacare Extra 35-OG, Omyacare S 60-AV; by Sensient company under the name Carbomat. Magnesium carbonate particles and magnesium hydrogen carbonate may also be mentioned.

[0346] - Particles of kaolin, talc, for example marketed under the ranges Imercare, Imercare Pharma; Luzenac Pharma by Imerys; Rose Talc by Nippon Talc, Hallopure Ultra by I-minerals (INCI: Halloysite (and) Kaolin).

[0347] - Natural or synthetic mica, such as the product with the INCI name Synthetic Fluor- phlogopite, and marketed under the names RonaFlair Silk Mica by the company Merck, Sericite PHN by the company Presperse, NHS-100 and NHS-150 by the company Myoshi Kasei, those marketed under the names PDM-NSO or FNK-100 by the company Topy, Mearhnica DD by the company BASF.

[0348] - Boron nitride, for example Ronaflair Boroneige SQ-6 products marketed by Merck, Softouch Boron Nitride Powder CC6058 by Momentive Performances, Boron Nitride SHP 3 by Mizushima Ferroalloy; silica and titanium dioxide composites, such as the TSG® series marketed by Nippon Sheet Glass; bismuth oxychloride;

[0349] - Glass or ceramic microcapsules; such as, for example, particles of borosilicate.

[0350] - Barium sulfates, such as Flake Shaped Barium products Sulfate H by the company Sakai Chemical, LLD-5 BASO4 (PL) by the company Daito Kasei (NCI: Barium sulfate (and) lauroyl lysine).

[0351] - diatomaceous earths, such as the company's Imercare references Imerys.

[0352] - their mixtures.

[0353] Preferably, the composition according to the invention comprises, as mineral filler, kaolin, mica, calcium carbonate, and silica, as well as their mixtures.

[0354] According to a particularly advantageous embodiment of the invention, the mineral filler content represents from 2 to 20% by weight, preferably from 2 to 15% by weight, relative to the total weight of the composition. Organic load

[0355] For the purposes of the invention, the term “organic filler” means solid particles of at least one hydrocarbon or silicone compound, or combinations thereof, regardless of their coating.

[0356] The fillers are in the form of particles and may also be surface-treated or not, using compounds such as those described previously in the context mineral fillers.

[0357] The fillers used in the compositions according to the present invention may be of lamellar, globular, spherical, fiber or any other intermediate shape between these defined shapes. The fillers may be spherical, that is to say comprise at least one generally rounded portion, in particular defining at least one portion of a sphere, preferably internally defining a concavity or a hollow (sphere, globules, bowls, horseshoe, etc.) or lamellar.

[0358] Suitable charges include:

[0359] - Micronized waxes, natural or synthetic.

[0360] - Metallic soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

[0361] - Natural organic materials such as polysaccharide powders, and in part in particular starch powders, in particular corn, wheat or rice starches, crosslinked or not, starch powders crosslinked by octenylsuccinate anhydride, marketed under the name Dry-Flo® by the company National Starch, waxy corn starch powders such as those marketed under the names C* GEL 04201 by the company Cargill, Corn Starch B by the company Roquette, and Organic Corn Starch by the company Draco Natural Products, Amaze Nordic Barley by the company Nouryon, Celus Bi Feel by the company Roelm.

[0362] - Cellulose, especially in the form of spherical particles, such as products from the Cellulobeads range from Daito Kasei (for example Cellulobeads D-10, Cel-lulobeads D-5 and Cellulobeads USF). You can also use Tego Feel CIO cellulose from the Evonik company or microcrystalline celluloses from the Vivapur range from the Rettenmaier company, or the Avicel range from the Dupont company.

[0363] - N-acylated amino acids at C8-C22 carbon atoms, the amino acid may be for example lysine, glutamic acid, alanine, preferably lysine. We can cite for example, lauroyl lysine marketed in particular under the names Amihope LL by the company Ajinomoto or Corum 5105 by the company Corum.

[0364] - Polyhydroxyalkanoates such as Polyhydroxybutyrate particles (marketed under the name Biosoft 915 by the company Micro Powders).

[0365] - Acrylic (co)polymer particles, and their derivatives, in particular: * polymethyl methacrylate (INCI name Methyl Methacrylate Crosspolymer), sold under the name Covabead LH85 by the company Sensient, or Polymethyl Methacrylate, under the names Sepimat P by the company SEPPIC, Microsphere M-100® by the company Matsumoto Yushi-Seiyaku; * polymethyl methacrylate / ethylene glycol dimethacrylate (INCI name Methyl Methacrylate / Glycol Dimethacrylate Crosspolymer) sold under the name Dow Corning 5640 Microsponge Skin Oil Adsorber by Dow Corning; * crosslinked acrylate (INCI name: Acrylates Crosspolymer) marketed for example under the name Ganzpearl GMP-0820 by the company Ganz Chemical, * polyallyl methacrylate / ethylene glycol dimethacrylate sold under the name Poly-Pore L200, Poly-Pore E200 by Amcol Health and Beauty Solutions Inc., * ethylene glycol dimethacrylate / lauryl methacrylate copolymer (INCI name: Lauryl Methacrylate / Glycol Dimethacrylate Crosspolymer) sold under the name Polytrap 6603 Adsorber by Amcol Health and Beauty Solutions Inc.; * crosslinked acrylate / alkyl acrylate copolymer (INCI name: Acrylates / Ethylhexyl Acrylate Crosspolymer) sold under the name Techpolymer ACP-8C by the company Sekisui Plastics, * ethylene-acrylate copolymer, such as that marketed under the name Flobeads® by the company Sumitomo Seika Chemicals.

[0366] - acrylonitrile copolymer particles. in particular hollow particles expanded sold under the name Expancel by the company Akzo Nobel, or microspheres marketed under the name Micropearl F 80 ED® by the company Matsumoto.

[0367] - Polyurethane particles, for example sold under the names D- 400, D-800 (INCI name: HDI / Trimethylol Hexyllactone Crosspolymer (and) Silica), CS-400 (INCI name: HDI / PPG / Polycaprolactone Crosspolymer (and) Silica), by Toshiki Company.

[0368] - Silicone polymer particles, advantageously chosen from: * silicone resin particles such as those with the INCI name Polymethylsilses-quioxane, notably marketed under the name Tospearl, notably Tospearl 145 A, by the company Momentive Performance Materials, * silicone elastomer particles coated with silicone resin, in particular silsesquioxane resin, such as the products marketed under the names KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105 (INCI name: Vinyl Di-methicone / Methicone Silsesquioxane Crosspolymer), or KSP-300 (INCI name: Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane Crosspolymer) by the company Shin Etsu; *silicone elastomer particles such as products marketed under the name Dowsil 9506 Cosmetic Powder, by the company Dow Corning (INCI name: Dimethicone / Vinyl Dimethicone Crosspolymer); * Methylsilanol / Silicate Crosspolymer particles, for example in the form of bowls such as those marketed in particular under the name TAK-110 by the company Takemoto Oil & Fat.

[0369] - Polyamide particles, such as Nylon®, in particular Nylon 12, Nylon 6 / 12; such as nylon powders sold under the names Orgasol 2002 EXS NAT COS, Orgasol 4000 EXD NAT COS Caresse, by the company Arkema.

[0370] - Tetrafluoroethylene (Teflon) polymer particles.

[0371] Preferably, if the composition comprises it, the organic filler may be chosen from cellulose particles, particles of C8-C22 N-acylated amino acids such as lauroyl-lysine, as well as mixtures thereof.

[0372] According to a particular embodiment of the invention, the organic filler content represents from 2 to 10% by weight, preferably from 3 to 8% by weight, relative to the total weight of the composition.

[0373] According to a particularly advantageous embodiment of the present invention, the composition may not comprise polymeric organic fillers, considered to be microplastics. It is recalled that, for the purposes of the invention, “microplastics” means solid particles, of stable form, of polymer comprising carbon atoms in the polymer chain (backbone), of synthetic origin or of chemically modified natural origin, insoluble in water (i.e.: less than 2 g / l; OECD Directive 105), of a size less than 5 mm (and of a size less than 15 mm for fibers). “Stable form” means particles remaining solid in the composition and after its use. For example, polymer particles forming a film in the composition or during its use are not considered to be of stable form.Thus, preferably, the composition according to the invention may not comprise particles of acrylic, acrylonitrile, polyurethane, polyamide, tetrafluoroethylene polymer or silicone polymer particles, as described above. However, if it does comprise them, their content would preferably be less than 5% by weight, more particularly less than 2% by weight and advantageously less than 1% by weight, relative to the total weight of the composition. Preferably, if the composition comprises them, the content of organic fillers of the aforementioned microplastic type is less than or equal to 0.01% by weight, relative to the total weight of the composition, and very advantageously, the composition is free of them.

[0374] Preferably, the composition may comprise at least one mineral filler chosen from kaolin, mica, calcium carbonate and silica, and mixtures thereof. The composition may also comprise at least one organic filler, particularly cellulose, C8-C22 N-acylated amino acids such as lauroyl lysine, and mixtures thereof.

[0375] The total content of filler(s) advantageously represents from 2 to 30% by weight, preferably from 2 to 25% by weight, relative to the total weight of the composition. COSMETIC ADDITIVES

[0376] The compositions according to the invention may comprise additives commonly used in care and / or makeup products such as active ingredients such as vitamins, for example vitamins A, E, C, B3, adenosine, hyaluronic acid and its salts; UV filters; waxes; pasty compounds; hydrophilic thickeners; hydrophobic thickeners other than the clays described above, such as for example hydrophobic silicas, such as the compounds with the following INCI names: Silica Silylate, Silica Dimethyl Silylate; surfactants other than the aforementioned non-ionic hydrocarbon surfactants with an HLB of less than or equal to 8; film-forming agents; dextrin esters; perfumes; preservatives; and mixtures thereof. Preferably, the composition does not comprise a polyphenol type compound.The term "polyphenol" means any compound having in its chemical structure at least two benzene groups, in free or fused form, each benzene group comprising at least one hydroxyl group (OH), preferably at least 2, or even at least 3 (OH) groups. In particular, the composition does not include tannic acid, or if it does, its content does not exceed 0.5% by weight, relative to the total weight of the composition.

[0377] It is a matter of routine operations to adjust the nature and quantity of the additives present in the compositions in accordance with the invention, so that the desired cosmetic properties thereof are not affected.

[0378] Of course, those skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the compositions according to the invention are not, or not substantially, altered by the envisaged addition. Wax

[0379] The composition according to the invention may comprise at least one hydrocarbon wax, polar or apolar, a silicone wax, as well as their mixtures.

[0380] For the purposes of the present invention, the term "wax" means a lipophilic compound, solid at room temperature, with a reversible solid / liquid state change, having a melting point greater than or equal to 30°C and up to 120°C.

[0381] For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the ISO 11357-3; 1999 standard. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “DSC Q2000” by the company TA Instruments with the software “TA Universal Analysis.

[0382] The measurement protocol is as follows: A 5 mg sample of wax is placed in a crucible and subjected to a first temperature rise from -20°C to 120°C, at a heating rate of 10°C / minute, then cooled from 120°C to -20°C at a cooling rate of 10°C / minute and finally subjected to a second temperature rise from -20°C to 120°C at a heating rate of 5°C / minute. During the second temperature rise, the melting point of the solid fatty substance is measured, corresponding to the temperature of the most endothermic peak of the observed melting curve, representing the variation of the difference in absorbed power as a function of temperature. The enthalpy of fusion of the wax (AHf) can also be measured, which is the integral of the entire melting curve obtained. This enthalpy of fusion of the wax is the amount of energy required to change the compound from the solid state to the liquid state. It is expressed in J / g. Hydrocarbon wax

[0383] Waxes can be of vegetable, mineral, animal and / or synthetic origin.

[0384] In particular, the waxes have a melting temperature preferably above higher than or equal to 35°C and better higher than or equal to 40°C. Non-polar wax

[0385] By "apolar hydrocarbon wax", for the purposes of the present invention, is meant a wax consisting solely of carbon and hydrogen atoms and free of heteroatoms, such as for example N, O, Si, P....

[0386] As examples of apolar waxes suitable for the invention, mention may in particular be made of hydrocarbon waxes such as microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes, microwaxes, in particular polyethylene waxes. Polar wax

[0387] Polar waxes can in particular be hydrocarbon or silicone.

[0388] For the purposes of the present invention, the term "polar hydrocarbon wax" means a wax whose chemical structure is formed essentially, or even consists of, carbon and hydrogen atoms, and comprising at least one heteroatom more particularly chosen from oxygen, optionally nitrogen, or mixtures thereof. It may thus contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

[0389] By “silicone wax” is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups.

[0390] According to a first preferred embodiment, the polar wax is a hydro- wax carbonaceous.

[0391] As hydrocarbon polar wax, a wax chosen from ester waxes and alcohol waxes is preferred.

[0392] According to the invention, the term “ester wax” means a wax comprising at least one ester function. Ester waxes may also be hydroxylated.

[0393] By “alcohol wax” is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl group (OH).

[0394] In particular, the following may be used as ester wax, alone or in mixtures: i) waxes of formula RiCOOR2 in which Ri and R2 represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 6 to 50, in particular from 10 to 50, which may contain a heteroatom such as for example O, N and whose melting temperature varies more particularly from 30 to 120 C. In particular, it is possible to use as ester wax a C2o-C4o alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C2o-C4O alkyl stearate. Such waxes are sold in particular under the names “Kester Wax K 82 P®”, “Hydroxypolyester K 82 P®”, “Kester Wax K 80 P®”, or “Kester Wax K82H” by the company Koster Keunen. Stearyl heptanoate and stearyl caprylate and their mixtures can also be used. ii) di-(trimethylol-1,1,1 propane) tetrastearate, iii) diester waxes of a dicarboxylic acid of general formula R3-(-OCO-R4-COO-R5), in which R3 and R5 are identical or different, preferably identical and represent a C4-C30 alkyl group and R4 represents a linear or branched C4-C30 aliphatic group and which may or may not contain one or more unsaturations. Preferably, the C4-C30 aliphatic group is linear and unsaturated. iv) Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having in particular linear or branched fatty chains, in C8-C32, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, as well as waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold in the Phytowax Castor range, for example Phytowax Castor 22L73®, or waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, such as those in the Phytowax Olive range, for example Phytowax Olive 18L57, marketed by the company Sophim. Such waxes are notably described in application FR2792190. (v) Waxes corresponding to partial or total, preferably total, esters of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol. By total esters, it is meant that all the hydroxyl functions of the glycerol are esterified. Examples include trihydroxy stearin (or glyceryl trihydroxystearate), tristearin (or glyceryl tristearate), tribehenin (or glyceryl tribehenate), alone or in a mixture. Suitable compounds include triesters of glycerol and 12-hydroxystearic acid, or hydrogenated castor oil, such as Thixcin R, Thixcin E, marketed by Elementis Specialties. (vi) Mention may also be made of waxes of animal or vegetable origin, such as beeswax, synthetic beeswax, camauba wax, candelilla wax, rice bran wax, Ouricury wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax, sunflower wax, in particular refined. vii) Mention may also be made of hydrocarbon waxes, polyoxyalkylenated or polyglycerolated, natural or synthetic, of animal or vegetable origin; the number of oxyalkylenated units (in C2-C4) may vary from 2 to 100, the number of glycerol units may vary from 1 to 20. As examples, mention may be made of polyoxyethylene beeswax, such as PEG-6 beeswax, PEG-8 beeswax; polyoxyethylene camauba waxes, such as PEG-12 camauba; lanolin waxes, hydrogenated or not, polyoxyethenate or polyoxypropylene, such as PEG-30 lanolin, PEG-75 lanolin; PPG-5 lanolin wax glyceride; polyglycerol beeswax, including polyglyceryl-3 Beewax, Acacia Decurrens / Jojoba / Sunflower Seed Wax / Polyglyceryl-3 Esters blend, polyglycerol vegetable waxes such as mimosa, jojoba, sunflower waxes, and blends thereof (Acacia Decurrens / Jojoba / Sunflower Seed Wax Polyglyceryl-3 Esters.

[0395] According to another embodiment, the polar wax may be an alcohol wax. As alcohol wax, mention may be made of mixtures of linear, saturated C3o-C5o alcohols such as, for example, Performacol 550 Alcohol wax from New Phase Technologie, stearic alcohol, cetyl alcohol, or mixtures thereof.

[0396] Preferably, if the composition comprises it, the wax is chosen from hydrocarbon waxes. More particularly, it is chosen from polar hydrocarbon waxes such as waxes of animal or vegetable origin, waxes of animal or vegetable origin obtained by catalytic hydrogenation of animal or vegetable oils; ester waxes such as waxes corresponding to partial or total esters, preferably total, of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol; as well as mixtures thereof. Silicone wax

[0397] By “silicone wax” is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups.

[0398] As silicone wax, we can cite for example, silicone beeswax, mixtures comprising a compound of the C30-45 Alkyldimethylsilyl Polypropylsil-sesquioxane type (INCI name), for example the product Dow Corning SW-8005 C30 Resin Wax marketed by the company Dow Corning. Mention may also be made of mixtures comprising a compound of the C30-45 Alkyl Methicone type (INCI name), such as for example the product Dow Corning® AMS-C30 Cosmetic Wax. Preferably, the silicone wax is C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane. It should be noted that this wax is not considered to be a film-forming polymer of the silicone resin type.

[0399] The content of wax(es), in the case where the composition comprises it, advantageously varies from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight, relative to the total weight of the composition.

[0400] According to one embodiment, the composition comprises at least one wax chosen from the total esters of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol. By total esters, it is meant that all the hydroxyl functions of the glycerol are esterified. By way of example, mention may be made of glyceryl trihydroxystearate (or trihydroxystearin), glyceryl tristearate (or tristearin), glyceryl tribehenate (or tribehenin), alone or as a mixture, preferably glyceryl tribehenate.

[0401] If the composition comprises it, the content of total ester of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol represents from 0.1 to 3% by weight, more particularly from 0.2 to 2% by weight, relative to the total weight of the composition.

[0402] Preferably, if the composition comprises it, the silicone wax content does not exceed 3% by weight relative to the total weight of the composition. Preferably, if the composition comprises it, the silicone wax content is between 0.1 and 2% by weight, relative to the total weight of the composition, preferably it is free of it. Pasty compound

[0403] The composition according to the invention may also comprise at least one pasty compound at room temperature and atmospheric pressure.

[0404] For the purposes of the present invention, the term "pasty" means a lipophilic compound with a reversible solid / liquid state change, exhibiting in particular in the solid state an anisotropic crystalline organization, and comprising at room temperature a liquid fraction and a solid fraction.

[0405] In other words, the onset melting temperature of the pasty compound may be lower than room temperature. The liquid fraction of the pasty compound measured at room temperature may represent 9 to 97% by weight of the pasty compound. This liquid fraction at room temperature preferably represents between 15 and 85%, more preferably between 40 and 85% by weight.

[0406] The melting point of the pasty fatty body is determined according to the same principle as that detailed previously for waxes. In the case of pasty compounds, however, the measurement protocol is as follows: A 5 mg sample of pasty fatty substance placed in a crucible is subjected to a first temperature rise from -20°C to 100°C, at a heating rate of 10°C / minute, then is cooled from 100°C to -20°C at a cooling rate of 10°C / minute and finally subjected to a second temperature rise from -20°C to 100°C at a heating rate of 5°C / minute. The melting point of the pasty fat is the temperature value corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of temperature. It should be noted that the liquid fraction by weight of the pasty fatty substance at room temperature is equal to the ratio of the enthalpy of fusion consumed at room temperature to the enthalpy of fusion of the pasty fatty substance. The heat of fusion of a pasty fat is the heat consumed by the fat to change from a solid to a liquid state. A pasty fat is said to be in a solid state when its entire mass is in crystalline solid form. A pasty fat is said to be in a liquid state when its entire mass is in liquid form. The enthalpy of fusion of the pasty fat is the amount of energy required to transform the pasty fat from the solid state to the liquid state. It is expressed in J / g. The enthalpy of fusion of the pasty fat is equal to the value under the curve of the thermogram obtained.

[0407] The pasty compound may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.

[0408] The pasty compound(s) may in particular be chosen from: - lanolin and its derivatives, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, oxypropylenated lanolins; - petroleum jelly (also called petrolatum), - ethers of pentaerythritol and C2-C4 polyalkylene glycol, for example, compounds with the following INCI names: PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether, and mixtures thereof. Examples include the mixture marketed under the name Lanolide, by the company Vevy, - fat-soluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50. Among the fat-soluble polyethers, copolymers of ethylene oxide and / or propylene oxide with long-chain C6-C30 alkylene oxides are considered in particular, more preferably such that the weight ratio of ethylene oxide and / or propylene oxide with alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, we will notably mention the product with the INCI name PEG-45 / Dodecyl Glycol Copolymer marketed for example under the brand name Elfacos ST9 by the company Akzo Nobel, - esters resulting from the condensation of a linear or branched, preferably saturated, C6-C10 dicarboxylic acid and an ester of diglycerol and monocarboxylic acids, optionally hydroxylated, linear or branched, preferably saturated, C6-C20, in particular the diester obtained by condensation of adipic acid and a mixture of diglycerol esters with a mixture of C6-C20 fatty acids such as caprylic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, in particular marketed under the reference Softisan® 649 by the company Cremer Oleo. (INCI name: Bis-Diglyceryl Polyacyladipate-2), - triglycerides of fatty acids, saturated or not, linear or branched, possibly mono or polyhydroxylated, preferably Ci2-Ci8, possibly hydrogenated (totally or partially); such as for example the glycerides of saturated fatty acids C12-C18 marketed under the name Softisan 100® by the company Cremer Oleo (INCI name: Hydrogenated Coco-Glycerides), - esters of dimer diol, or polyol, and dimer diacid such as for example: * esters of dilinoleic alcohol dimer and dilinoleic acid whose hydroxyl groups are esterified by a mixture of phytosterols, behenyl alcohol and isostearyl alcohol, for example the ester sold under the name Plandool G by the company Nippon Fine Chemical (INCI name: Bis-Behenyl / Isostearyl / Phytosteryl Dimer Dilinoleyl Dimer Dilinoleate); * esters of dilinoleic acid and a mixture of phytosterols, isostearyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol, for example the ester sold under the name Plandool H or Plandool S by the company Nippon Fine Chemical (INCI name: Phytosteryl / Isostearyl / Cetyl / Stearyl / Behenyl Dimer Dilinoleate); - butters of vegetable origin such as mango butter, such as that marketed under the reference Lipex 203 by the company Aarhuskarlshamn, shea butter, in particular that whose INCI name is Butyrospermum Parkii Butter, such as that marketed under the reference Sheasoft® by the company Aarhuskarlshamn, cupuacu butter (Rain forest RF3410 from the company Beraca Sabara), murumuru butter (Rain Forest RF3710 from the company Beraca Sabara), cocoa butter; as well as orange wax such as, for example, that marketed under the reference Orange Peel Wax by the company Koster Keunen, - fully or partially hydrogenated vegetable oils, such as hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated vegetable oils such as hydrogenated vegetable oil mixture soy, copra, palm and rapeseed oil, for example the mixture marketed under the reference Akogel® by the company Aarhuskarlshamn (INCI name Hydrogenated Vegetable Oil), partially hydrogenated trans isomerized jojoba oil manufactured or marketed by the company Desert Whale under the commercial reference Iso-Jojoba-50®, partially hydrogenated olive oil such as, for example, the compound marketed under the reference Beurrolive by the company Soliance, - hydrogenated castor oil esters, such as dimer hydrogenated castor oil di-linoleate, for example Risocast-DA-L sold by Kokyu Alcohol Kogyo, hydrogenated castor oil isostearate, for example Salacos HCIS (VL) sold by Nisshin Oil, - and mixtures thereof.

[0409] If the composition comprises at least one pasty compound, its content varies from 0.5 to 5% by weight, and preferably from 0.5 to 3% by weight, relative to the total weight of the composition. Dextrin ester

[0410] The composition may optionally comprise at least one ester of dextrin and fatty acid, in particular C12 to C24, preferably C14 to C18, or mixtures thereof. More preferably, the dextrin ester is an ester of dextrin and C12-C18 fatty acid, in particular C14-C18. Preferably, the dextrin ester is chosen from dextrin palmitate and dextrin myristate. These dextrin esters are, for example, commercially available, in particular under the name RHEOPEARL from the company Chiba Floor Milling. Co

[0411] If the composition comprises it, the content varies from 0.5 to 8% by weight, preferably from 0.5 to 5% by weight, relative to the total weight of the composition.

[0412] The invention also relates to a method for making up and / or caring for the skin and / or lips, in particular the lips, in which the composition according to the invention is applied.

[0413] It is further indicated that the compositions according to the invention more particularly comprise a cosmetically (or physiologically) acceptable medium, that is to say which has a pleasant color, odor and feel and does not generate unacceptable discomfort, that is to say tingling, tightness, redness, likely to discourage the user from applying such compositions.

[0414] Throughout the description, including the claims, the expression "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified; "at least one" meaning "one or more".

[0415] The expressions “between... and...” and “ranging from... to...” must be understood inclusively, unless otherwise specified.

[0416] Unless otherwise indicated, the contents are expressed as active matter of the ingredient(s) considered.

[0417] Furthermore, the sum of the quantities of the ingredients of the composition represents 100% by weight of the composition.

[0418] The invention is illustrated in more detail by the examples presented below.

[0419] Raw materials are named by their chemical name or their INCI name. EXAMPLES Viscosity measurement protocol

[0420] The viscosity measurement is carried out at 25°C with a sample of the composition, at least 24 hours after its manufacture (storage at room temperature), using a RHEOMAT RM 180 viscometer equipped with a spindle no. 2, 3 or 4, the measurement being carried out after 10 minutes of rotation of the spindle within the formula, at a shear of 200 revolutions / min (rpm). Tights measurement protocol

[0421] Material used: * White supplement strip 150cm*25cm (Supplier: Soudotique, reference: DFSUP15025B) * White round replacement 38mm diameter (Supplier: Soudotique, reference: DESUPDIAM38B) * Stable Micro Systems Texturometer (model: TA.XT. plus) and its “Exponent” software * Round measuring mobile allowing the fixing of the 38 mm diameter supplementary round.

[0422] Preparation of the deposit: * Mark out the length of the deposit (10cm) on a strip of white tape. * Apply the composition packaged in a hot water bottle with a dipping applicator so as to obtain 4 layers, as follows: a) remove the applicator without wiping off the excess on the edges and on the "leather" side of the support, apply the composition over the 10 cm length. Make as many passes as desired, always in the same direction, over the entire length and without turning the applicator over, to obtain a deposit of uniform thickness. (=application 1); b) rotate the supplement strip 180° (so that the direction of application of the second layer of composition is in the opposite direction); c) remove the applicator without wiping off the excess on the edges and apply a new layer of composition on the previous one, over the length of the 10 cm applied, under the same conditions as step 1 (= application 2); - repeat steps b) and c) twice; * Leave to dry for 1 hour on a hot plate at 32°C.

[0423] Measuring the tights with a texturometer:

[0424] The test parameters are given below: Approach Speed ​​(or Pre-Speed) 1 mm / s Speed ​​(from contact detection) 0.5 mm / s Retraction Speed ​​(or Post-Speed) 40 mm / s Force (and corresponding pressure) 800 g Hold Time 5 s Trigger Force 5 g Maximum Tracking Speed ​​5 mm / s

[0425] The adhesive is characterized by the detachment work measured during unloading (tensile phase), corresponding to the peak force (expressed positively in g) and the area (expressed positively in g / sec) under the time axis.

[0426] The higher the peak force value, the stickier the deposit.

[0427] 3 samples are prepared and 2 measurements are carried out on the same sample; first in the center of the sample, the next at a different location on the sample not at the ends of the strip; a new white supplementary circle is placed in the mobile at each new measurement.

[0428] The result is the average of the measurements on the three samples. Protocol for measuring holding and transfer 1. Test preparation:

[0429] Support: Beige supplale (2.5 x 5 cm) (sold by Soudotique).

[0430] Spread the composition (D) over the entire surface 3 times in a row to obtain a homogeneous deposit. Repeat the operation on two other strips. Leave the deposit to dry on a plate heated to 32°C for 45 minutes. Possibly take a photo of each support with the deposit (made up) before the request. 2. Requests:

[0431] Preparation of a tissue for each request: Fold each tissue twice along the long edge and then twice the other way to form a square. Dry resistance:

[0432] Rub once with the handkerchief folded lengthwise one of the three made-up supports; the force applied is that normally exerted when removing make-up from the skin or lips. Observe the condition of the rubbed support as well as the used surface of the handkerchief, in particular the remaining coloring, the transferred coloring. Possibly take a photo.

[0433] Note that the evaluation of the transfer resistance is made with this stress.

[0434] In the event that several passes are made, they would then be made with the same force and always in the same direction (i.e. after each pass, the handkerchief is lifted to be repositioned at the "beginning" of the strip in order to be reapplied to the deposit in the same way as in the previous pass). Possibly take a photo between each step or only at the end of the evaluation. This type of process can be implemented to evaluate the overall resistance of the deposit.

[0435] Water resistance:

[0436] Insert the second coated support without folding it into a centrifuge tube. Add 10 grams of demineralized water. Centrifuge for 10 minutes at 450g. Optionally take a photo of the support after mixing, immediately after the operation. Rub once with a tissue along the length of the support, without waiting, with the same force as that applied for dry resistance. Observe the condition of the rubbed support as well as the used surface of the handkerchief, in particular the remaining coloring, the transferred coloring. Possibly take a photo.

[0437] The protocol for multiple passes is the same as that detailed previously for dry resistance. Oil resistance:

[0438] Implement the same protocol as for water resistance, on the third made-up support, replacing the water with the same quantity of olive oil (Refined Olive Oil - Aarhuskarlshamn). Rating:

[0439] For each request, note the result according to the table below:

[0440] [Tables2] Deposit rating State of the deposit Fabric rating Surface of the fabric in contact with the deposit - - Total or partial removal of the deposit on the rubbed area; the surface of the support appears in places 5 Very intense staining - very significant to total transfer of the color - Partial removal resulting in a significantly and visibly less intense staining of the deposit. 4 Intense staining - significant transfer of the color + Reduction in the intensity of the color of the deposit perceptible but which does not reveal the support 3 Medium staining - average transfer of the color ++ No substantial variation in the color of the deposit 2 Slight staining - little transfer of the color +++ No variation in the color of the deposit 1 No staining or barely visible staining - no to very little transfer of the color Examples 1 1. Composition

[0441] The following composition was prepared, the list of ingredients and the contents in mass percentages of which are gathered in the table below.

[0442] The following composition was prepared, the list of ingredients and the contents in mass percentages of which are gathered in the table below.

[0443] [Tables3] Phases Ingredients (INCI name) Composition 1 Al Isododecane (Isodecane, Ineos) 16.89 Al Trimethylsiloxysilicate (SR1000, Momentive performance Materials) 5 Al Nylon-611 / Dimethicone copolymer (Dowsil 2-8179 Gellant, Dow) 3.33 A2 Polyglyceryl-6 polyricinoleate (SY-Glyster CRS-75, Sakamoto Yakuhin) 3.44 A2 Dicapryl ether 1.15 A3 Disteardimonium hectorite (Bentone 38 VCG, Elementis) 1.37 A4 Calcium carbonate (Omyacare Extra 35-OG, Omya) 5.75 B1 Water 30.76 B1 Pullulan (Pullulan cosmetic grade, Hayashibara) 7.69 B2 Glycerin 5 B2 Alcohol denatured. 9.62 C Mica (Mearlmica SV, Sun Chemicals) 2.5 C Red 7 (Unipure Red LC 3079, Sensient) 7.5 2. Preparation of the compositions

[0444] Preparation of aqueous phase B: at room temperature mix B1 for 5 minutes in a speedmixer at 3500 rpm then add B2 and stir again for 5 minutes at 3500 rpm Preparation of the fatty phase: In a heating pan, place the ingredients of phase Al, stirring with the Rayneri rotor stator at 1000 rpm for 10 minutes at 60°C until completely dissolved, then pour in A2, then A3 once the mixture is homogenized, and continue stirring for 10 minutes. Allow the resulting mixture to cool to room temperature and introduce A4, stirring for 10 minutes until the fillers are well dispersed. Preparation of the emulsion: at room temperature, slowly pour the aqueous phase B into the previous preparation A, while stirring with the Rayneri rotor stator. Leave to stir for 5 minutes at 3500 rpm. Preparation of phase C: place the ingredients of phase C in the bowl of an IKA MV20 grinder and mix at maximum speed 4 times for 15 seconds, making sure After every 15 seconds, remove any powder that may have adhered to the walls. Add the resulting phase C while stirring at Rayneri 3500 rpm for another 5 minutes until the composition is homogenized. 3. Evaluation of compositions

[0445] A homogeneous composition is obtained, without release after 24 hours at room temperature.

[0446] For lip makeup, composition 1 is very easy to apply with a dip applicator, allowing you to obtain a matte, intense and even color.

[0447] The film obtained after drying is not very sticky, comfortable, does not transfer and does not migrate into fine lines.

[0448] The deposit was evaluated in a test of resistance to mechanical and chemical attacks (dry friction, water, oil) according to the resistance and transfer protocol detailed previously.

[0449] The table below brings together the results obtained:

[0450] [Tables4] Composition 1 Type of aggression Dry Water Oil Note: state of the deposit +++ +++ ++ Note: state of the fabric surface in contact with the deposit 1 1 2

[0451] Surprisingly, composition 1 has very good hold and little or no transfer even though the silicone resin content is relatively low. Comparative example 2 1. Compositions

[0452] The following compositions were prepared, the list of ingredients and the contents in mass percentages of which are gathered in the table below. Composition 2 is in accordance with the invention, composition A is a comparative composition because it is free of pullulan.

[0453] [Tables5] Phases Ingredients (INCI name) Composition 2 Composition A Al Polyglyceryl-6 Polyricinoleate (SY-Glyster CRS-75, Sakamoto Yakuhin) 3.44 3.44 Al Dicaprylyl ether (Cetiol OE, BASF) 1.15 1.15 Al Undecane (and) Tridecane (Cetiol UT, BASF) 16.86 16.86 Al Trimethylsiloxysilicate (SR1000, Momentive performance Materials) 5 5 Al Nylon-611 / Dimethicone copolymer (Dowsil 2-8179 Gellant, Dow) 3.33 3.33 A2 Disteardimonium Hectorite (Bentone 38 VCG, Elementis) 1.37 1.37 A3 Calcium carbonate Omyacare Extra 35-OG, Omya) 5.75 5.75 B1 Water 30.76 38.45 B1 Pullulan (Pullulan cosmetic grade, Hayashibara) 7.69 0 B2 Glycerin 5 5 B2 Denatured alcohol. 10 10 C Mica (Mearlmica SV, Sun Chemicals) 2.5 2.5 C Red 7 (Unipure Red LC 3079, Sensient) 7.5 7.5 2. Preparation of the composition

[0454] Preparation of aqueous phase B: at room temperature mix B1 for 5 minutes in a speedmixer at 3500 rpm then add B2 and stir again for 5 minutes at 3500 rpm Preparation of the fatty phase: In a heating pan, introduce the ingredients of phase Al, and stir the Rayneri rotor stator at 2000 rpm for 10 minutes at 75°C until completely dissolved, then still stirring, pour A2, then A3 when the mixture is homogenized. Continue stirring for 10 minutes. Allow to cool and add A4, stirring for another 10 minutes until the fillers are well dispersed and the mixture has returned to room temperature. Emulsification: at room temperature, slowly pour aqueous phase B into the previous preparation A, while stirring the Rayneri rotor stator. Leave to stir for 5 minutes at 3300 rpm. Preparation of phase C: Place the ingredients of phase C in the bowl of an IKA MV20 grinder and mix at maximum speed 4 times for 15 seconds, taking care after each 15 seconds to remove any powder that may have adhered to the walls. Add the resulting phase C while stirring at Rayneri 3300 rpm for another 5 minutes, until the composition is homogenized. 3. Evaluation of compositions

[0455] [Tableauxô] Composition Comments Composition 4 invention Homogeneous composition, no release after 24 hours at room temperature When applied to the lips, the composition is very easy to apply with a dip applicator, allowing for a matte, intense and even color. The film obtained after drying is not very sticky, comfortable, does not transfer and does not migrate into fine lines. Composition A comparative Homogeneous composition, no release after 24 hours at room temperature When applied to the lips, the composition is very easy to apply with a dip applicator, allowing for a matte, intense and even color. The film obtained after drying is more sticky than composition 1, and transfers more after the oil test. The film does not migrate into fine lines.

[0456] The deposit was evaluated in a test of resistance to mechanical and chemical attacks (dry friction, water, oil) according to the resistance and transfer protocol detailed previously.

[0457] The table below brings together the results obtained:

[0458] [Tables?] Composition 1 Composition A Type of aggression Dry Water Oil Dry Water Oil Note: state of the deposit +++ +++ ++ +++ +++ ++ Note: state of the fabric surface in contact with the deposit 1 1 2 1 1 4

Claims

Claims

1. Cosmetic composition for making up human keratin materials, in particular the skin and / or the lips, preferably the lips, in the form of a water-in-oil emulsion, comprising: - at least 3% by weight, relative to the total weight of the composition, of pullulan; - at least 12% by weight, relative to the total weight of the composition, of at least one first apolar hydrocarbon oil comprising from 8 to 16 carbon atoms, - at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone acrylamide copolymers, and mixtures thereof, - at least one coloring matter.

2. Composition according to claim 1, characterized in that the pullulan content is between 4 and 15% by weight, more particularly between 5 and 10% by weight, relative to the total weight of the composition.

3. Composition according to any one of the preceding claims, characterized in that the first apolar hydrocarbon oil is chosen from branched C8-C16 alkanes, such as preferably isododecane, isodecane, isohexadecane, C8-9 Isoalkane, C1-13 Isoalkane, and mixtures thereof; from linear alkanes, preferably C8-C14, and mixtures thereof, such as preferably n-dodecane, n-tetradecane, C9-12 Alkane, undecane-tridecane mixture; as well as mixtures thereof; and preferably from isododecane, undecane, tridecane, C9-12 Alkane, alone or in mixtures.

4. Composition according to any one of the preceding claims, characterized in that the content of first apolar hydrocarbon oil(s) represents from 12 to 40% by weight, preferably from 12 to 35% by weight, relative to the total weight of the composition.

5. Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from: - non-glycerolated silicone resins chosen from alkyl-siloxysilicate, arylsiloxysilicate, alkylaryl siloxysilicate, polysilsesquioxane resins, as well as their mixtures; more particularly from silicone resins with the following INCI names: Trimethylsiloxysilicate, Phenylpropyldimethylsiloxysilicate, Polymethylsilsesquioxane, Polypropyl- silsesquioxane, as well as mixtures thereof; - glycerolated silicone resins, in particular of formula: (RSSiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R^SiO2 / 2M^^ in which - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - each R2 is a mono- or poly-glycerol group of the following general formula (2) -(CH2)2—C1H21—O—(CH2CH(OH)CH2O)iR4 (2), wherein R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and the subscripts 1 and i are integers that satisfy the conditions 0 <l< 15 et 0<i<5, - each R3 is an identical or different group of general formula (3), (4), (5) or (6) below: —(CH2)2—CmH2m—(SiOR^j—SiRS (3) —(CH2)2—CmH2m—SiR'kl—(OSiR*3)3_kl) (4) —(CH2)2—CmH2m—SiR'kl—(OSiRWOSiR1,)^^ (5) —(CH2)2—CmH2m—SiR^—(OSiR'^OSiR^OSiRM^K^ (6) Or - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - the indices m, j and ki to k3 are integers which satisfy the following conditions: 0 <m<5, 0<j<500, 0<kl<2, 0<k2<2 et 0<k3<2 ; - the indices a, b, c, d, e and f are numbers that satisfy the following conditions: 0 <a<400, 0<b<200, 0<c<400, 0<d<320, 0<e<320, 0<f<1000 et 0,5<(a+b+c) / f<l,5 ; et de préférence de formule [(CH3)3SiOi / 2]a[R(CH3)2SiOi / 2]b(SiO4 / 2)f (21) où R désigne le groupe 3-glyceroxypropyle de structure -C3H6OCH2-CH(OH)CH2OH ; les indices a, b et f sont des entiers qui satisfont aux conditions 0<a<400, 0<b<30, 0 <f<1000 et 0,5 <(a+b) / f<l,5 ; - silicone acrylate copolymers chosen from vinyl polymers grafted with a carbosiloxane dendrimer, in particular with the INCI name Acrylates / Polytrimethyl siloxymethacrylate Copolymer, from copolymers comprising (meth)acrylic groups and polydimethylsiloxane groups, in particular with the INCI name Acrylates / Dimethicone Copolymer, and mixtures thereof; - mixtures thereof.

6. Composition according to any one of the preceding claims, characterized in that the silicone film-forming polymer is chosen from silicone resins, non-glycerolated or glycerolated, and preferably non-glycerolated, in particular chosen from Trimethylsiloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, as well as their mixtures.

7. Composition according to any one of the preceding claims, characterized in that the content of silicone film-forming polymer represents from 2 to 25% by weight, preferably from 3 to 20% by weight, relative to the total weight of the composition.

8. Composition according to any one of the preceding claims, characterized in that the composition comprises at least one mineral lipophilic thickener, in particular chosen from lipophilic clays, more particularly from lipophilic clays of the hectorite type comprising at least one quaternary ammonium group, bentonites comprising at least one quaternary ammonium group, or mixtures thereof, and preferably from Disteardimonium Hectorite, Stearalkonium Hectorite, Quatemium-18 Hectorite, as well as mixtures thereof, and even more preferably Disteardimonium Hectorite.

9. Composition according to any one of the preceding claims, characterized in that the content of mineral thickener represents from 0.2 to 4% by weight, preferably from 0.3 to 3% by weight, relative to the total weight of the composition.

10. Composition according to any one of the preceding claims, characterized in that the water content is at least 20% by weight, preferably between 20 and 50% by weight, preferably between 20 and 40% by weight, relative to the total weight of the composition.

11. Composition according to any one of the preceding claims, characterized in that the composition optionally comprises at least one second oil, different from the first oil(s), chosen from non-volatile hydrocarbon oils, polar or apolar, from volatile or non-volatile silicone oils, as well as their mixtures.

12. Composition according to the preceding claim, characterized in that the second oil is chosen from non-volatile polar hydrocarbon oils such as: - C10-C26 alcohols; - ethers of formula ROR', carbonates of formula RO(CO)OR', formulas in which, identical or not, the groups R, R' represent a hydrocarbon group comprising at most 16 carbon atoms, saturated or unsaturated, branched or unbranched; - oils comprising one or more ester functions and comprising at least one hydrocarbon group, linear or branched, saturated, unsaturated or aromatic, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil may optionally comprise one or more ether or hydroxyl functions; - liquid polyesters resulting from the reaction of a mono- or polyunsaturated acid dimer, the fatty acid comprising from 16 to 22 carbon atoms; - as well as their mixtures; and preferably from vegetable oils;ester oils, comprising 1 to 4 ester functions, and comprising at least one hydrocarbon group, linear or branched, saturated, unsaturated or aromatic, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil possibly comprising one or more ether or hydroxyl functions; ether oils of formula ROR' where R, R', identical or not, represent a hydrocarbon group comprising at most 16 carbon atoms, saturated or not, branched or not; mixtures thereof.;

13. Composition according to any one of claims 11 or 12, characterized in that the content of second oil(s), if the composition comprises any, does not exceed 15% by weight, preferably varies from 0.1 to 15% by weight, relative to the total weight of the composition.

14. Composition according to claim 11, characterized in that if the composition comprises at least one silicone oil, volatile or non-volatile, their content does not exceed 5% by weight, advantageously does not exceed 3% by weight, preferably does not exceed 1% by weight, relative to the total weight of the composition; preferably the composition is free of them.

15. Composition according to any one of the preceding claims, characterized in that the coloring matter is chosen from powdery coloring matters, liposoluble dyes, water-soluble dyes, and mixtures thereof.

16. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-ionic hydrocarbon or silicone surfactant with an HLB of less than or equal to 8, chosen from (poly)oxyethylenated, (poly)oxypropylenated C8-C30 alcohols, (poly)oxyethylenated, (poly)oxypropylenated C8-C30 esters, polyoxyalkylenated, preferably polyhydroxylated, C12-C20 fatty acid polyesters having from 4 to 50 moles of ethylene oxide, sorbitan alkyl(C8-C30)- and polyalkyl(C8-C30)- esters, alkyl(C8-C30)- and polyalkyl(C8-C30)- esters (poly)glycerolated, alone or as mixtures; non-ionic silicone surfactants chosen from oxyalkylenated polydimethylmethylsiloxanes (C2 - C3), with HLB < 8, preferably with the following INCI names: PEG / PPG-8 / 8 Dimethicone, Bis-PEG / PPG-14 / 14 Di-methicone, PEG / PPG-18 / 18 Dimethicone, PEG / PPG-19 / 19 Dimethicone, PEG-3 Dimethicone, PEG-10 Dimethicone, as well as mixtures thereof.

17. Composition according to any one of the preceding claims, characterized in that it comprises at least one polyglycerolated non-ionic hydrocarbon surfactant of HLB < 8, more particularly chosen from: - esters of isostearic acid and polyglycerol having from 2 to 10 moles of glycerol units such as Polyglyceryl-4 Isostearate, Polyglyceryl-3 Diisostearate; Polyglyceryl-2 Diisostearate, Polyglyceryl-10 Isostearate, Polyglyceryl-2 Triisostearate; - stearic acid and polyglycerol esters having 2 or 3 moles of glycerol units such as Polyglyceryl-2 Sesquistearate, Poly-glyceryl-3 Distearate, Polyglyceryl-2 Stearate - oleic acid and polyglycerol esters having 2 to 3 moles of glycerol units such as Polyglyceryl-2 Oleate, Polyglyceryl-3 Oleate, Polyglyceryl-2 Dioleate; Polyglyceryl-3 Dioleate;- polyglyceryl polyricinoleate(s) having from 3 to 6 moles of glycerol units such as Polyglyceryl-3 Polyricinoleate; Polyglyceryl-5; Polyglyceryl-6 Polyricinoleate; - mixtures thereof.;

18. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-ionic polyglycerolated hydrocarbon surfactant chosen from polyglyceryl polyricinoleate(s) having from 3 to 6 moles of glycerol units, in particular Polyglyceryl-6 Polyricinoleate.

19. Composition according to any one of claims 16 to 18, characterized in that the content of hydrocarbon or silicone surfactant(s), preferably non-ionic hydrocarbon surfactant(s), represents from 2 to 10% by weight, preferably from 2 to 7% by weight, relative to the total weight of the composition.

20. Composition according to any one of the preceding claims, characterized in that it comprises at least one polyol which is liquid at room temperature, in C2-C8, preferably in C3-C6, saturated or unsaturated, linear or branched, comprising from 2 to 6 hydroxyl groups, more particularly chosen from glycerin, diglycerin, glycols or alkanediols, in C3-C8, linear or branched, saturated, in particular propylene glycol, propanediol, butylene glycol, pentanediol, pentylene glycol, caprylyl glycol, dipropylene glycol, as well as mixtures thereof, and preferably glycerin.

21. Composition according to the preceding claim, characterized in that the polyol content varies from 3 to 20% by weight, in particular from 4 to 15% by weight, relative to the total weight of the composition.

22. Composition according to any one of the preceding claims, characterized in that it comprises at least one C2-C6 monoalcohol, more particularly C2-C4, preferably chosen from ethanol, isopropanol, tert-butanol or butanol, or mixtures thereof, and preferably at least ethanol.

23. Composition according to the preceding claim, characterized in that the monoalcohol content represents from 3 to 20% by weight, preferably from 5 to 15% by weight, relative to the total weight of the composition.

24. Composition according to any one of the preceding claims, characterized in that it comprises at least one wax chosen from the total esters of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol, preferably glyceryl trihydroxystearate, glyceryl tristearate, glyceryl tribehenate, alone or as a mixture, preferably glyceryl tribehenate.

25. Composition according to the preceding claim, characterized in that the wax content chosen from the total esters of a saturated, optionally hydroxylated, C16-C30 carboxylic acid with glycerol represents from 0.1 to 3% by weight, more particularly from 0.2 to 2% by weight, relative to the total weight of the composition.

26. Composition according to any one of the preceding claims, characterized in that it comprises: - at least one mineral filler chosen from silica, perlite, zeolites, carbonate or hydrogen carbonate of alkaline earth metals, such as calcium, magnesium, hydroxyapatite, kaolin, talc, synthetic or natural mica, boron nitride, glass or ceramic microcapsules, barium sulfate, diatomaceous earths, mixtures thereof; preferably chosen from kaolin, mica, calcium carbonate, and silica, as well as mixtures thereof;- among the organic fillers chosen from micronized waxes, natural or synthetic, metallic soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, polysaccharide powders, cellulose, N-acylated amino acids with C8-C22 carbon atoms, polyhdyroxyalkanoates, particles of acrylic (co)polymers, acrylonitrile (co)polymer, polyurethane, silicone polymers, polyamide, tetrafluoroethylene, and mixtures thereof, preferably chosen from cellulose, N-acylated amino acids with C8-C22, and mixtures thereof; - mixtures thereof.;

27. ​​Composition according to the preceding claim, characterized in that the mineral filler content represents from 2 to 20% by weight, preferably from 2 to 15% by weight, relative to the total weight of the composition.

28. Composition according to claim 26, characterized in that the organic filler content represents from 2 to 10% by weight, more particularly from 3 to 8% by weight, relative to the total weight of the composition.

29. Method for making up human keratin materials, in particular the skin and / or the lips, preferably the lips, in which the composition according to any one of the preceding claims is applied.