TWO-STEP EYEBROW MAKEUP METHOD WITH A FELT-TIP COMPOUND AND A COMPOUND WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, AND A SILICONE GUM

Abstract

TITLE: TWO-STEP EYEBROW MAKEUP METHOD WITH A FELT-TIP COMPOUND AND A COMPOUND WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, AND A SILICONE GUM. The present invention relates to a coating method, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours, comprising at least the following steps: 1) the application of a first composition (A) "Base Coat" packaged in an assembly including a felt-tip applicator; said composition (A) comprising, in particular in a physiologically acceptable medium: i) an aqueous phase ii) at least one film-forming polymer; iii) at least one coloring material;2) the application, over the layer formed by composition (A), of a second layer formed by a composition (B) "Top Coat" comprising, in particular in a physiologically acceptable medium: a) at least one non-glycerol silicone resin; b) at least one glycerol silicone resin; c) at least one silicone gum; d) at least one oily phase comprising at least one volatile hydrocarbon oil. Figure for the abbreviation: Figure 2;

Description

Title of the invention: TWO-STEP EYEBROW MAKEUP METHOD WITH A FELT-TIP COMPOUND AND A COMPOUND WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, AND A SILICONE GUM

[0001] The present application relates to the field of makeup of keratinous materials in particular of eyebrows including eyebrow hairs, the skin of implantation of said hairs and their contours.

[0002] In the field of eyebrow makeup, consumers have access to several types of solutions: - Eyebrow pencils, such as the NYX MICRO BROW PENCIL®, are easy to use but only last a day. They often have a pigmented base that transfers color onto the skin. - Felt-tip pens, such as the commercial product NYX PROFESSIONAL MAKEUP LIFT & SNATCH!®, are also easy to use but only last a day. They often contain water-based formulas with colorants. - In-salon tattoo services, which are very painful but last for several months. - anhydrous gels such as the commercial products Inked Waterproof Brow Gel® by Urban Decay (Mintel ID 7578707) and Up to 3 Day Styling Gel® by Maybelline (Mintel ID 10361806) containing isododecane and the combination of an MQ resin: TRIMETHYLSILOXYSILICATE and a silicone polyamide: NYLON-611 / DIMETHICONE COPOLYMER.

[0003] Users of makeup formulations of keratinous materials such as eyebrows and skin around the eye and eyebrows seek products with longer lasting power, which is reflected in particular by better resistance of the film deposited to oily substances such as sebum and makeup remover oils.

[0004] There remains a need to find new compositions for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, which make it possible to obtain makeup with better retention of the deposit over time, in particular better resistance to oily substances such as sebum and makeup remover oils.

[0005] Unexpectedly, the inventors found that it is possible to achieve these objectives using a coating process, in particular a care and / or Makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin on which said hairs are implanted and their contours, comprising at least the following steps: 1) the application of a first composition (A) “Base Coat” packaged in a set including a felt-tip applicator; said composition (A) comprising, in particular in a physiologically acceptable medium: i) an aqueous phase; ii) at least one film-forming polymer; iii) at least one coloring matter; 2) the application, on the layer formed by composition (A), of a second layer formed by a composition (B) "Top Coat" comprising, in particular in a physiologically acceptable environment: a) at least one non-glycerol silicone resin; b) at least one glycerol-based silicone resin; c) at least one silicone eraser; d) at least one oily phase comprising at least one volatile hydrocarbon oil.

[0006] This discovery is the basis of the invention.

[0007] The present invention also relates to a set or kit for coating, in particular for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, comprising at least 1) a composition (A) as defined above; 2) a composition (B) as defined above; said compositions (A) and (B) being conditioned separately. Definitions

[0008] In the context of the present invention, the term "keratinous materials" includes, in particular, eyebrows, including eyebrow hairs, the skin in which said hairs are implanted, and their contours. The term "keratinous materials," as used in the present invention, also extends to synthetic false eyebrows.

[0009] By "physiologically acceptable" means compatible with said keratinous materials, which has a pleasant color, odor and feel and which does not generate unacceptable discomforts (tingling, pulling), likely to deter the consumer from using this composition.

[0010] By "glycerolated silicone resin", we mean any silicone resin comprising at least one organosiloxane motif comprising one or more monoglycerol(s) or polyglycerol(s) group(s) in its chemical structure.

[0011] In particular, the glycerol silicone resin contains at least one organosiloxane motif of the type RR'R”SiOi / 2 in which R, R' and R'”, identical or different, designate hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerol silicone resin contains at least one dimethylsiloxane motif R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

[0012] By “hydrocarbon radical”, we mean a radical containing predominantly hydrogen and carbon atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether and carboxylic functions.

[0013] By “monoglycerol group” is meant any group comprising in its chemical structure a -O-CH2-CHOH-CH2OH group

[0014] By "polyglycerol group", we mean any group comprising in its chemical structure a chain comprising a repetition of at least 2 glycerol motifs -(O-CH2-CHOH-CH2)m-.

[0015] For the purposes of the present invention, the term "pen" refers to a grasping instrument consisting of a tube ending in a point and containing a reservoir of liquid which is dispensed from the point when it is applied to a support.

[0016] The term "felt tip" refers to a tip made of felt or synthetic fibers.

[0017] In particular, within the context of the present invention, the term "felt-tip pen" is distinct from a ballpoint pen or any device based on simple bristles used for applying eyebrow makeup compositions. COMPOSITION (A) BASE COAT

[0018] The composition (A) Base Coat according to the invention, packaged in an assembly including a felt-tip applicator, comprises, in particular in a physiologically acceptable medium: i) an aqueous phase; ii) at least one film-forming polymer; iii) at least one coloring matter. AQUEOUS PHASE

[0019] The aqueous phase comprises water and optionally ingredients soluble or miscible in water such as water-soluble solvents.

[0020] A suitable water for the invention may be 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.

[0021] In the present invention, "water-soluble solvent" means a compound that is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25°C and atmospheric pressure).

[0022] The water-soluble solvents usable in the composition of the invention may also be volatile.

[0023] Among the water-soluble solvents that can be used in the composition according to the invention, we can mention in particular monoalcohols having 2 to 5 carbon atoms such as, for example, ethanol and isopropanol, and mixtures thereof, glycols having 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes, as well as mixtures thereof, and preferably monoalcohols having 2 to 5 carbon atoms such as ethanol and isopropanol, and mixtures thereof.

[0024] Water may be present in a content ranging from 10 to 90% by weight, and preferably from 30 to 85% by weight, relative to the total weight of the composition (A). FILM-GENERATING POLYMERS

[0025] By "film-forming polymer" is meant a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on the skin.

[0026] The film-forming polymer present in the composition according to the invention can be chosen from: - proteins such as plant-based proteins like wheat and soy proteins; animal-based proteins such as keratins, for example keratin hydrolysates and sulfonic keratins; - anionic, cationic, amphoteric or non-ionic chitin or chitosan polymers; - cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as quaternized cellulose derivatives; - acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; - vinyl polymers, such as polyvinylpyrrolidones, methyl vinyl ether and malic anhydride copolymers, vinyl acetate and crotonic acid copolymer, vinylpyrrolidone and vinyl acetate copolymers; vinylpyrrolidone and caprolactam copolymers; polyvinyl alcohol; - Polyesters, particularly anionic polyester and / or polyesteramide polymers, especially those dispersible in water, comprising monomers bearing a -SO3M functional group, where M represents a hydrogen atom, an ammonium ion (NH4+), or a metal ion, such as Na+, Li+, K+, Mg2+, Ca2+, Cu2+, Fe2+, or Fe3+. Examples include the polymers described in US documents 3,734,874; 4,233,196; and 4,304,901. Advantageously, polyester polymers are chosen. film-forming agents based on at least one dicarboxylic acid, at least one diol and at least one bifunctional aromatic monomer further bearing a -SO3M group as described above; - Fatty chain polyesters, polyamides, and epoxy ester resins; - Polyurethane polymers, in particular anionic, cationic, non-ionic or amphoteric polyurethanes, acrylic polyurethanes, polyvinylpyrrolidone polyurethanes, polyester polyurethanes, polyether polyurethanes, polyureas, polyureas, polyurea / polyurethanes, - polymers of natural origin, possibly modified, such as: . arabic gums, guar gum, xanthan gum derivatives, karaya gum; . alginates and carrageenans; . glycosaminoglycans, hyaluronic acid and its derivatives; . shellac resin, sandarac gum, dammars, elemis, copals; . deoxyribonucleic acid; . muccopolysaccharides such as hyaluronic acid, chondroitin sulfate; and mixtures thereof.

[0027] According to a particularly preferred form, the composition (A) of the invention comprises at least one film-forming polymer selected from polyvinylpyrrolidones (PVP).

[0028] The film-forming polymer can be solubilized or dispersed in the aqueous medium of the composition.

[0029] By "solubilized in aqueous medium", we mean a polymer that can be soluble in water or in the water and solvent mixture as defined above.

[0030] By "dispersed in an aqueous medium," we mean a polymer insoluble in water or in the water-solvent mixture as defined above, in the form of solid particles dispersed in the aqueous medium. Such dispersions may be a latex, i.e., a dispersion obtained by emulsion polymerization, or a pseudolatex, i.e., a dispersion obtained by dispersing the already synthesized polymer. The techniques for preparing these dispersions are well known to those skilled in the art.

[0031] More particularly, composition (A) comprises a content of film-forming polymer(s) ranging from 0.5% to 20% by weight, and preferably ranging from 1% to 15% by weight, relative to the total weight of composition (A). COLORING MATERIALS

[0032] The composition (A) according to the invention comprises at least one coloring material.

[0033] The coloring materials may be chosen from mineral pigments, organic pigments, mother-of-pearl, water-soluble dyes, and mixtures thereof. Pigments

[0034] 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. Mineral pigments

[0035] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0036] The term "mineral pigment" means any pigment that meets the definition in the Ullmann Encyclopedia under the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include zirconium or cerium oxides, as well as zinc, iron (black, yellow, or red), or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric aluminum ferrocyanide, titanium dioxide, and metallic powders such as aluminum powder and copper powder. The following mineral pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, and ZrO₂ in mixtures with TiO₂, ZrO₂, Nb₂O₅, CeO₂, and ZnS.

[0037] The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can go up to 100 µm, preferably from 200 nm to 500 µm, and more preferably from 300 nm to 100 µm.

[0038] According to a particular embodiment of the invention, the pigments have a size characterized by a D

[50] greater than 100 nm and up to 100 µm, preferably from 200 nm to 5 µm, and more preferably from 300 nm to 1 µm.

[0039] The sizes are measured by static light scattering using a commercial particle size analyzer, the Malvern Master Sizer 3000®, which allows for the determination of the particle size distribution of all particles over a wide range from 0.01 µm to 1000 µm. The data are processed based on the classical Mie scattering theory. This theory is best suited for size distributions ranging from submicron to multimicron, and it allows for the determination of an "effective" particle diameter. This theory is notably described in Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

[0040] D

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

[0041] According to a particular embodiment of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, the latter preferably being present in the oily phase of the composition according to the invention.

[0042] According to a particular embodiment of the invention, the pigments can be coated according to the invention by at least one compound selected 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.

[0043] According to a particular mode, the pigments can be coated according to the invention with an N-acylated amino acid or one of its salts which can 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.

[0044] 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 be, in particular, a glutamic acid derivative and / or one of its salts, and more specifically a stearoyl glutamate, such as aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include the black iron oxide pigments CI77499, red CI77491, and yellow CI77492, sold under the trade name NAI® by MIYOSHI KASEI.

[0045] According to a preferred embodiment, the pigments according to the invention can be coated with isopropyl titanium triisostearyl titanate. Examples of pigments treated with isopropyl titanium triisostearate (ITT) include titanium dioxide pigments and black, red, and yellow iron oxide pigments sold under the trade names 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 KOBO.

[0046] Among the mineral pigments, we can also mention nacres.

[0047] They can be chosen from white pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent 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 pearlescent pigments based on bismuth oxychloride. Organic pigments

[0048] The pigments that can be used according to the invention can also be organic pigments.

[0049] By "organic pigment" is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on organic pigments. The organic pigment may in particular be chosen from the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0050] The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the Color Index under references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments coded in the Color Index under references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under references CI 61565, 61570, 74260, the orange pigments coded in the Color Index under the references CI 1725, 15510, 45370, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and pigments obtained by oxidative polymerization of indole derivatives,phenolic compounds as described in patent FR2 679 771.

[0051] 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 fixation of the organic pigments on the core.

[0052] The pigment can also be a lacquer.

[0053] By "lacquer", we mean insolubilized dyes adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0054] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0055] Among organic dyes, we can mention cochineal carmine. We can also mention the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 4 (CI 15510), D&C Red33 (CI17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green (CI 61570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090), D&C BLACK 2 (CI 77266).

[0056] Examples of lacquers include products known as D&C YELLOW 5 (CI 19140), D&C BLACK 2 (CI 77266), D&C BLUE 1 (CI 42090), and their mixtures. Water-soluble coloring agents

[0057] By "water-soluble colouring material", in the sense of the invention, means any compound generally organic, natural or synthetic, soluble in an aqueous phase or water-miscible solvents and capable of colouring.

[0058] As examples of suitable water-soluble colorants for the invention, synthetic or natural water-soluble colorants may be cited, for example, FDC Red 4, D&C Red 6, D&C Red 22, D&C Red 28, D&C Red 30, D&C Red 33, D&C Red 40, D&C Orange 4, D&C Yellow 5, D&C Yellow 6, D&C Yellow 8, FDC Green 3, D&C Green 5, betanin (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, riboflavin.

[0059] As an example, we can cite the product known under the name DC RED 40 (CI 16035).

[0060] According to a particular form, the composition (A) of the invention comprises at least one colouring material selected from D&C YELLOW 5 (CI 19140), BLACK 2 (CI 77266), D&C BLUE 1 (CI 42090), DC RED 40 (CI 16035), and mixtures thereof.

[0061] The colouring material(s) may be present in the composition (A) according to the invention in a content ranging from 0.01 to 15% by weight, in particular from 0.01 to 10% by weight, and in particular from 0.02 to 5% by weight, relative to the total weight of the composition (A). SURFACTANTS

[0062] The composition (A) according to the invention may also include at least one surfactant.

[0063] Non-ionic surfactants, and even more particularly silicone-based non-ionic surfactants, are particularly suitable for the invention.

[0064] The term "surfactant" refers to any amphiphilic molecule, meaning that it has two parts of different polarities: one lipophilic (miscible in oil) and nonpolar, and the other hydrophilic (miscible in water) and polar. Surfactants are characterized by a Hydrophilic Lipophilic Balance (HLB) value, where HLB is the ratio of the hydrophilic to 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).

[0065] For emulsifiers, the HLB generally ranges from 3 to 8 for the preparation of W / O emulsions and from 8 to 18 for the preparation of O / W emulsions, while foaming surfactants generally have an HLB greater than 20.

[0066] The HLB or hydrophilic-lipophilic balance of the surfactant(s) used according to the invention can be determined by the GRIFFIN method or the DA VIES method.

[0067] By "non-ionic surfactant" is meant any molecule having surfactant properties not having an ionic charge (cationic or anionic) in its chemical structure.

[0068] The term “siliconized surfactant” means any molecule having surfactant properties and comprising at least one chain including at least one -Si-O- motif to which groups are attached, on silicon atoms. Certain organic groups may be used to link several of these chains together.

[0069] The composition according to the invention further comprises at least one silicone non-ionic surfactant selected in particular from (poly)oxyalkylated and preferably (poly)oxyethylated polydimethylsiloxanes, alkyl or alkoxy dimethicone copolyols, and mixtures thereof.

[0070] Preferably the silicone non-ionic surfactant comprises polyoxyalkyene chains, more particularly polyoxyethylene, polyoxypropylene or their combinations, on the main chain (lateral or pendant polyoxyethylene, polyoxypropylene chains) and more particularly polyoxyethylene chains.

[0071] The number of ethylene oxide motifs can range from 0 to 100, preferably from 2 to 50 and even more particularly from 5 to 20. The number of propylene oxide motifs can range from 0 to 80 and more particularly is equal to 0. Note that the number of oxyalkylene motif(s) (oxyethylene, oxypropylene) is not zero.

[0072] Such silicone surfactants include those called PEG-10 Dimethicone sold by Shin Etsu under the name KF-6017®, PEG / PPG-14 / 4 Dimethicone sold by the company Evonik Goldschmidt under the brand AB IL B 8851®.

[0073] Also suitable are alkyl or alkoxy dimethicone copolyols with a dangling or end-shaped alkyl or alkoxy chain on a silicone backbone, having, for example, 6 to 22 carbon atoms and comprising at least one oxypropylene moiety and / or at least one oxyethylene moiety. The surfactant may be a linear or branched C8-C22 alkyl dimethicone copolyol, comprising at least one oxypropylene moiety and / or at least one oxyethylene moiety. For example, cetyl dimethicone copolyol (INCI name: CETYL PEG / PPG-10 / 1 DIMETHICONE), such as the product marketed under the name Abil EM-90® by Evonik Goldschmidt, may be cited.

[0074] Preferably, the silicone non-ionic surfactant is chosen from among oxyalkylated polydimethylsiloxanes and preferably oxyethylated ones.

[0075] According to a particularly preferred method, PEG / PPG-14 / 4 DIMETHICONE will be used.

[0076] The non-ionic surfactant(s) may be present in a content ranging from 0.01 to 10% by weight, in particular ranging from 0.1 to 7.5% by weight, or even from 0.1 to 5% by weight, relative to the total weight of the composition (A). POLYOLS

[0077] Composition (A) may also include at least one water-miscible polyol at room temperature (25 °C), in particular selected from polyols having from 2 to 20 carbon atoms, preferably having from 2 to 10 carbon atoms, and preferably having from 2 to 8 carbon atoms, such as glycerin, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, caprylyl glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as alkyl(Cl-C4)ether of mono-, di- or tripropylene glycol, alkyl(Cl-C4)ethers of mono-, di- or triethylene glycol; polyethylene glycols; C2-C8 polyhydric alcohols; and mixtures thereof. Glycerin will be used more particularly.

[0078] According to a preferred embodiment of the invention, the polyol(s) is / are present, in a content varying from 1 to 20% by weight, and more particularly ranging from 5 to 15% by weight, relative to the total weight of the composition (A). MONOALCOOLS

[0079] In addition, the composition according to the invention may include at least one monoalcohol having 2 to 5 carbon atoms such as, for example, ethanol, isopropanol and mixtures thereof.

[0080] According to a preferred embodiment of the invention, the monoalcohol is present in a content varying from 1% to 10% by weight, preferably in a content ranging from 3% to 7% by weight, relative to the total weight of the composition (A). CHARGES

[0081] The composition (A) according to the invention may further comprise at least one of the fillers commonly used in the field of cosmetics.

[0082] By "charges", one must understand colourless or white particles, mineral or synthetic, lamellar or non-lamellar.

[0083] The fillers may be present at a rate of 0.01 to 60% by weight, more particularly from 3 to 10% by weight, relative to the total weight of the composition (A).

[0084] The fillers that can be used are generally mineral or synthetic, lamellar or non-lamellar.

[0085] Representative examples of these fillers include talc, natural mica or synthetic mica such as fluorphlogopite, silica, kaolin, nylon and polyethylene powders, Teflon, starch, boron nitride, polymer microspheres such as Expacel® (Nouryon), silicone resin microbeads, and carbonate. precipitated calcium, magnesium carbonate or hydrocarbonate, bismuth oxychloride and mixtures thereof. ADDITIVES

[0086] Composition (A) may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, softeners, sequestrants, UV filters and mixtures thereof.

[0087] Finally, the composition (A) may also contain other additives, in particular to control its viscosity, adjust its colour or its reflective effect.

[0088] Of course, a person 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 composition according to the invention are not, or substantially not, altered by the envisaged addition. VISCOSITY

[0089] The compositions (A) according to the present invention are generally liquid at 25°C and atmospheric pressure (1.013.105 Pa).

[0090] They have a viscosity ranging from 0.05 to 7 Pa.s, preferably ranging from 0.1 to 3 Pa.s, more preferably ranging from 0.1 to 1 Pa.s, more particularly from 0.1 to 0.5 Pa.s, and even more particularly ranging from 0.1 to 0.3 Pa.s.

[0091] Viscosity measurement is measured using a Contraves TV or Rhéomat 180 type device at 25°C, with a No. 2 or No. 3 spindle depending on the viscosity range, after 10 minutes of rotation at a speed of 200 revolutions per minute. FELT-TIP APPLICATOR

[0092] Fig. 1 represents schematically, in elevation, an example of an applicator pen suitable for applying composition (A) of the invention.

[0093] The [Fig.2], which is a longitudinal section along ILII of the [Fig.1], comprises a body 2 of elongated shape along a longitudinal axis X, provided at one end with an application element 3.

[0094] The applicator 1 also includes a closing element which in the illustrated example is in the form of a cap that can be attached to the body 2, for example by snapping it into place in order to obtain a tight seal of the applicator when not in use.

[0095] In the example considered, the body 2 is closed at the end opposite the application element 3 by a bottom 5 which is for example snapped or held by friction in the body 2.

[0096] The applicator 2 contains the composition (A) of the invention which impregnates, for example, a block 7 with a porous material, for example, wadding, which can be surrounded by a sheath 8 whose outer diameter corresponds approximately to the inner diameter of body 2.

[0097] In the illustrated example, the block 7 occupies most of the height of the applicator 1 and rests at one end against the bottom 5.

[0098] The transport of the product to the application element 3 is carried out by capillarity.

[0099] In the illustrated example, a drill bit 10 is applied at one end against the block 7 and at the other end against the application element 3. The wick 10, as well as the application element 3, are engaged in a chimney 12 which, in the example considered, is made in one piece with the body 2 by molding of thermoplastic material.

[0100] The application element 3 also forms a wick and can be made of the same material or not as the wick 10.

[0101] The application element 3, as well as the wick 10, can be made independently of each other, in any material allowing the transport of the product by capillarity, in particular any material made of compressed fibers, porous composite, foam, cellulose, nylon, polyester; in sintered mineral or plastic material, for example in sintered elastomer beads.

[0102] The body wall can be substantially non-deformable, with the product being transferred to the area to be treated by capillary action without creating overpressure in the reservoir. The application element 3 is axially fixed relative to the body 2 during application, in the example considered.

[0103] Of course, the invention is not limited to the example embodiment described and many modifications can be made without departing from the scope of the present invention.

[0104] For example, the application element 3 can come directly into contact with the block 7 in the reservoir defined by the body 2 without an intermediate wick 10.

[0105] In yet another variant, block 7 is absent.

[0106] The application element 3 can be given various shapes. In the illustrated example, the tip of the application element 3 is wedge-shaped when viewed from the side in the direction of arrows II in [Fig. 1], but the tip of the application element 15 could be given other shapes, for example conical, frustoconical, double-pointed, chamfered, concave-edged, or others.

[0107] The application element 3 can also be covered with fibers on its surface, for example by flocking.

[0108] The wall of the body 2 could, if necessary, be made of a more flexible material so as to allow the user to create overpressure inside the tank to increase the flow rate of product at the application, for example.

[0109] In yet another variant, the application element 3 is made monolithically with the block 7.

[0110] Preferably, within the framework of the present invention, the application element 3 remains in permanent fluidic communication with the composition contained in the reservoir.

[0111] Preferably, the applicator according to the present invention is without a valve, in particular between the reservoir and the application element 3.

[0112] Preferably, the applicator according to the present invention does not require any pressure on the body 2 to promote the flow of the composition through the application element 3.

[0113] To use the applicator, the user grasps the body 2 in the manner of a pen and can bring the tip of the application element into contact with the eyebrows (including the eyebrow hairs, the skin on which said hairs are implanted and their contours), in particular from the inner edge to the outer edge of the area to be made up.

[0114] According to a particular embodiment of the invention, the felt tip can be in the form of a brush. COMPOSITION (B) TOP COAT

[0115] Composition (B) “Top Coat” according to the invention comprises, in particular in a physiologically acceptable medium:

[0116] a) at least one non-glycerol silicone resin;

[0117] b) at least one glycerol-coated silicone resin;

[0118] c) at least one silicone rubber;

[0119] d) at least one oily phase comprising at least one volatile hydrocarbon oil. NON-GLYCEROLATED SILICONE RESINS

[0120] The composition (B) according to the invention comprises at least one non-glycerol silicone resin a).

[0121] More generally, the term "resin" refers to a compound with a three-dimensional structure. Silicone resins are also called silicone resins or "siloxane resins." Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

[0122] The nomenclature of silicone resins is known as MDTQ, the resin being described according to the different siloxane monomeric units it comprises, each of the letters MDTQ characterizing a type of unit.

[0123] The letter M represents the Monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being bonded to a single oxygen atom in the polymer comprising this unit.

[0124] The letter "D" signifies a Difunctional unit R1 R2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.

[0125] The letter T represents a Trifunctional RlSiO3 / 2 unit.

[0126] Such resins are described, for example, in "Encyclopedia of Polymer Science" and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or even US 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484.

[0127] In the motifs M, D, T defined above, R, namely RI, R2 and R3, represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0128] 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.

[0129] Various silicone resins of different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the dangling chains.

[0130] As examples of silicone resins that can be used in the compositions according to the invention, MQ type silicone resins, T type silicone resins, MQT type silicone resins, and mixtures thereof may be used. MQ Resins

[0131] By way of example of MQ type silicone resins, alkylsiloxysilicates of formula [(Rl)3SiOi / 2]x(SiO4 / 2)y (MQ units) may be cited, in which x and y are integers from 50 to 80, and such that the RI group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0132] As an example of MQ silicone resins of the Trimethylsiloxysilicate type, we can cite those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name “KF-7312J®” by the company Shin-Etsu, “DC 749®”, “DC 593®” by the company Dow Corning. T Resins

[0133] As an example of T-type silicone resins, we may cite polysilsesquioxanes 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 terminal groups.

[0134] Preferably, polymethylsilsesquioxane resins in which R represents a methyl group can be used, such as, for example, those commercially available:

[0135] - by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating CH3SiO3 / 2 units (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2 units (D units) and having an average molecular weight of about 10000 g / mol, or

[0136] - by the company SHIN-ETSU under the references KR-220L® which are composed of T units with the formula CH3SiO3 / 2 and have Si-OH (silanol) terminal groups, under the reference KR-242A® which comprise 98% T units and 2% dimethyl D units and have Si-OH terminal groups, or under the reference KR-251® comprising 88% T units and 12% dimethyl D units and have Si-OH terminal groups. MQT Resins

[0137] As a resin comprising MQT motifs, those cited in US document 5 110 890 are known in particular.

[0138] A preferred form of MQT-type resins is MQT-propyl resin (also called MQTPr). Such resins usable in the compositions according to the invention include, in particular, those described and prepared in application WO 2005 / 075542.

[0139] The MQ-T-propyl resin preferably comprises the following units: (i) ((Rl)3SiO1 / 2)a (ii) ((R2)2SiO2 / 2)b (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with RI, R2 and R3 independently represent a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d=l, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0140] Preferably, the siloxane resin comprises the following units: (i) ((Rl)3SiO1 / 2)a (ii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with RI and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, RI being preferably a methyl group and R3 being preferably 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 = l, eta, b, cetd being mole fractions, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0141] The siloxane resins usable according to the invention can be obtained by a process comprising the reaction of A) an MQ resin comprising at least 80 mole percent of ((Rl)3SiO1 / 2)a and (SiO4 / 2)d units RI representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, a and d being greater than zero, the a / d ratio being between 0.5 and 1.5; and of B) a propyl resin T comprising at least 80 mole percent of (R3SiO3 / 2)c units, R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, provided that at least 40 mole percent of the R3 groups are propyl groups, where the mass ratio A / B is between 95:5 and 15:85, preferably the mass ratio A / B is 30:70.

[0142] Advantageously, the mass ratio A / B is between 95.5 and 15.85. Preferably, the A / B ratio is less than or equal to 70:30. These preferred ratios have been shown to allow comfortable deposition.

[0143] Preferably, the composition (B) according to the invention comprises, as a silicone resin, at least one MQ type resin, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker, under the name KF-7312J® by Shin-Etsu, DC 749®, DC 593® by Dow Corning, under the reference Silsoft 74 Fluid® by Momentive Performance Materials.

[0144] A trimethylsiloxysilicate resin in isododecane solution, particularly in a 75% by weight active substance solution, will be used in particular. in isododecane as the commercial product sold under the reference Silsoft 74 Fluid® by the company Momentive Performance Materials.

[0145] According to a particular embodiment of the invention, the non-glycerol silicone resin(s) is / are present in the composition (B) in a content, expressed as active matter, ranging from 4 to 35% by weight, preferably ranging from 6 to 30% by weight, and more preferably from 8 to 25% by weight, relative to the total weight of the composition (B). GLYCEROLATED SILICONE RESIN

[0146] The composition (B) according to the invention comprises at least one glycerol silicone resin b).

[0147] The glycerol-based silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol groups.*

[0148] According to a particular embodiment of the invention, the glycerol silicone resin(s) is / are present in a content, expressed as active matter, ranging from 0.1 to 40% by weight, preferably ranging from 0.2 to 30% by weight, and more preferably from 0.5 to 15% by weight, relative to the total weight of the composition (B).

[0149] The glycerol-siliconized resin(s) according to the invention are preferably chosen from those of the following formula (1). (Rl3SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(Rl2SiO2 / 2)d(R^^ (1) in which - each RI, 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 of the latter; - each R2 is a mono- or poly-glycerol group of the following general formula (2) -(CH2)2-C1H21-O-(CH2CH(OH)CH2O)iR4 (2) in which - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, and - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is an identical or different group of general formula (3), general formula (4), general formula (5) or general formula (6) below: -(CH2)2-CmH2m-(SiORl2)j-SiRl3(3) -(CH2)2-CmH2m-SiRlkl-(OSiRl3)3 kl (4) -(CH2)2-CmH2m-SiRlkl-(OSiRlk2(OSiRl3)3 k2)3 kl (5) -(CH2)2-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiRl3)3_k3)3_k2)3_ki (6) where - each RI, 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 of the latter; - the indices m, j and kl to k3 are integers that satisfy the conditions 0< m < 5, 0 < j < 500, 0< kl < 2, 0 < k2 < 2 and 0 < k3 < 2; - the indices a, b, c, d, e and f are numbers that satisfy the conditions 0 < a < 400, 0

[0150] The glycerol-coated silicone resins according to the invention are described in Shin Etsu's US patent application US20200332065A1.

[0151] According to a particular method, the glycerol-coated silicone resin(s) of formula (1) as defined above are chosen from those of which - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; - the index i in the general formula (2) of the monoglycerol or polyglycerol group R2 is an integer that satisfies the condition 0 < i < 3. ​

[0152] According to a particular mode, the glycerol silicone resin(s) of formula (1) are in solid form at 25 °C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

[0153] According to a particular mode, the glycerol-siliconized resin(s) have an average molecular weight by weight ranging from 1000 to 100000.

[0154] The glycerol-coated silicone resin(s) according to the invention are amphiphilic, that is, they have two parts with different polarities. Generally, one is lipophilic (soluble or dispersible in an oil phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by their HLB (Hydrophilic-Lipophilic Balance) value, the HLB being the ratio between the hydrophilic and lipophilic parts 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 glycerol-coated silicone resin(s) according to the invention preferably varies from 0.1 to 15 according to Griffin's method.

[0155] The glycerol-coated silicone resin(s) according to the invention can be obtained by a preparation process comprising the hydrosilylation step A) of a silicone resin containing a hydrosilyl group of formula (7) below (Rl3SiO1 / 2)aHnRl3nSiO1 / 2)b+c(Rl2SiO2 / 2)d(RlSiO3 / 2)e(SiO4 / 2)f (7) in which: - each RI, 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 of the latter; - 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 and 0.5 < (a+b+c) / f < 1.5; - n is an integer that satisfies the condition 1 < n < 3, with B) one or more compounds that are chosen from the compounds ending with 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-(SiORl2)rSiRl3 (9) CH2=CH-CmH2m-SiRlkl-(OSiRl3)3kl (10) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRl3)3 k2)3 kl (11) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiRl3)3 k3)3 k2)3 kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 <l<15, 0<i<5; - the indices m, j and kl to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said silicone resin containing a hydrosilyl group of formula (7) reacting with at least one compound of formula (8).

[0156] The hydrosilylation reaction is carried out in the presence, for example, of a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R4,1, m, i, j and kl to k3 are as defined above.

[0157] Silicone resin containing a hydrosilyl group used as a starting material

[0158] The silicone resin containing a hydrosilyl group of formula (7) can be in solid or liquid form at 25°C, although, in terms of film-forming ability, it is preferably solid. From a utility standpoint, 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.

[0159] 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 are used. Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred for their storage stability and lack of volatility.

[0160] 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 selected from the organosilicon compounds of general formulas (13) and (14) below, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) below and one or more compounds selected 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: Rl3SiOSiRl3 (13) Rl3SiXl (14) HnRl(3 n)SiOSiRl(3 n)Hn (15) HnRl(3 n)SiX2 (16) where - each RI, 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 of the latter; - XI and X2 are hydrolyzable functional groups; and - n satisfies the condition 1 < 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.

[0161] In general formulas (13), (14), (15) and (16), the examples and preferred range for RI are the same as those mentioned above.

[0162] In the general formula (14), XI is a hydrolyzable functional group that 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. Of these, from the point of view of availability and rate of hydrolysis, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0163] In the general formula (16), X2 is a hydrolyzable functional group that 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. Of these, from the point of view of availability and rate of hydrolysis, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0164] In the general formula (17), X3 is a hydrolyzable functional group that 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. Of these, an alkoxy group is preferred; from the standpoint of availability and hydrolysis rate, a methoxy or ethoxy group is preferred. The hydrolyzable X3 groups on the molecule may be similar or different groups.

[0165] 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-octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Among these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

[0166] 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.

[0167] 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.

[0168] Furthermore, in the general formulas (15) and (16), n satisfies the condition 1 < n < 3. In the general formula (15), the "n" associated with the H and RI bonded to one silicone atom and the "n" associated with the H and RI bonded to the other silicone atom can be identical or different.

[0169] Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0170] Examples of hydrolyzable silane of general formula (17) include tetrachlorosilane, tetramethoxysilane, and tetraethoxysilane. Examples of partially hydrolyzed condensates of hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silane include soluble glass, sodium silicate, and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0171] 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 metallic salts of these hydrolyzable silanes may be added 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. RlSiX43 (18) Rl2SiX52(19) where - each RI is an alkyl, aryl or aralkyl group identical or different from 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 of the latter; - X4 and X5 are hydrolyzable functional groups.

[0172] In general formulas (18) and 19), the examples and preferred ranges for RI are the same as those mentioned above.

[0173] In the general formula (18), X4 is a hydrolyzable functional group that 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. Of these, from the standpoint of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred. The X4 hydrolyzable groups on the same molecule may be the same or different.

[0174] In the general formula (19), X5 is a hydrolyzable functional group that 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. Of these, from the standpoint of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred. The X5 hydrolyzable groups on the same molecule may be similar or different.

[0175] Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, rethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane, and methyltrichlorosilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, and methyltrichlorosilane are preferred.

[0176] Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane, and dimethyldichlorosilane. Of these, dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldichlorosilane are preferred.

[0177] A specific example of a process for preparing the silicone resin containing a hydrosilyl group used as a raw material in the present invention is described. A solvent (in particular, an organic solvent) and a hydrolysis raw material (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), the condensates of partial hydrolysis of these hydrolyzable silanes, and the metal salts of these hydrolyzable silanes) are loaded into a reactor, an acid is added as a catalyst, and water is added dropwise while stirring. It is also possible in this case to add the organic solvent after the dropwise addition of water has been completed.Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0178] 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 within this range, the heat of reaction of the hydrolysis reaction The concentration of 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 within this range, it is possible to further suppress the deactivation of hydrosilyl groups.

[0179] In order to eliminate a decrease in the reaction rate due to retention and an increase in the 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 hydrolysis.

[0180] 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, methylethyl ketone, diethyl ketone and methylisobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane.

[0181] 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. Because 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.

[0182] 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 from 5 to 50%. Within this range, the reaction system remains uniform and the reaction proceeds efficiently.

[0183] 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 small amounts, with an amount in the range of 0.001 to 10% of the overall reaction system being preferred.

[0184] After adding water drop by drop as mentioned above, the hydrolysis reaction is carried out by heating the system to a temperature between 50 and 150°C, preferably between 80 and 120°C, for approximately 2 to 8 hours. During this time, carrying out the reaction at a temperature below the boiling point of the organic compound containing hydrosilyl groups used can further suppress the deactivation of the hydrosilyl groups.

[0185] 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 between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably at 25°C.

[0186] After the above hydrolysis, the system is neutralized at 10–40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this point, using a strong basic catalyst and a weak basic catalyst together prevents the deactivation of the hydrosilyl group and further promotes the condensation reaction of the organosilicon resin. 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 combinations of a strong basic catalyst with a weak basic catalyst, from the perspective of easily achieving a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, making it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

[0187] The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. Performing 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 yielding 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 amount of addition within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, thus yielding a resin of the target molecular weight.

[0188] After neutralization, the alcohols formed, the solvent, and excess water can be removed by heating between 95 and 120°C under normal or reduced pressure. Then, after confirmation that the alcohols formed, the solvent, and excess water have been removed, the condensation reaction is carried out by heating between 120 and 150°C for approximately 2 to 5 hours. This yields an organosilicon resin containing a hydrosilyl group.

[0189] In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio between the combined molar amount of the compounds of general formulas (13), (14), (15) and (16) and 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 from 0.3:1 to 2:1, and more preferably from 0.6:1 to 1.3:1.

[0190] Furthermore, the ratio between the combined molar quantity of compounds of general formulas (13) and (14) and the combined molar quantity of compounds of general formulas (15) and (16), expressed as the molar ratio ((13)+(14)) :((15)+(16)), is preferably from 0.3:1.0 to 2.0:1.0, and more preferably from 0.6:1.0 to 1.3:1.0. By setting the values ​​within these ranges, the amount of hydrosilyl groups included in the organosilicon resin containing hydrosilyl groups can be varied quantitatively more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulas (15) and (16) are loaded, it is possible to quantitatively vary the amount of hydrosilyl groups included on the organosilicon resin.

[0191] In the process described above for preparing a silicone resin containing hydrosilyl groups, after carrying out the hydrolysis, in the presence of an acid catalyst, of a mixture of one or more compounds selected from the organosilicon compounds of general formulas (13) and (14) with one or more compounds selected from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes and metallic salts of these hydrolyzable silanes, it is possible to add also gradually, drop by drop, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group, of general formulas (15) and (16).

[0192] Next, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably performed by heating to a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example, 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 within this temperature range, the deactivation of the hydrosilyl groups can be further suppressed.

[0193] In the process of preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups are deactivated, can occur. [Chem 1] ............If.....'0....... < 2 °) 'siô V2 ^ where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

[0194] However, by appropriately determining the order in which the raw materials are added, i.e., by hydrolyzing a mixture of one or more compounds selected from the organosilicon compounds of general formulas (13) and (14) with one or more compounds selected from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes, and metallic salts of these hydrolyzable silanes, and then adding one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) and carrying out a rehydrolysis, the above reaction (20) can be kept to a minimum. This reaction can be further suppressed by cleverly modifying the quantities in which the raw materials are added and the type of catalyst used.

[0195] The amount of hydrosilyl groups included in the organosilicon resin thus obtained is easily adjustable, and it is even possible to introduce a large amount of hydrosilyl groups by varying the amount of the organosilicon compound containing hydrosilyl groups that is loaded. 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 method of addition, the molecular weight range, shape, and other characteristics of the organosilicon resin can be adjusted, making it possible to prepare an organosilicon resin containing hydrosilyl groups for the intended application.

[0196] 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 (Rl3SiO1 / 2) and (HnRl3nSiO1 / 2) as essential constituents, and also of D units (Rl2SiO2 / 2) and T units (RlSiO3 / 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 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 performing operations such as filtration. The average molecular weight can be determined as the mass molecular weight equivalent of polystyrene in gel permeation chromatography (GC).

[0197] Process for preparing glycerol-coated silicone resin

[0198] A specific example of a process for preparing the glycerol-siliconized resin according to the invention is described below.

[0199] As mentioned above, the glycerol-coated 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: (Rl3SiO1 / 2)a(HnRl3nSiO1 / 2)b+c(Rl2SiO^ (7) in which - each RI is an alkyl, aryl or aralkyl group identical or different from 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 of the latter; - 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 and 0.5 < (a+b+c) / f < 1.5; - n is an integer that satisfies the condition 1 < n < 3 with (B) one or more compounds which are chosen from the compounds ending with 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-(SiORl2)j-SiRl3 (9) CH2=CH-CmH2m-SiRlkl-(OSiRl3)3 kl (10) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRl3)3 k2)3 kl (11) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiRl3)3k3)3k2)3kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15, and 0 < i < 5; - the indices m, j and kl to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said includes a compound of general formula (8).

[0200] 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 in hydrosilyl groups / terminal unsaturated groups, which is preferably from 0.5 to 2.0, and more preferably from 0.8 to 1.2.

[0201] 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 therefore the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0202] Furthermore, if necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and 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 a reactivity standpoint, ethanol, 1-propanol, and 2-propanol are preferred.

[0203] The amount of solvent used is preferably from 1 to 80%, and more preferably from 5 to 50%, of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0204] The conditions of the addition reaction are not particularly limited, although reflux heating at a temperature between 50 and 150°C, in particular between 80 and 120°C, for about 1 to 10 hours is preferred.

[0205] 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 from 0.001 to 5.0%, and in particular from 0.01 to 1.0%, of the overall system. By fixing the amount of activated carbon within this range, the discoloration of the sample can be better suppressed.

[0206] After the addition reaction, if necessary, a step to remove the remaining hydrosilyl groups may be included. Particularly in cases where use in applications such as cosmetic preparations is planned, there is a possibility that these hydrosilyl groups may become deactivated over time due to dehydrogenation reactions, which poses a safety concern. Therefore, it is preferable to include a step to maintain the hydrosilyl groups.

[0207] An example of a step for removing hydrosilyl groups is the process of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as that an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, followed by neutralization through the addition of an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts 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 standpoint of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being especially favored.Examples of 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. Generally, instead of using the acid or base alone, it is preferable to use them with water and heat them to a temperature no higher than the boiling point of water.

[0208] After the addition reaction, if necessary, a deodorization step to reduce the odor may be included. When use in applications such as cosmetic preparations is planned, in particular, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common silicones modified with polyethers can be explained as follows. When an addition reaction between a polyether etherized with allyl groups and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as side reactions, forming a polyether etherized with propenyl groups. This propenyl-etherized polyether has no reactivity with the hydrogen polyorganosiloxane and therefore remains in the system as an impurity.It is believed that when water reacts with this propenyl-etherified polyether, the propenyl ether hydrolyzes, giving rise to propionaldehyde, which emits an unpleasant odor. The above hydrolysis reaction is known to be further promoted in the presence of an acidic 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 development of an unpleasant odor.

[0209] Typical examples of the deodorization step include two approaches. The first is that in which, 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 band purification (JP No. 2137062).

[0210] 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-point acid, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Similarly, from the point of view of treatment effectiveness, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

[0211] The processing temperature is preferably set at 80°C or less to avoid oxidation of the 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.

[0212] From a productivity standpoint, the preferred method is to add an aqueous solution to the post-reaction solution to adjust the pH to 7 or less and to perform strip purification after stirring under heating. Strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. To efficiently purify the strip under these temperature conditions, it is preferable to perform this operation under reduced pressure; when performed at normal pressure, the operation is preferably carried out under a flow of inert gas such as nitrogen or argon.

[0213] 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).

[0214] Hydrogenation reactions include methods involving the use of hydrogen and methods involving the use of metal hydrides, and there are also homogeneous 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.

[0215] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron, and others, in uncombined form or as a compound. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support can be, for example, activated carbon, silica, silica-alumina, alumina, or zeolite. These catalysts can 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. Furthermore, the reaction system becomes slightly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0216] 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 in batches or continuously. When it is a batch process, the reaction time depends, for example, on the amount of catalyst and the temperature, but it is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to a suitable fixed pressure. The endpoint 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.

[0217] The amount of aldehyde included in the glycerol-siliconized resin that has been purified by this acid treatment and this hydrogenation treatment can be fixed at 70 ppm or less, preferably at 20 ppm or less, and more preferably at 10 ppm or less.

[0218] It is also possible to combine the two types of deodorization steps mentioned above. In the approach involving acid treatment, the 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 eliminated. In the approach involving a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound formed. However, the aldehyde condensate that forms with the condensation of some 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 that remain 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).

[0219] The average molecular weight of the glycerol-siliconized resin of average formula (1) preferably varies from 1000 to 100000; from the point of view of performance and ease of operations such as filtration, the average molecular weight preferably varies from 3000 to 50000. Here and here- below, the average molecular weight by weight can be determined as the average molecular weight by weight equivalent to polystyrene in gel permeation chromatography (GC).

[0220] The glycerol-siliconized 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.

[0221] In particular, the glycerol-coated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b<30et0<c< 30, l'indice i dans la formule générale (2) est un nombre entier qui satisfait à condition 0 < i < 3 et j (3) < j < 10 sous forme d'un solide 25°c présente, de préférence une masse moléculaire moyenne en poids varie comprise 1000 100000 plus préférentiellement, 3000 50000.

[0222] The glycerol-coated silicone resins according to the invention have a hydrophilic-lipophilic equilibrium (HLB), as determined by Griffin's formula, preferably from 0.1 to 15, and more preferably from 1.0 to 8.0.

[0223] According to a preferred embodiment, the composition of the invention comprises at least one glycerol-coated silicone resin of formula (1) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate corresponding to the following formula (21): [(CH3)3SiO1 / 2]a [R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - R designates the 3-glyceroxypropyl group with the structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.5.

[0224] According to a particularly preferred form, the glycerol silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution in at least one volatile oil.

[0225] For the purposes of this invention, "volatile oil" means any oil capable of evaporating upon contact with the skin in less than one hour at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1,300 Pa.

[0226] The volatile oil according to the invention can be chosen from the group consisting of hydrocarbon oils, silicone oils, and their mixtures.

[0227] By "hydrocarbon oil" is meant an oil containing predominantly hydrogen and carbon atoms and possibly one or more functions selected from among the hydroxyl, ester, ether and carboxylic functions.

[0228] For the purposes of the present invention, the term "siliconized oil" means an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.

[0229] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0230] Examples include C8-C16 isoalkanes (also called isoparaffins) such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and, for example, oils sold under the trade names Isopar® or Permetyl®. Isododecane is preferred.

[0231] By way of example of volatile silicone oil usable in the invention, volatile silicone oils may be cited, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 centistokes (2.106 to 8.106 m2 / s), and containing in particular 2 to 7 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups containing 1 to 10 carbon atoms. Examples of volatile silicone oils usable in the invention include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctylisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) is preferred.

[0232] According to a particularly preferred form, the glycerol silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution with about 49-50 wt% active matter in isododecane and a weight average molecular mass of 11000. VOLATILE HYDROCARBONATE OILS

[0233] Composition (B) according to the invention comprises an oily phase comprising at least one volatile hydrocarbon oil.

[0234] Oil means any fatty substance in liquid form at ambient temperature (25°C) and atmospheric pressure (760 mm Hg or 1.013.105 Pa).

[0235] The term "oil phase" means an organic liquid phase at room temperature (25°C) and atmospheric pressure that is immiscible in water. It comprises at least one oil and any ingredient soluble or miscible in said phase.

[0236] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0237] Examples include C8-C16 isoalkanes (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®.

[0238] C8-C16 branched esters such as isohexyl neopentanoate can also be mentioned. Other volatile hydrocarbon oils such as petroleum distillates, particularly those sold under the name Shell Soit® by Shell, can also be used.

[0239] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the volatile linear alkanes comprising from 6 to 14 carbon atoms.

[0240] By way of example of linear alkanes suitable for the invention, mention may be made of alkanes described in Cognis patent applications WO 2007 / 068371 and WO2008 / 155059 (mixtures of distinct alkanes differing by at least one carbon atom). These alkanes are obtained from fatty alcohols, themselves derived from coconut or palm oil.

[0241] By way of example of linear C6-C14 alkanes suitable for the invention, one can cite n-hexane (C6); n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), and their mixtures.

[0242] Notable examples include n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references Parafol 12 97® and Parafol 14 97® respectively, as well as their mixtures.

[0243] According to another embodiment, a mixture of n-dodecane and n-tetradecane is used. In particular, the dodecane / tetradecane mixture in the weight ratio 85 / 15 marketed by Biosynthis under the reference Vegelight 1214® may be used.

[0244] According to yet another embodiment, a mixture of volatile linear alkanes in C9-C12 with INCI name: C9-12 Alkane is used, such as the product marketed by the company Biosynthis under the reference Vegelight Silk®.

[0245] According to yet another embodiment, a mixture of n-undecane (Cl 1) and n-tridecane (Cl3) is used, such as those obtained in examples 1 and 2 of application WO2008 / 155059 from Cognis and such as that sold under the trade name Cetiol Ultimate® by BASF.

[0246] According to a particularly preferred embodiment, the volatile hydrocarbon oil is selected from among C8-C16 branched alkanes, and more particularly isododecane, the mixture of volatile linear alkanes in C9-C12 and the mixture of n-undecane (C11) and n-tridecane (C13), as well as mixtures thereof.

[0247] According to a particularly preferred embodiment, the composition (B) of the invention comprises at least one volatile oil selected from the C8-C16 isoalkanes (also called isoparaffins), alone or in mixtures, in particular isododecane.

[0248] The volatile hydrocarbon oil or oils are preferably present in the composition at levels less than or equal to 80% by weight, preferably from 40 to 70% by weight, relative to the total weight of the composition (B). SILICONE GUMS

[0249] The composition according to the present invention comprises at least one silicone gum (c).

[0250] By silicone gum, we mean more particularly non-crosslinked linear polyorganosiloxanes, in particular polydimethylsiloxanes, optionally hydroxylated, phenylated, or vinylized, or combinations thereof. It should be noted that the silicone gums used according to the invention are not silicone elastomers.

[0251] According to the present invention, a silicone gum is also not considered to be a silicone oil.

[0252] More specifically, the silicone gum (c) is selected from polyorganosiloxanes with a weight molecular mass greater than or equal to 180,000 g / mol. Preferably, the silicone gum is selected from polyorganosiloxanes with a weight molecular mass greater than or equal to 400,000 g / mol.

[0253] Molecular masses by weight are measured in a conventional manner in the field, for example using gel permeation chromatography coupled with static light scattering (GPC-MALLS)

[0254] Preferably, the viscosity of the silicone gum is greater than or equal to 300,000 cSt, advantageously greater than or equal to 400,000 cSt, preferably greater than or equal to 800,000 cSt, more particularly less than or equal to 10,000,000 cSt (at 25°C, measured according to ASTM D-445). More particularly, the viscosity is between 800,000 and 5,000,000 cSt (at 25°C, measured according to ASTM D-445).

[0255] It is preferable that the silicone gum (c) does not have a functional group such as an amino group.

[0256] The silicone gum (c) may be selected in particular from silicones of formula:

[0257] [Chem 2] in which: RI, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, R3 and R4 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, a vinyl radical, an aryl radical, or a hydroxyl radical. X is an alkyl radical containing 1 to 6 carbon atoms, a hydroxyl radical, an alkoxy radical containing 1 to 6 carbon atoms, and n and p being integers chosen such that the molecular mass of silicone gum is greater than or equal to 180,000 g / mol, advantageously greater than or equal to 400,000 g / mol.

[0258] In general, n and p can each take values ​​from 0 to 5000, more particularly from 0 to 3000, knowing that n and p are not naught simultaneously.

[0259] According to a particular embodiment, the silicone gum (c) is selected from polydimethylsiloxane gums, in particular those of INCI name Dimethicone, polydimethylsiloxane gums comprising at least one aryl radical, in particular those of INCI name: Diphenyl Dimethicone, gums of INCI name Dimethiconol, or mixtures thereof, and preferably gums of INCI name Dimethicone, alone or in mixtures.

[0260] The silicone gum(s) can be used alone or in mixture, in particular with one or more volatile or non-volatile oils.

[0261] According to a particular embodiment of the invention, the silicone gum (c) is in the form of a solution in one or more volatile or non-volatile oils.

[0262] Preferably, the volatile or non-volatile oil, identical or different from those mentioned above, is chosen from volatile silicones; non-volatile polydimethylsiloxane oils; polyphenylmethylsiloxane oils; isoparaffins, in particular C8-C16 such as isododecane; methylene chloride; pentane; dodecane; tridecane; tetradecane; or mixtures thereof.

[0263] In a particularly preferred manner, the oil is chosen from C8-C16 isoparaffins, alone or in mixture, in particular isododecane.

[0264] When the silicone gum (c) of the invention is used in the form of a mixture, more particularly as a solution in one or more oils as described above, the proportion of silicone gum preferably represents, from 5 to 40% by weight, and more preferably from 10 to 30% by weight, relative to the total weight of said mixture (or solution).

[0265] Preferably, the composition (B) comprises a silicone gum(s) (c) content, expressed as active material, ranging from 2 to 35% by weight, and more particularly from 5 to 25% by weight relative to the total weight of the composition (B).

[0266] Among the silicone gums that can be used in the context of the present invention, we can mention Dimethicone gums (all the R and X radicals are methyl groups), sold for example under the names Silsoft SE 30, Silsoft B3820 BLEND® (in isododecane) by the company Momentive Performance Materials, Belsil DM 500000 by the company Wacker, KF-9043 (in isododecane) by the company Shine Etsu.

[0267] Among the Dimethiconol gums (the R radicals are methyl groups and the X radicals are hydroxyl groups), we can mention in particular those sold under the names Xiameter® PMX-1401 Fluid (in cyclopentasiloxane), Xiameter PMX-1503 Fluid (in a Dimethicone), Xiameter® PMX-1403 Fluid (in a dimethicone) by the company Dow Corning, the products of the Mirasil D-DML-LV range marketed by the company Elkem Silicones, Silsoft 1215 (in cyclopentasiloxane) by the company Momentive Performance Materials.

[0268] With regard to Diphenyl dimethicone type gums (R3 and R4 representing an aryl group, the other radicals R and X representing methyl groups) one can cite for example Mirasil C-DPDM (in cyclopentasiloxane) marketed by the company Elkem Silicones.

[0269] Among dimethicones of the (polydimethylsiloxane) (methylvinylsiloxane) type, such as SE63® sold by GE Bayer Silicones, poly(dimethylsiloxane) (diphenyl) (methylvinylsiloxane) copolymers and mixtures thereof. LIPOPHILIC THICKENER

[0270] According to a preferred form, the composition (B) according to the invention further comprises at least one lipophilic thickener.

[0271] The term “lipophilic thickener” means any lipophilic or lipophilicly soluble molecule in the oily phase of the composition capable of increasing the viscosity of the composition.

[0272] As a lipophilic thickener, at least one lipophilic clay will preferably be used.

[0273] Clay refers to a material based on hydrated silicates and / or aluminosilicates with a lamellar structure.

[0274] Clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as ammonium chloride in CIO₃ at C22, in particular steralkonium chloride or di-stearyl di-methyl ammonium chloride.

[0275] They can be chosen from among bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

[0276] Preferably, they are chosen from among the hectorites and the bentonites.

[0277] According to a particularly preferred form, a lipophilic clay selected from hydrophobic modified bentonites and hydrophobic modified hectorites, in particular by a quaternary ammonium chloride in C22 C1O, will be used, 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 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 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 Stearinerie Dubois Fils, Myglyol Gel T® from Cremer Oleo, Tixogel® CGT 6030, Tixoge® DBA 6060, Tixoge® FTN, Tixoge® FTN 1564, Tixoge® IPM, TITixogeXOGEL® LAN, Tixoge® LAN 1563 by BYK Additives Inc; - a hectorite modified by 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 by 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.

[0278] In particular, a hectorite modified by distearyl dimethyl ammonium chloride (INCI name: Disteardimonium Hectorite) will be used, such as, for example, that marketed under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialities.

[0279] The lipophilic thickener(s) may be present in the composition at concentrations ranging, preferably, from 0.5 to 10% by weight, and more preferably from 1 to 6% by weight, relative to the total weight of the composition (B). COSMETIC ADDITIVES

[0280] Composition (B) may contain conventional cosmetic additives, preservatives, perfumes, antioxidants, moisturizing agents, lipophilic actives such as vitamins, lipophilic UV filters, fillers.

[0281] Of course, a person 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 composition according to the invention are not, or substantially not, altered by the envisaged addition.

[0282] The composition (B) used according to the invention may be a care and / or makeup composition for keratinous materials, in particular for eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours.

[0283] According to a particularly preferred form, the composition (B) of the invention is anhydrous.

[0284] For the purposes of the invention, the expression "anhydrous composition" means respectively a composition which contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water by weight of its total weight, and in particular a composition free of water.

[0285] Such compositions are in particular prepared according to the general knowledge of the person skilled in the art.

[0286] Composition (B) of the invention may be in the form of an assembly or kit for conditioning and applying a coating composition for keratinous materials, comprising: - a conditioning device comprising said composition (B) as previously described, - an applicator of said composition.

[0287] The container may delimit one or more compartment(s). The container may, for example, be in the form of a tube.

[0288] Such an applicator may be attached to a cap mounted reversibly on said container between a closing position of said container and a makeup position.

[0289] Alternatively, such an applicator can be irreversibly mounted on said container. Examples of such applicators include felt-tip pens and brushes, which may be made of synthetic fibers.

[0290] It is understood that within the framework of the present invention, the weight percentages given for a compound or a family of compounds are always expressed in weight relative to the total weight of the composition.

[0291] Throughout the application, the expression "includes a" or "comprises a" shall be understood as meaning "containing at least one" or "comprising at least one", unless otherwise specified.

[0292] It is understood that the following examples are provided for illustrative purposes only and are in no way limiting the scope of protection conferred by this application. EXAMPLES OF PREPARATION

[0293] Example 1: Preparation of a 60 wt% isododecane solution of a silicone resin modified by 3-glyceroxypropyl groups

[0294] A reactor was loaded with 1300 g of a 50% isododecane solution of a powdered organosilicon resin containing a hydrosilyl group, of average composition formula (E4) (weight average molecular weight, 4480; amount of hydrogen gas evolution, 8.0 mL / g), 30.7 g of glycerol monoallyl ether of formula (E5), 1300 g of 2-propanol and 0.7 g of a 0.5% chloroplatinic acid solution in 2-propanol, and the reaction was carried out by heating for 6 hours at 100°C. The solvent was then removed by heating under reduced pressure. Next, 325 g of ethanol were added, after which 6.5 g of a 5% aqueous sodium hydroxide solution were added, hydrolyzing the unreacted hydrosilyl groups, after which neutralization was carried out by adding 0.8 g of concentrated hydrochloric acid.After neutralization, 195 g of 0.01 N aqueous hydrochloric acid were added, hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene, and neutralization was carried out with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was then heated under reduced pressure to drive off the solvent and filtered, yielding an isododecane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). (Me3SiO 1 / 2)27.s(HMe2SiO 1 / 2) 1.6(8^4 / 2)35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiO 1 / 2)27.s(R2Me2SiO 1 / 2) 1.5(8^4 / 2)35.3 (E6) R2 = -CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H. .

[0295] Examples of eyebrow makeup composition

[0296] The following pencil lead type (Al) Base Coat composition was prepared.

[0297] [Tables 1] Phase Ingredients (INCI name or chemical name) Composition (Al) A BLACK 2 (and) LAURETH-21 2.0 YELLOW 5 / CI 19140 0.006 BLUE 1 / CI 42090 0.12 B POLY VINYLPYRROLIDONE 0.4 Glycerin 6.3 Ethanol 5.3 RED 40 / CI 16035 0.9 PEG / PPG-14 / 4 DIMETHICONE 0.5 CAPRYLYL GLYCOL 0.6 PHENOXYETHANOL 0.7 SODIUM DEHYDROACETATE 0.1 Water qs 100

[0298] The following Top Coat compositions (Bl) and (B2) were prepared.

[0299] Contents are indicated as % by weight of raw material, unless otherwise stated opposite.

[0300] [Tables2] Ingredients (INCI name) Composition B 1 (comparative) Composition B2 (invention) Glycerol-based silicone resin: (3-GLYCEROXYPROPYL)DIMETHYLSILOX Y TRIMETHYLSILOXYSILICATE - Formula ( 21) in 50% solution in isododecane obtained in Example 1 9,1 9,1 TRIMETHYLSILOXYSILICATE (in solution in isododecane; 75% by weight of resin; Silsoft 74 Fluid® from Momentive Performance Materials) 18 18 NYLON-611 / DIMETHICONE COPOLYMER (Dowsil 2-8179 Gellant® from Dow Corning) 12% MA (*) 0 Silicone gum: DIMETHICONE in blend in isododecane (Silsoft B3820 Blend from Momentive Performance Materials) 0 12% MA (*) DISTEARDIMONIUM HECTORITE 5 5 (Bentone 38 VCG® Rheological Additive from Elem entis) PROPYLENE CARBONATE 1.65 1.65 ISODODECANE Qsp 100 Qsp 100

[0301] (*) MA = active ingredient Composition preparation protocol

[0302] Disteardimonium hectorite was pre-dispersed in isododecane. All ingredients were added to an Olsa-type tank, then heated to 70°C and homogenized for 30 min, then cooled to room temperature (25°C).

[0303] Tests to measure durability: Resistance to makeup remover oil: A layer of pencil was deposited on Supplale® in a 4 x 5 cm rectangle. If necessary, a layer of top coat (50mg) was applied evenly over the layer of pencil with a beveled brush. The deposit was left to dry for 24 hours. We performed 5 colorimetric data measurements on each deposit (T0) on the 4 corners and at the center of Supplale® with a CM 700d® spectrophotometer (Minolta) (illuminant D65, angle 10°, specular component excluded). We placed 3 drops of cleansing oil (Shu Uemura - Ultime 8 Cleansing Oil®) on the deposit. The deposit to be evaluated was rubbed in a circular motion 4 times. We rinsed it with water. We dabbed with a tissue to remove the excess water. We repeated the operation 5 times on each deposit. The deposit was left to dry for 24 hours. We performed 5 colorimetric data measurements (T5) on each deposit. The variation of the AE color between T0 and T5 was measured in the CIE L*a*b* system, using the CM 700d Spectrophotometer. The value of AE is calculated according to the following equation: AE = [(L* - L*0)2 + (a* - a0*)2 + (b* - b0*)2]1 / 2 where L*a*b* represent the values ​​of the coordinates in the CIE Lab 76 color space, measured after the test, and Lo*, a0*b0* represent the values ​​measured before the test. Results

[0304] The results obtained are shown in the table below:

[0305] [Tables3] Comparative Invention Al Al + Bl Al + B2 AE 5.97 2.10 0.96 Standard deviation AE 0.45 0.74 0.36

[0306] The results of comparative tests showed that the two-step makeup process comprising the application of composition (A1) followed by the application of composition (B2) according to the invention, comprising the association of a non-glycerol silicone resin, a glycerol silicone resin, a silicone gum and a volatile oil, led to makeup having excellent resistance to makeup remover oil unlike the one-step makeup process applying composition (A1) or followed by the application of the top coat outside the invention because it lacks silicone gum and comprises a silicone polyamide.

Claims

Demands

1. A coating method, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours, comprising at least the following steps: 1) the application of a first composition (A) “Base Coat” supplied in an assembly including a felt-tip applicator; said composition (A) comprising, in particular in a physiologically acceptable medium: i) an aqueous phase ii) at least one film-forming polymer; iii) at least one colorant; 2) the application on the layer formed by composition (A), of a second layer formed by a composition (B) “Top Coat” comprising, in particular in a physiologically acceptable medium: a) at least one non-glycerol silicone resin; b) at least one glycerol silicone resin; c) at least one silicone gum;d) at least one oily phase comprising at least one volatile hydrocarbon oil;

2. A process according to claim 1, characterized in that the composition (A) comprises water in a content of 10 to 90% by weight, and preferably 30 to 85% by weight, relative to the total weight of the composition (A).

3. A method according to claim 1 or 2, characterized in that the composition (A) comprises at least one film-forming polymer selected from polyvinylpyrrolidones (PVP).

4. A process according to any one of the preceding claims, characterized in that the composition (A) comprises a film-forming polymer(s) content of 0.5% to 20% by weight, and preferably of 1% to 15% by weight, relative to the total weight of the composition (A).

5. A method according to any one of the preceding claims, characterized in that, in composition (A), the coloring matter is selected from mineral pigments, organic pigments, mother-of-pearl, water-soluble dyes, and mixtures thereof.

6. A process according to any one of the preceding claims, characterized in that the composition (A) comprises at least one colouring material selected from D&C YELLOW 5 (CI 19140), BLACK 2 (CI 77266), D&C BLUE 1 (CI 42090), DC RED 40 (CI 16035), and mixtures thereof.

7. A process according to any one of the preceding claims, characterized in that the composition (A) comprises a content of colouring matter(s) ranging from 0.01 to 15% by weight, in particular from 0.01 to 10% by weight, and in particular from 0.02 to 5% by weight, relative to the total weight of the composition (A).

8. A process according to any one of the preceding claims, characterized in that the composition (A) comprises at least one surfactant, preferably a non-ionic surfactant, and more particularly a silicone non-ionic surfactant, and even better PEG / PPG-14 / 4 DIMETHICONE.

9. A process according to the preceding claim, characterized in that the composition (A) comprises a content of non-ionic surfactant(s) ranging from 0.01 to 10% by weight, in particular ranging from 0.1 to 7.5% by weight, or even from 0.1 to 5% by weight, relative to the total weight of the composition (A).

10. A process according to any one of the preceding claims, characterized in that the composition (A) comprises at least one water-miscible polyol at room temperature (25 °C), in particular selected from polyols having from 2 to 20 carbon atoms, and more particularly glycerin.

11. A process according to any one of the preceding claims, characterized in that the composition (A) comprises at least one monoalcohol having from 2 to 5 carbon atoms such as, for example, ethanol, isopropanol and mixtures thereof, glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes, and mixtures thereof, and preferably monoalcohols having from 2 to 5 carbon atoms such as ethanol and isopropanol, and mixtures thereof.

12. A method according to any one of the preceding claims, characterized in that the composition (A) has a viscosity ranging from 0.05 to 7 Pa.s, preferably ranging from 0.1 to 3 Pa.s, plus preferentially ranging from 0.1 to 1 Pa.s, more particularly from 0.1 to 0.5 Pa.s, and even more particularly ranging from 0.1 to 0.3 Pa.s.

13. A method according to any one of the preceding claims, characterized in that the felt-tip applicator is an applicator pen comprising a block of porous material impregnated with composition (A), and a wick enabling the transport of composition (A) by capillary action.

14. A method according to any one of the preceding claims, characterized in that the felt tip is in the form of a brush.

15. A method according to any one of the preceding claims, characterized in that the composition (B) comprises at least one non-glycerol silicone resin selected from MQ type silicone resins, in particular of the Trimethylsiloxysilicate type.

16. A process according to claim 15, characterized in that the Trimethylsiloxysilicate type resin is in solution in isododecane.

17. A process according to any one of the preceding claims, characterized in that the composition (B) comprises a content of non-glycerol silicone resin(s), expressed as active material, ranging from 4 to 35% by weight, preferably ranging from 6 to 30% by weight, and more preferably from 8 to 25% by weight, relative to the total weight of the composition (B).

18. A process according to any one of the preceding claims, characterized in that the composition (B) comprises a content of glycerol-siliconized resin(s), expressed as active material, ranging from 0.1 to 40% by weight, preferably ranging from 0.2 to 30% by weight, and more preferably from 0.5 to 15% by weight, relative to the total weight of the composition (B).

19. A method according to any one of the preceding claims, characterized in that in composition (B), the glycerol-based silicone resin contains at least one organosiloxane motif of the type RR'R”SiO1 / 2 in which R, R' and R'”, identical or different, denote hydrocarbon radicals, at least one of which of said radicals contains a monoglycerol group or a polyglycerol group

20. A process according to claim 19, characterized in that, in composition (B), the glycerol silicone resin contains at least one dimethylsiloxane motif R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

21. A method according to any one of the preceding claims, wherein in composition (B), the glycerol-coated silicone resin(s) are selected from those of the following formula (1). (R*3SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R^ KD in which - each R1, identical 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; - each R2 is a mono- or polyglycerol group of the following general formula (2) —(CH2)2—CÆ—O—(CH2CH(OH)CH2O)iR4(2) in which - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, and - the indices 1 and i are integers satisfying the conditions 0 < 1 < 15 and 0 <i< 5, - chaque R3 est un groupe identique ou différent de formule générale (3), de formule générale (4),of general formula (5) or general formula (6) below —(CH2)2—CmH2m—(SiOR'jj—SiR1, (3) —(CH2)2—CmH2m—SiR*kl—(OSiR*3)3_kl (4) —(CH2)2—CmH2m—SiR'kl—(OSiRWOSiR1,^^ (5) —(CH2)2—CmH2m—SiR'kl—(OSiR'^OSiR'^OSiR1^ 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 group - the indices m, j, and k1 to k3 are integers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; - the indices a, b, c, d, e and f are numbers that satisfy the conditions, 0 < a < 400, 0 ​

22. A method according to claim 21, characterized in that in composition (B), the glycerol silicone resin(s) of formula (1) are chosen from those whose - indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; - the index i in the general formula (2) of the polyglycerol group R2 is an integer which satisfies the condition 0 < i < 3.

23. A method according to any one of claims 21 or 22, characterized in that, in composition (B), the glycerol-siliconized resin(s) of average formula (1) are in solid form at 25 °C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

24. A method according to any one of claims 20 to 23, characterized in that, in composition (B), the glycerol-siliconized resin(s) has (have) a hydrophilic-lipophilic equilibrium (HLB), as determined by Griffin's formula, ranging from 0.1 to 15, and more preferably from 1.0 to 8.

0.

25. A process according to any one of claims 21 to 24, wherein the composition (B) comprises at least one glycerolated silicone resin of formula (1) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate corresponding to the following formula (21): [(CH3)3SiO1 / 2]a[R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - 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 and 0.5 < (a+b) / f < 1.

5.

26. A process according to claim 25, characterized in that the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in solution in at least one volatile oil.

27. ​​A method according to any one of the preceding claims, characterized in that the composition (B) comprises at least one volatile oil selected from the C8-C16 isoalkanes, alone or in mixtures, in particular isododecane.

28. A process according to any one of the preceding claims, characterized in that the composition (B) comprises a volatile hydrocarbon oil(s) content of less than or equal to 80% by weight, preferably from 40 to 70% by weight, relative to the total weight of said composition (B).

29. A process according to any one of the preceding claims, characterized in that in composition (B), the silicone gum is selected from polydimethylsiloxane gums, in particular of INCI name Dimethicone, polydimethylsiloxane gums comprising at least one aryl radical in particular of INCI name: Diphenyl Dimethicone), gums of INCI name Dimethiconol, or mixtures thereof, and preferably gums of INCI name Dimethicone, alone or in mixtures.

30. A process according to any one of the preceding claims, characterized in that the silicone gum (c) is selected from polyorganosiloxanes of molecular mass by weight greater than or equal to 180000g / mol, preferably greater than or equal to 400000 g / mol.

31. A process according to any one of the preceding claims, characterized in that, in composition (B), silicone gum (c) is used in the form of a mixture with one or more volatile or non-volatile oils, preferably selected from volatile silicones; non-volatile polydimethylsiloxane oils; polyphenylmethylsiloxane oils; isoparaffins, in particular C8-C16 such as isododecane; methylene chloride; pentane; dodecane; tridecane; tetradecane; or mixtures thereof; preferably from C8-C16 isoparaffins, in particular isododecane.

32. A method according to any one of the preceding claims, characterized in that the composition (B) comprises a silicone gum(s) content, expressed as active material, ranging from 2 to 35% by weight, and more particularly from 5 to 25% by weight, relative to the total weight of the composition (B).

33. A method according to any one of the preceding claims, characterized in that composition (B) further comprises at least one lipophilic thickener, preferably a lipophilic clay, and more particularly a hectorite modified by distearyl dimethyl ammonium chloride with INCI name: DISTEARDIMONIUM HECTORITE.

34. A process according to claim 33, characterized in that the composition (B) comprises a content of lipophilic thickener(s) ranging from 0.5 to 10% by weight, and more preferably from 1 to 6% by weight, relative to the total weight of the composition (B).

35. A process according to any one of the preceding claims, characterized in that the composition (B) contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water, relative to the total weight of the composition, and in particular is free of water.

36. A set or kit for coating, in particular for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, comprising at least 1) a composition (A) as defined in any one of claims 1 to 14; and 2) a composition (B) as defined in any one of claims 15 to 35; said compositions (A) and (B) being packaged separately.

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