Two-step eyebrow makeup process with a first composition of pencil lead type and a second composition with a non-glycerol silicone resin, a glycerol silicone resin, a silicone polyamide

Abstract

A two-step eyebrow makeup method with a first pencil-type composition and a second composition with a non-glycerol silicone resin, a glycerol silicone resin, or a silicone polyamide. 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 from which said hairs are implanted, and their contours, comprising at least the following steps: 1) the application of a first composition (A) "Base Coat" of pencil-type composition comprising, in particular in a physiologically acceptable medium: i) at least one wax, ii) at least one non-volatile oil, and iii) at least one pigment, and 2) the application, over the layer formed by composition (A), of a second layer formed by a composition (B) "Top Coat" comprising,particularly in a physiologically acceptable environment: a) at least one non-glycerol silicone resin; b) at least one glycerol silicone resin; etc.) at least one silicone polyamide; d) at least one oily phase comprising at least one volatile hydrocarbon oil.

Description

Title of the invention: Two-step eyebrow makeup method with a first composition of pencil lead type and a second composition with a non-glycerol silicone resin, a glycerol silicone resin, a silicone polyamide

[0001] The present application relates to the field of makeup using keratinous materials, in particular eyebrows including eyebrow hairs, the skin in which said hairs are implanted 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. - Pens, which are also easy to use but only last a day. They are often made with water-based formulas containing dyes. - Tattoo parlor services, which are very painful, but last for several months. - anhydrous gels such as the commercial products Urban Decay's Inked Waterproof Brow Gel® (Mintel ID 7578707) and Maybelline's Up to 3 Day Styling Gel® (Mintel ID 10361806) containing isododecane and a 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 by using a coating process, 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” of the type used for pencil lead comprising, in particular in a physiologically acceptable environment: i) at least one wax, ii) at least one non-volatile oil, and iii) at least one coloring agent, and 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; and b) at least one glycerol-based silicone resin; and (c) at least one silicone-coated polyamide; and d) at least one oily phase comprising at least one volatile hydrocarbon oil.

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

[0007] Thus, a first object of the present invention is 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” of the type used for pencil lead comprising, in particular in a physiologically acceptable environment: i) at least one wax, ii) at least one non-volatile oil, and iii) at least one coloring agent, and 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; and b) at least one glycerol-based silicone resin; and c) at least one silicone polyamide d) at least one oily phase comprising at least one volatile hydrocarbon oil.

[0008] A second object of the present invention is a coating set or kit, in particular for the care and / or makeup of keratinous materials, in particular eyebrows and the skin around the eye and eyebrows, comprising at least 1) a composition (A) as defined above; and 2) a composition (B) as defined above; said compositions (A) and (B) being conditioned separately. Definitions

[0009] In the context of the present invention, the term "keratinous materials" refers in particular to 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.

[0010] By "physiologically acceptable" is meant 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] By “monoglycerol group” is meant any group comprising in its chemical structure a -O-CH2-CHOH-CH2OH group

[0015] 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.

[0016] Composition (A) Pencil lead type base coat

[0017] The composition (A) Base Coat of the type for pencil lead according to the invention, comprises, in particular in a physiologically acceptable medium: i) at least one wax, ii) at least one non-volatile oil, and iii) at least one coloring material. Wax(s)

[0018] For the purposes of this invention, "wax" means a solid, rigid lipophilic compound at room temperature (25 °C) with a reversible solid / liquid phase change, a melting point above 30 °C up to 120 °C, a hardness greater than 0.05 MPa, and exhibiting in the solid state an orga- anisotropic crystalline nisation.

[0019] By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture and to obtain crystallization of this wax in the oils of the mixture when said mixture is brought back to room temperature.

[0020] According to the invention, the composition more specifically comprises at least one hard wax. By "hard wax" for the purposes of the present invention, we mean a wax having a melting point of 65 to 120°C, more preferably between 70 and 100°C.

[0021] Advantageously, by “hard” wax in the sense of the present invention, we mean a wax having at 20 °C a hardness greater than 5 MPa, in particular ranging from 5 to 30 MPa, preferably greater than 6 MPa, better still ranging from 6 to 25 MPa.

[0022] To perform these hardness measurements, the wax is melted at a temperature equal to the melting point of the wax + 20 °C. For this purpose, 30 g of wax is placed in a 100 ml beaker with a diameter of 50 mm, itself positioned on a heated magnetic stirrer. Approximately 15 g of molten wax is poured into a stainless steel container 80 mm in diameter and 15 mm deep, previously heated to 45 °C in an oven. The wax is then allowed to recrystallize in a room temperature-controlled at 20 °C for 24 hours before taking the measurement. The mechanical properties of the wax or wax mixture are determined in a room temperature-controlled at 20 °C using the texture analyzer sold under the name TA-XT2i by Swantech, equipped with a stainless steel cylinder with a diameter of 2 mm.The measurement process comprises three stages: a first stage after automatic detection of the sample surface, where the stylus moves at a measurement speed of 0.1 mm / s and penetrates the wax to a depth of 0.3 mm; the software records the maximum force reached; a second stage, called the relaxation stage, where the stylus remains in this position for one second, and the force is recorded after one second of relaxation; and finally, a third stage, called the retraction stage, where the stylus returns to its initial position at a speed of 1 mm / s, and the retraction energy of the probe (negative force) is recorded. The hardness value corresponds to the maximum compressive force measured in Newtons divided by the surface area of ​​the texture analyzer cylinder, expressed in mm², in contact with the wax. The resulting hardness value is expressed in megapascals (MPa).

[0023] The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER.

[0024] The measurement protocol is as follows: A 15 mg sample of wax placed in a crucible is subjected to an initial heating from 0 °C to 120 °C at a rate of 10 °C / minute, then is cooled from 120 °C to 0 °C at a rate of 10 °C / minute and finally subjected to a second temperature ramp from 0 °C to 120 °C at a heating rate of 5 °C / minute. During the second temperature ramp, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the wax sample is measured as a function of temperature. The melting point of the compound is the temperature value corresponding to the peak of the curve representing the variation in the difference in power absorbed as a function of temperature.

[0025] The waxes that can be used in the compositions according to the invention can be chosen from solid and rigid waxes at room temperature, of animal, vegetable, mineral, synthetic origin, and their mixtures.

[0026] Generally speaking, waxes of vegetable or mineral origin will be preferred. Animal or synthetic waxes may also be suitable for the invention.

[0027] Examples of hard waxes include Camauba wax, candelilla wax, BIS-PEG-12 DIMETHICONE CANDELILLATE wax such as, for example, SILICONYL CANDELLILA WAX® marketed by KOSTER KEUNEN, hydrogenated Jojoba wax such as, for example, that marketed by DESERT WHALE, hydrogenated palm oil such as that marketed by SIO, rice bran wax, Sumac wax, ceresin waxes, laurel wax, Chinese insect wax, Shellac wax, hydrogenated olive oil such as Waxolive® from SOLIANCE, waxes obtained by hydrogenation of esterified olive oil with C12 to C18 fatty alcohols such as those sold by SOPHIM under the trade names Phytowax Olive 12L44®, 14L48®, 16L55® and 18L57®,Waxes obtained by hydrogenating esterified castor oil with cetyl or behenic alcohol, such as those sold under the names Phytowax Ricin 16 L 64® and Phytowax Ricin 22 L 73® by SOPHIM; hydrogenated camelina wax; Ouricury wax; Montan wax; ozokerite waxes, such as Wax SP 1020 P® ​​marketed by Strahl & Pitsch; microcrystalline waxes, such as that sold under the trade name Microwax HW® by PARAMELT; hydrogenated coconut oil (INCI name: HYDROGENATED COCOGLYCERIDES), such as that sold under the trade names Softisan 100® or Softisan 142 by SASOL; and polymethylene waxes, such as that sold under the trade name Cirebelle 303® by the company SASOL, polyethylene waxes such as, for example, those sold under the trade names Performalene-PL Polyethylene ®,Performalene 400 Polyethylene®, Performalene 655 Polyethylene® and Performalene 500-L® Polyethylene by the company, New Phase 27 Technologies, alcohol-polyethylene waxes such as, for example, that marketed under the name Performacol 425 Alcohol® by BARECO, the ethylene / acrylic acid 95 / 5 copolymer sold under the trade name Cire AC 540® by Honeywell, hydroxyoctacosanyl hydroxystearate such as, for example, that sold under the trade name Elfacos C 26® by AKZO, octacosanyl stearate such as, for example, that marketed under the name Kester Wax K 82 H® by KOSTER KEUNEN, stearyl stearate such as, for example, that marketed under the name Liponate SS® by LIPO CHEMICALS, pentaerythritol distearate such as, for example, that marketed under the name Cutina PES® by COGNIS, the adipate mixture of dibehenyl, dioctadecyl adipate and di-eicosanyl adipate (INCI name dialkyl adipate in Cl8-22),The mixture of dilauryl adipate and ditetradecyl adipate (INCI name: C12-C14 dialkyl adipate), the mixture of dioctadecyl sebacate, didocosyl sebacate, and dieicosyl sebacate (INCI name: Cl8-22 dialkyl sebacate), the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate, and dieicosyl octanedioate (INCI name: Cl8-22 dialkyl octanedioate), such as those marketed by COGNIS, pentaerythrityl tetrastearate, such as Lipo Chemicals' Liponate PS-4®, and tetracontanyl stearate, such as KOSTER's Kester Wax K76 H®. KEUNEN, stearyl benzoate such as, for example, Finsolv 116® from FINETEX, behenyl fumarate such as, for example, Marrix 222® from AKZO BERNEL, di-(trimethyloi-1,1,1-propane tetrastearate such as, for example, that offered under the name "HEST 2T-4S®" by HETERENE,didotriacontanyl distearate, such as Kester Wax K82D® from KOSTER KEUNEN; polyethylene glycol with 4 oxyethylene units (PEG-4), such as that sold under the trade name Clariant Licowax KST1®; hexanediol disalycilate 28, such as Betawax RX-13750® marketed by CP Hall; dipentaerythritol hexastearate, such as that sold under the trade name Hest 2P-6S® by HETERENE; ditrimethylolpropane tetrabehenate, such as that sold under the trade name Hest 2T-4B® by HETERENE; jojoba esters, such as that sold under the trade name Floraester HIP® by FLORATECH; mixtures linear carboxylic acid (C20-40) / saturated hydrocarbons (INCI name: C20-40 Acid polyethylene) such as, for example,Performacid 350 Acid® from NEW PHASE TECHNOLOGIES, synthetic wax of the Fischer-Tropsch type such as that marketed under the, Rosswax 100® reference by the ROSS company, stearic alcohol, behenic alcohol, dioctadecyl carbonate such as, for example, Cutina KE 3737®, sucrose polybehenate such as, for example, Crodaderm B® from the CRODA company, and mixtures thereof.

[0028] The waxes mentioned above can also be used in the form of commercially available mixtures, for example, under the names PERFORMACOL 425 ALCOHOL® (INCI name C20-40 ALCOHOLS (and) POLYETHYLENE which is a mixture of 85% by weight of C20-C40 fatty alcohols and 15% by weight of polyethylene) from the company NEW PHASE TECHNOLOGIES; KOSTER KPC-56® (Mixture of 87.5% by weight cetyl stearate, 7.5% by weight behenic alcohol and 5% by weight palm kernel glycerides), KPC-60® (Mixture of 87.5% by weight stearyl stearate, 7.5% by weight behenic alcohol and 5% by weight palm kernel glycerides), KPC-63® (Mixture of 87.5% by weight behenyl stearate, 7.5% by weight behenic alcohol and 5% by weight palm kernel glycerides) and KPC-80® (Mixture of 86% by weight synthetic beeswax, 7.5% hydrogenated vegetable oil and 6.5% by weight behenic alcohol) from the company KOSTER KEUNEN.

[0029] According to a particular embodiment of the invention, the composition (A) comprises at least one hard wax selected from Candelilla wax, INCI name EUPHORBIA CERIFERA (CANDELILLA) WAX / CANDELILLA CERA, rice bran wax, INCI name ORYZA SATIVA (RICE) BRAN WAX / ORYZA SATIVA CERA, and a microcrystalline wax, INCI name MICROCRYSTALLINE WAX / CERA MICROCRISTALLINA, a polyethylene wax, a mixture of waxes of INCI name: C20-40 ALCOHOLS (and) POLYETHYLENE, hydrogenated coconut oil of INCI name: HYDROGENATED CO-COGLYCERIDES, and their mixtures.

[0030] According to a particular embodiment of the invention, the composition (A) comprises the wax or wax(s), in a concentration of 20 to 50% by weight and preferably 25 to 45% by weight relative to the total weight of the composition. Non-volatile oil

[0031] The composition of the invention comprises at least one non-volatile oil.

[0032] The term "oil" means any fatty substance in liquid form at room temperature (20-25°C) and at atmospheric pressure (760 mmHg or 10⁵ Pa). These oils can be of vegetable, mineral, or synthetic origin.

[0033] The non-volatile oil or oils may be chosen from the group consisting of hydrocarbon oils, silicone oils and their mixtures.

[0034] The non-volatile oil(s) is / are present in the composition of the invention, preferably at a content ranging from 5 to 20% by weight, more preferably- approximately 7 to 15% by weight relative to the total weight of the composition.

[0035] For the purposes of the present invention, "siliconized oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group, and more particularly an organopolysiloxane.

[0036] The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether, carboxylic functions.

[0037] By "non-volatile oil" is meant an oil remaining on the keratin material at ambient temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 2.66 Pa, preferably less than 0.13 Pa. By way of example, the vapor pressure can be measured according to the static method or by the isothermal effusion method, depending on the vapor pressure (OECD standard 104). Non-volatile hydrocarbon oils

[0038] By way of example of a non-volatile hydrocarbon oil that can be used in the invention, we may cite: - hydrocarbon oils of vegetable origin, such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl / octyldodecyl / phytostearyl glutamate; triglycerides consisting of fatty acid esters and glycerol, in particular, whose fatty acids may have chain lengths ranging from C4 to C36, and, in particular, from C18 to C36, these oils being linear or branched, saturated or unsaturated; These oils may include, in particular, heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, pumpkin seed oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe vera oil, sweet almond oil, peach kernel oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, carrot oil, safflower oil, hemp oil,rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grapeseed oil, pistachio oil, butternut squash oil, pumpkin oil, quinoa oil, rosehip oil, sesame oil, soybean oil, sunflower oil, castor oil, and watermelon oil, and mixtures thereof, or C4 to C1 fatty acid triglycerides, in particular caprylic / capric acid triglycerides, notably those sold by the company Stéarineries Dubois or in particular those sold under the brand name, Miglyol 810®, 812® and 818® nominations by Dynamit Nobel, - linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam, squalane; - synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether; - synthetic esters, such as oils with the formula R1COOR2, in which RI represents a remnant of at least one linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched one, containing from 1 to 40 carbon atoms, provided that RI + R2 is greater than or equal to 10. The esters may be selected, in particular, from esters of alcohol and fatty acids, such as cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, stearate octyldodecyl stearoyl, hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates,and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, ethyl 2-hexyl 4-diheptanoate and palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol diethyl 2-hexanoate and mixtures thereof, C12-C15 alcohol benzoates, C12-C15 alkyl ethylhexanoate such as the commercial product ACTIVEMOL EH-25® from Innospec Active Chemicals, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters such as isostearyl lactate, di-isostearyl malate; , - esters of pentaerythritol, such as dipent-taerythritol tetrahydroxystearate / tetraisostearate, - esters of diol dimers and diacid dimers, - diol dimer and diacid dimer copolymers and their esters, such as dilinoleyl diol / dilinoleic dimer copolymers and their esters, - polyol and diacid dimer copolymers, and their esters, - liquid fatty alcohols at room temperature with branched and / or unsaturated carbon chains having 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, oleic alcohol; - higher fatty acids such as oleic acid, linoleic acid, li- nolenic; - carbonates such as dicapryl carbonate; - acetates; - citrates; - their mixtures. Non-volatile silicone oils

[0039] Examples of non-volatile silicone oils include: - polydimethylsiloxanes (INCI name: Dimethicone) in particular, with viscosities ranging from 50 to 500 mm2 / s (est), notably 350 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 350® by WACKER, XIAMETER PMX-200 SILICONE FLUID® 350CS by DOW CORNING; polydimethylsiloxanes with viscosities ranging from 50 to 150 mm2 / s (est), notably 100 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 100® by WACKER, XIAMETER PMX-200 SILICONE FLUID 100CS® by DOW CORNING. - phenylated silicone oils such as phenyl trimethicones, phenyl dhne-thicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethyl-siloxysilicates.

[0040] According to a preferred method, the non-volatile oil or oils is / are chosen from synthetic esters, C4 to Ci8 fatty acid triglycerides, and mixtures thereof.

[0041] The quantity of non-volatile oil(s)(c) is generally adjusted to control the texture and mechanical properties of the composition (A) according to the invention, in particular in terms of application comfort and lead retention.

[0042] In particular, the non-volatile oil or oil(s) may be present at a rate of 5 to 30% by weight and in particular of 10 to 20% by weight of the total weight of the composition. Coloring agent

[0043] The composition (A) according to the invention comprises at least one coloring material.

[0044] The coloring materials may be selected from mineral pigments, organic pigments, mother-of-pearl, liposoluble dyes, and mixtures thereof.

[0045] The term "pigments" means white or colored particles, mineral or organic, insoluble in an aqueous medium, intended to color and / or opacify the composition and / or the resulting deposit. These pigments may be white or colored, mineral and / or organic.

[0046] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0047] 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 mixed with TiO₂, ZrO₂, Nb₂O₅, CeO₂, and ZnS.

[0048] 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 5 µm, and more preferably from 300 nm to 1 pm.

[0049] 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 1 Opm, preferably from 200 nm to 5 pm, and more preferably from 300 nm to 1 pm.

[0050] The sizes are measured by static light scattering using a commercial particle size analyzer, specifically 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 pm to 1000 pm. 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 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.

[0051] D

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

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] Among mineral pigments, nacres can also be mentioned. They can be chosen from white pearlescent pigments such as mica coated with titanium 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.

[0058] The pigments that can be used according to the invention can also be organic pigments.

[0059] 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 among the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0060] 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 codified in the Color Index under references CI 1725, 15510, 45370, 71105, the red pigments coded in the Color Index under references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and the pigments obtained by oxidative polymerization of indole and phenolic derivatives as described in patent FR2 679 771.

[0061] 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.

[0062] The pigment can also be a lacquer. By lacquer, we mean insolubilized dyes adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0063] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0064] Among the organic dyes, we can mention cochineal carmine. We can also mention the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0065] As examples of lacquers, we can cite the product known under the name D&C Red 7 (CI 15 850 :1). Fat-soluble coloring agents

[0066] By "liposoluble colouring material", in the sense of the invention, is meant any compound generally organic, natural or synthetic, soluble in an oily phase or solvents miscible with a fat and capable of colouring.

[0067] As suitable fat-soluble colorants for the invention, the following may be cited in particular: synthetic or natural fat-soluble colorants such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red, carotenes (3-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan Brown, quinoline yellow, annatto, curcumin.

[0068] Preferably, the coloring matter(s) is / are present, preferably, in the composition at a content less than or equal to 50% by weight, preferably of 25 to 40% by weight, more specifically 3 to 15% by weight relative to the total weight of the composition.

[0069] Preferably, the composition (A) according to the invention comprises at least one powdered colouring material of the mineral pigment type, in particular selected from titanium dioxides, black, red or yellow iron oxides, coated or uncoated, ferric aluminium iron-rocyanide, and mixtures thereof. Surfactants

[0070] The composition (A) according to the invention may also include at least one emulsifying and / or dispersing surfactant.

[0071] More particularly suitable for the invention are fatty acid esters of glycol, C4-C24 fatty acid esters, in particular C8-Ci8, linear or branched, saturated or unsaturated (palmitate, stearate, oleate), of oxyethylenated or non-oxyethylenated sorbitan, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol (polyethylene glycol monostearates or monolaurates), fatty acid esters of glucose derivatives, alkyl polyglucosides, condensation products of an α-diol, a monoalcohol and mixtures thereof.

[0072] We can also mention polyol fatty acid esters such as sorbitol mono-, di-, tri- or sesquioleate, sorbitol mono-, di-, or tri-stearate or of

[0073] One can also mention partial esters resulting from the reaction of at least one linear or branched fatty acid in the C8-C40 and preferably in the C8-C22, saturated or unsaturated, in particular ricinoleic acid or 12-hydroxystearic acid, with at least one polyol such as glycerol, polyglycerol, pentaerythritol, saccharide alcohols such as sorbitol, and in particular polyglycerol esters, and - esters resulting from the reaction of sorbitan with at least one linear or branched fatty acid, saturated or unsaturated.

[0074] Representative examples of this type of compound include: - POLYGLYCERYL-2 TRIISOSTEARATE such as the commercial product sold under the name RISOREX PGIS23® by the company KOKYU ALCOHOL KOGYO; - SORBITAN TRISTEARATE such as the commercial product sold under the name SP SPAN 65 MBAL-PW-(MV)® by the company CRODA; and their mixtures.

[0075] The choice of these surfactant(s) and / or dispersing agent(s) and their corresponding quantities is of course within the competence of a person skilled in the art.

[0076] In this case, the composition according to the invention may comprise from 0.05 to 10% by weight of surfactant(s), relative to the total weight of the composition.

[0077] With regard more particularly to the dispersing agent, it may be present at a rate of 2 to 10%, more particularly 3 to 7% by weight, relative to the weight of the composition according to the invention. Charges

[0078] The composition according to the invention may further comprise at least one of the fillers commonly used in the field of cosmetics.

[0079] By "fillers" we mean colorless or white particles, mineral or synthetic, lamellar or non-lamellar, intended to give body or rigidity to the composition and / or softness, matte finish and uniformity to the makeup.

[0080] The fillers which may be present at a rate of 0.01 to 60% by weight, more particularly from 3 to 10% in the composition according to the invention, are generally mineral or synthetic, lamellar or non-lamellar.

[0081] 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® (NOBEL INDUSTRIES), silicone resin microbeads, precipitated calcium carbonate, magnesium carbonate or hydrocarbonate, bismuth oxychloride and mixtures thereof. Additives

[0082] The composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners like zinc stearate, trace elements, softeners, sequestrants, UV filters and mixtures thereof.

[0083] Finally, the composition according to the invention may also contain other additives, in particular to control its viscosity, adjust its color or its reflective effect.

[0084] Propylene carbonate can be used in particular as a useful agent for controlling viscosity.

[0085] 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.

[0086] According to a particularly preferred form, the composition (A) of the invention is anhydrous.

[0087] 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 water-free composition.

[0088] According to one embodiment, the composition (A) of the invention may further comprise an aqueous phase comprising water and water-soluble organic solvents or miscible in water such as lower monoalcohols having 1 to 5 carbon atoms such as ethanol and isopropanol, 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.

[0089] The composition (A) according to the invention is formulated in a conventional manner in the form of a pencil lead.

[0090] According to a particular embodiment of the invention, the pencil lead can be in retractable form.

[0091] Generally, wax-type compounds are melted and combined with the other liquid components. Various compounds, including solids such as pigments and fillers, are then added to this mixture, and the whole is homogenized again. The resulting matrix is ​​then formulated as pencil lead using conventional processes. Composition (B) Top Coat

[0092] Composition (B) “Top Coat” according to the invention comprises, in particular in a physiologically acceptable environment: a) at least one non-glycerol silicone resin; and b) at least one glycerol-based silicone resin; and c) at least one silicone polyamide d) at least one oily phase comprising at least one volatile hydrocarbon oil. Non-glycerol silicone resin

[0093] Composition (B) according to the invention comprises at least one non-glycerol silicone resin.

[0094] 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, polydimethylsiloxane is not a silicone resin.

[0095] The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known as MDTQ, the resin being described according to the different siloxane monomeric units it comprises, each of the letters MDTQ characterizing a type of unit.

[0096] The letter M represents the Monofunctional unit of formula RiR2R3SiOi / 2, the silicon atom being bonded to a single oxygen atom in the polymer comprising this unit.

[0097] The letter "D" signifies a Difunctional unit RiR2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.

[0098] The letter T represents a RiSiO3 / 2 Trifunctional Unit.

[0099] 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.

[0100] In the motifs M, D, T defined above, R, namely RB 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.

[0101] 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.

[0102] 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.

[0103] Examples of silicone resins that can be used in the compositions according to the invention include, for example, MQ-type silicone resins, T-type silicone resins, MQT-type silicone resins, and mixtures thereof. MQ resins:

[0104] By way of example of MQ type silicone resins, alkylsiloxy-silicates of formula [(Ri)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.

[0105] Examples of MQ silicone resins of the Trimethylsiloxysilicate type include those marketed under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker, under the name "KF-7312J®" by Shin-Etsu, and "DC 749®" and "DC 593®" by Dow Corning. T Resins:

[0106] As an example of T-type silicone resins, we may cite polysilses-quioxanes 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.

[0107] Preferably, polymethylsilsesquioxane resins can be used in which R represents a methyl group, such as those commercially available: - by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: a polymer comprising repeating CH3SiO3 / 2 units (T units), which can also comprising up to 1% by weight of (CH3)2SiO2 / 2 units (D units) and having an average molecular weight of approximately 10000 g / mol, or - by the company SHIN-ETSU under the references KR-220L® which are composed of T units of formula CH3SiO3 / 2 and have Si-OH terminal groups (silanol), under the reference KR-242A® which include 98% T units and 2% dimethyl D units and have Si-OH terminal groups or under the reference KR-251® which include 88% T units and 12% Dimethyl D units and have Si-OH terminal groups. MQT Resins:

[0108] As examples of resins comprising MQT motifs, those cited in US document 5,110,890 are known.

[0109] 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 the application WO 2005 / 075542.

[0110] The MQ-T-propyl resin preferably comprises the following units: (i) ((R1)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= 1, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0111] Preferably, the siloxane resin comprises the following units: (i) ((R1)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 preferably being 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.

[0112] 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 ((Ri)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.

[0113] 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.

[0114] Preferably, the composition (B) according to the invention comprises, as a silicone resin, at least one MQ type resin, more particularly of the Trimethylsi-loxysilicate 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.

[0115] A Trimethylsiloxysilicate type resin in solution in isododecane will be used in particular, in particular in a solution of 75% by weight of active matter in isododecane such as the commercial product sold under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS.

[0116] According to a particular embodiment of the invention, the non-glycerol silicone resin(s) is / are present in the composition in an active material content ranging from 4 to 35% by weight relative to the total weight of the composition, 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). Glycerol-based silicone resin

[0117] Composition (B) according to the invention comprises at least one glycerol-coated silicone resin.

[0118] The glycerol-based silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol groups.*

[0119] According to a particular embodiment of the invention, the glycerol silicone resin(s) is / are present in an active material content ranging from 0.1 to 40% by weight relative to the total weight of the composition, 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).

[0120] The glycerol-siliconized resin(s) according to the invention are preferably chosen from those of the following formula (1). [Chem 1] (R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f(l) in which - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - each R2 is a mono- or poly-glycerol group of the following general formula (2)

[0121] [Chem 2] —(CH2)2—QHa—O—(CH2CH(OH)CH2O);R4 (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 a group identical or different from general formula (3), general formula (4), general formula (5) or general formula (6) below [Chem 3] —(CH2)2—CmH2m—(SiORyj—SiR>3 (3) [Chem 4] —(CH2)2—CmH2m—SiRL—(OSiR'3)3 kl) (4) [Chem 5] —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (5) [Chem 6] —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k2)3 kl (6) Or - each R1, whether 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 thereof - the indices m, j and ki 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

[0122] Glycerol-coated silicone resins according to the invention are described in SHIN ETSU's US patent application US20200332065A1.

[0123] 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.

[0124] 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.

[0125] According to a particular mode, the glycerol-siliconized resin(s) have an average molecular weight by weight ranging from 1000 to 100000.

[0126] 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 resins according to the invention preferably varies from 0.1 to 15 according to Griffin's method.

[0127] 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. [Chem 7] (R13SiO1 / 2)aHnR>3-nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 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 which are chosen from the compounds ending with an alkenyl group of general formulas (8), (9), (10), (11) and (12) below. [Chem 8] CH2=CH-ClH21-O-(CH2CH(OH)CH2O)iR4(8) [Chem 9] CH2=CH-CmH2m-(SiOR12)j-SiR13 (9) [Chem 10] CH2=CH—CmH2m—SiR'kl—(OSiR13)3 kl (10) [Chem 11] CH2=CH—CmH2m—SiRlkl—(OSiR'k2(OSiR13)3 k2)3 kl (11) [Chem 12] CH2=CH—CmH2m—SiR'kl—(OSiRlk2(OSiR1k3(OSiR13)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 < 1 < 15, 0 <i<5; - the indices m, j and kl to k3 are integers which 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).

[0128] 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.

[0129] Silicone resin containing a hydrosilyl group used as a starting material.

[0130] 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 with a boiling point of A temperature higher than the reflux temperature during hydrolysis is preferred.

[0131] 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, methylethyl ketone, diethyl ketone and methylisobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol.From the point of view of storage stability and lack of volatility, octamethylcyclotetrasiloxane and decamethylcyclopenta-siloxane are preferred.

[0132] 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 metallic salts of these hydrolyzable silanes.

[0133] [Chem 13] RSSiOSiRS (13) [Chem 14] RSSiX1 (14) [Chem 15] HnR*(3.n)SiOSiR1(3.n)Hn(15) [Chem 16] HjjR'q n)SiX2 (16) 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 of the latter; - X1 and X2 are hydrolyzable functional groups; and - n satisfies the condition 1 < n < 3. [Chem 17] 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.

[0134] In general formulas (13), (14), (15) and (16), the examples and preferred range for R1 are the same as those mentioned above.

[0135] In the general formula (14), X1 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 hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] Examples of organosilicon compounds of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinyl- Chlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane. Of these, trimethylchlorosilane and trimethylethoxysilane are preferred.

[0140] 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.

[0141] 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 R1 bonded to one silicone atom and the "n" associated with the H and R1 bonded to the other silicone atom can be identical or different.

[0142] Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0143] 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.

[0144] 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.

[0145] [Chem 18] R'SiX43 (18) [Chem 19] R12SiX52 (19) Or - each R1 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

[0146] In general formulas (18) and 19), the examples and preferred ranges for R1 are the same as those mentioned above.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] A specific example of a process for preparing silicone resin containing a hydrosilyl group serving 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 the organosilicon compounds of general formulas (13) and (14), one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16), and one or more compounds selected from the hydrolyzable silanes of general formula (17), the condensates of partial hydrolysis of these hydrolyzable silanes, and the metallic 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.

[0152] 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 on the hydrolysis starting product 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.

[0153] 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.

[0154] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane.

[0155] 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, the 1-Propanol and 2-Propanol are particularly preferred.

[0156] 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.

[0157] 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 on the order of 0.001 to 10% of the overall reaction system being preferred.

[0158] After adding water dropwise 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, by carrying out the reaction at a temperature below the boiling point of the organic compound containing hydrosilyl groups used, the deactivation of the hydrosilyl groups can be further suppressed.

[0159] 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.

[0160] After the above hydrolysis, the system is neutralized between 10 and 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this point, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is prevented and the condensation reaction of the organosilicon resin is further promoted. Examples of such strongly basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate.Regarding 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.

[0161] The basic catalyst must be used in a quantity greater than the molar equivalent of the acid catalyst. Performing the neutralization with a quantity of Adding a basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, leading to an increase in molecular weight and the production of 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 added within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, resulting in a resin of the target molecular weight.

[0162] 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 confirming 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.

[0163] In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio between the combined molar quantity of the compounds of general formulas (13), (14), (15) and (16) and the molar quantity 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.

[0164] 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.

[0165] 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 metal salts of these hydrolyzable silanes, it is also possible to add gradually, drop by drop, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group, of general formulas (15) and (16).

[0166] Next, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably performed by heating at 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.

[0167] 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 20] S io K, HK. „ ( wiiW-Si OH-* & <> <2°) S»! A- where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

[0168] 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.

[0169] 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.

[0170] The silicone resin containing a hydrosilyl group obtained as described above It has the average formula (7) above and is composed of Q units (SiO4 / 2) and M units (R* 3SiOi / 2 and (HnR*3 nSiOi / 2)) as essential constituents, and also D units (R*2 SiO2 / 2) and T units (R'SiO3 / 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 perspective of performance and ease of performing operations such as filtration. The average molecular weight can be determined as the equivalent average molecular weight of polystyrene in gel permeation chromatography (GC).

[0171] Process for preparing glycerol-coated silicone resin

[0172] A specific example of a process for preparing the glycerol-siliconized resin according to the invention is described below.

[0173] 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: (R13SiO1 / 2)a(HnR13nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (7) in which - each R1 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 selected from the compounds ending in an alkenyl group of general formulas (8), (9), (10), (11) and (12) below. CH2=CH-CiH21-O-(CH2CH(OH)CH2O)iR4(8) CH2=CH-CmH2m-(SiOR12)j SiR>3 (9) CH2=CH—CmH2m—SiR'kl—(OSiR'3)3 kl (10) CH2=CH—CmH2m—SiRki—(OSiR1k2(OSiR13)3 k2)3 kl (11) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)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 < 1 < 15, and 0 < i < 5; - the indices m, j and ki to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < ki < 2, 0 < k2 < 2 and 0 < k3 < 2; said includes a compound of general formula (8).

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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 system overall. By fixing the amount of activated carbon within this range, the discoloration of the sample can be better suppressed.

[0180] 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.

[0181] An example of a step for removing hydrosilyl groups is the process of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, followed by neutralization by adding an amount of acidic 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 perspective of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being especially preferred.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.

[0182] 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 etherified 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 etherified with propenyl groups. This propenyl-etherified polyether has no reactivity with the hydrogen polyorganosiloxane and therefore remains in the system as an impurity.It is thought that when water acts on this propenyl-etherified polyether, the propenyl ether hydrolyzes, giving rise to the . Propionaldehyde, which gives off an unpleasant odor. It is known that the hydrolysis reaction described above is further favored in the presence of an acid catalyst. Therefore, when polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and causing the unpleasant odor.

[0183] 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).

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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).

[0188] 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.

[0189] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron, and others, either in uncombined form or as a compound. In this case, a catalyst support is not required. However, when a catalyst support is used, it 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 weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0190] 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.

[0191] 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.

[0192] 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 as a result. However, the aldehyde condensate that forms with the condensation of some of the aldehyde remains in the system even after such treatment, and removal by stripping is also difficult. Therefore, by alkylating the unsaturated double bonds that remain when the solution following the addition reaction is hydrogenated, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible (WO2002 / 05588).

[0193] The average molecular weight by weight of the glycerol-siliconized resin of average formula (1) varies, preferably, from 1000 to 100000; from the point of view of performance and ease of operations such as filtration, the average molecular weight by weight varies preferably from 3000 to 50000. Here and 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).

[0194] 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.

[0195] 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 la condition 0 < i < 3 et l'indice j dans la formule générale (3) satisfait à la condition 0 < j < 10 est sous la forme d'un solide à 25° C et présente, de préférence une masse moléculaire moyenne en poids qui varie de préférence comprise de 1000 à 100000 et plus préférentiellement, de 3000 à 50000.

[0196] 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.

[0197] 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):

[0198] [Chem 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.

[0199] According to a particularly preferred form, the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxy silicate of formula (21) is in solution in at least one volatile oil.

[0200] 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 1300 Pa.

[0201] The volatile oil according to the invention can be chosen from the group consisting of hydrocarbon oils, silicone oils, and their mixtures.

[0202] 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.

[0203] 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.

[0204] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0205] Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and, for example, oils sold under the trade names Isopar® or Permetyl®. Isododecane is preferred.

[0206] 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 x 10⁶ to 8 x 10⁶ m² / s), and containing, in particular, 2 to 7 silicon atoms, these silicones optionally 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, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) is preferred.

[0207] According to a particularly preferred form, the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution with 49.5% by weight of active matter in isododecane as the product manufactured under the trade name X-25-9138A® by SHIN ETSU with a weight average molecular mass of 11000. volatile hydrocarbon oil

[0208] Composition (B) according to the invention comprises an oily phase comprising at least one volatile hydrocarbon oil.

[0209] Oil means any fatty substance in liquid form at room temperature (25 °C) and atmospheric pressure (760 mm Hg or 105 Pa).

[0210] 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.

[0211] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0212] Examples include C8-C16 petroleum-derived 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®.

[0213] 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 the Shell company, can also be used.

[0214] 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.

[0215] As an example of linear alkanes suitable for the invention, mention may be made of the alkanes described in Cognis patent applications WO 2007 / 068371, or WO2008 / 155059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from coconut or palm oil.

[0216] By way of example of linear C6-C14 alkanes suitable for the invention, 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 mixtures thereof.

[0217] 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.

[0218] 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®.

[0219] According to yet another embodiment, a mixture of C9-C12 linear volatile alkanes with INCI name C9-12 ALKANE is used, such as the product marketed by the company BIOSYNTHIS under the reference VEGELIGHT SILK®.

[0220] 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.

[0221] According to a particularly preferred embodiment, the volatile hydrocarbon oil is selected from C8-C16 branched alkanes, and more particularly isododecane, the mixture of C9-C12 volatile linear alkanes and the mixture of n-undecane (C11) and n-tridecane (Cl3).

[0222] According to a particularly preferred embodiment, the composition (B) of the invention comprises at least one volatile oil selected from petroleum-derived C8-C16 isoalkanes (also called isoparaffins), in particular isododecane.

[0223] The volatile hydrocarbon oil or oils are preferably present in the composition of the invention at levels less than or equal to 80% by weight, preferably from 40 to 70% by weight relative to the total weight of said composition (B). Silicone polyamide

[0224] Composition (B) according to the invention comprises at least one silicone polyamide.

[0225] Silicone polyamides are preferably solid at room temperature (25°C) and atmospheric pressure (760 mm Hg).

[0226] For the purposes of this invention, polymer means a compound having at least 2 repeating motifs, preferably at least 3 repeating motifs and even better 10 repeating motifs.

[0227] The silicone polyamides in the composition of the invention may be polyorganosiloxane polymers such as, for example, those described in documents USA5,874,069, USA5,919,441, USA6,051,216 and USA5,981,680. According to the invention, the silicone polymers may belong to the following two families: (1) polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and / or (2) polyorganosiloxanes comprising at least two amide groups, these two groups being located on grafts or branches.

[0228] According to a first variant, the silicone polymers are polyorganosiloxanes as defined above and whose motifs capable of establishing hydrogen interactions are arranged in the polymer chain.

[0229] Silicone polymers may more particularly be polymers comprising at least one motif conforming to the general formula (I):

[0230] [Chem.22] Ri R 4^X3— -- x ---$ m I < n LR, R [Chem.22] r ■ _jr / in which: G' represents C(O) when G represents -C(O)-NH-Y-NH-, and G' represents -NH- when G represents -NH-C(O)-YC(O)- R4, R5, R6 and R7, whether identical or different, represent a group chosen from: - hydrocarbon groups, linear, branched or cyclic, in Cl to C40, saturated or unsaturated, which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, and which may be partially or totally substituted by fluorine atoms, - aryl groups from C6 to C10, possibly substituted by one or more alkyl groups from C4 to Cl, - polyorganosiloxane chains containing or not one or more oxygen, sulfur and / or nitrogen atoms, The Xs, whether identical or different, represent a di-yl alkylene group, linear or branched from Cl to C30, which may contain one or more oxygen and / or nitrogen atoms in its chain. Y is a linear or branched divalent alkylene, arylene, cycloalkylene, alky-larylene or arylalkylene group, saturated or unsaturated, in Cl to C50, which may contain one or more oxygen, sulfur and / or nitrogen atoms, and / or bear as a substituent one of the following atoms or groups of atoms: fluorine, hydroxy, cycloalkyl in C3 to C8, alkyl in Cl to C40, aryl in C5 to C10, phenyl possibly substituted by 1 to 3 alkyl groups in Cl to C3, hydroxyalkyl in Cl to C3 and amino alkyl in Cl to C6, or Y represents a group corresponding to formula (23): [Chem 23] (23) in which T represents a trivalent or tetravalent hydrocarbon group, linear or branched, saturated or unsaturated, in C3 to C24, possibly substituted by a polyorgano-siloxane chain, and which may contain one or more atoms chosen from O, N and S, or T re- presents a trivalent atony chosen from N, P and Al, and R8 represents a linear or branched Cl-alkyl group at C50, or a polyorganosiloxane chain, which may include one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups which may or may not be linked to another chain of the polymer, n is an integer from 2 to 500, preferably from 2 to 200, and m is an integer from 1 to 1000, preferably from 1 to 700 and even better from 6 to 200. Preferably, m is an integer from 50 to 150.

[0231] According to one embodiment of the invention, 80% of the R4, R5, R6, and R7 of the polymer are preferably selected from methyl, ethyl, phenyl, and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the R4, R5, R6, and R7 of the polymer are methyl groups.

[0232] According to the invention, Y can represent various divalent groups, optionally comprising one or two additional free valences for forming bonds with other units of the polymer or copolymer. Preferably, Y represents a group selected from: - linear alkylene groups in Cl to C2O, preferably in Cl to C1O, - branched alkylene groups that may include rings and non-conjugated unsaturations, from C30 to C56, - the cycloalkylene groups in C5-C6, - phenylene groups possibly substituted by one or more alkyl groups in Cl to C40, - Alkylene groups in Cl to C20, comprising 1 to 5 amide groups, - alkylene groups in C20 to C1, comprising one or more substituents, chosen from hydroxyl groups, cycloalkanes in C3 to C8, hydroxyalkyl groups in C3 to C1 and al-kylamines in C6 to C1, - polyorganosiloxane chains of formula (24) or (25): [Chem 24] [Chem 86] If O (25) If______ in which R4, R5, R6, R7, T and m are as defined above.

[0233] According to the second variant, polyorganosiloxanes can be polymers comprising at least one motif conforming to formula (II): [Chem 26] R: (H) ...................i.......If........ O.................... If............O............... R" W m. (II) in which R4 and R6, identical or different, are as defined above for formula (I), R10 represents a group as defined above for R4 and R6, or represents the group of formula -XG-R12 in which X and G are as defined above for formula (I) and RI2 represents a hydrogen atom or a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, in Cl to C50 having optionally in its chain one or more atoms chosen from O, S and N, optionally substituted by one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more alkyl groups in Cl to C4, R11 represents the formula group -XG-R12 in which X, G and R12 are as defined above, mi is an integer ranging from 1 to 998, and m2 is an integer ranging from 2 to 500.

[0234] According to a particular embodiment of the invention, the silicone polyamide can be a homopolymer, that is to say a polymer comprising several identical motifs, in particular motifs of formula (I) or of formula (II).

[0235] According to another particular embodiment of the invention, a silicone polyamide consisting of a copolymer comprising several different formula units (I) can also be used, that is to say, a polymer in which at least one of the R4, R5, R6, R7, X, G, Y, m and n is different in one of the units. The copolymer can also be formed of several formula patterns (II), in which at least one of the R4, R6, R10, R11, mi and m 2 is different in at least one of the patterns.

[0236] A polymer comprising at least one formula motif (I) and at least one formula motif (II) may also be used, the formula motifs (I) and the formula motifs (II) being either identical or different from each other.

[0237] According to a variant of the invention, a polymer can also be used comprising more or less a hydrocarbon motif having two groups capable of establishing hydrogen interactions selected from the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and their combinations.

[0238] These copolymers can be block polymers, sequenced polymers or grafted polymers.

[0239] According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula -C(O)NH and -HNC(O).

[0240] In this case, the film-forming agent may be a polymer comprising at least one motif of formula (III) or (IV): [Chem 27] 3 iv C....... 0 R" R / 0 (HD Or [Chem 28] R: "$1 XH X SiO ..........Si XNH Ç y C R* _ IC OO ...': " (IV) in which R4, R5, R6, R7, X, Y, m and n are as defined above.

[0241] In these polyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500 and especially from 50 to 200, and n ranges particularly from 1 to 500, preferably from 1 to 100 and even better, from 4 to 25; and X is preferably a linear or branched alkylene chain having from 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially from 5 to 15 carbon atoms and more particularly from 10 carbon atoms, and Y is preferably a linear or branched alkylene chain or one that may include rings and / or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and even better from 2 to 6 carbon atoms, in particular from 6 carbon atoms.

[0242] In formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene portion at least one of the following: - 1 to 5 amide, urea, urethane, or carbamate groups, - a cycloalkyl group at C5 or C6, e - a phenylene group possibly substituted by 1 to 3 identical or different alkyl groups in Cl to C3.

[0243] In formulas (III) and (IV), the alkylene groups may also be substituted by at least one element chosen from the group consisting of: - a hydroxyl group, - a cycloalkyl group at C3 to C8, - one to three alkyl groups in Cl to C40, - a phenyl group possibly substituted by one to three alkyl groups in Cl to C3, - a hydroxyalkyl group in Cl at C3, and - an aminoalkyl group in Cl to C6.

[0244] In these formulas (III) and (IV), Y can also represent a group of formula (29): [Chem 29] (29) where R8 represents a polyorganosiloxane chain, and T represents a group of formula (30): [Chem 30] (30) w (CH^ ™.™™> (CH^ —- (Œ3x 0¾¾ in which a, b and c are independently integers from 1 to 10, and R13 is a hydrogen atom or a group such as those defined for R4, R5, R6 and R7.

[0245] In formulas (III) and (IV), R4, R5, R6 and R7 preferably represent independently a linear or branched Cl-alkyl group at C40, preferably a CH3, C2H5, nC3H7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups.

[0246] According to a preferred embodiment, the silicone polyamide comprises at least one motif of formula (III) and / or (IV).

[0247] As previously seen, the polymer may comprise identical or different formula (III) or (IV) motifs.

[0248] Thus, the polymer can be a polyamide containing several formula (III) or (IV) motifs of different lengths, or a polyamide conforming to formula (V): [Chem 31] in which X, Y, n, R4 to R7 have the meanings given above, m3 and m4 which are different, are chosen from the range of 1 to 1000, and p is an integer from 2 to 300. ,In this formula, the motifs can be structured to form either a block copolymer, a random copolymer, or an alternating copolymer.

[0249] In this copolymer, the units can be not only of different lengths but also of different chemical structures, for example having different Y values. In this case, the polymer can conform to formula (VI): [Chem 32] in which R4 to R7, X, Y, m3, uq, n and p have the meanings given above and Y1 is different from Y but chosen from the groups defined for Y.

[0250] As before, the different motifs can be structured to form either a block copolymer, a random copolymer, or an alternating copolymer.

[0251] In this first embodiment of the invention, the film-forming agent may also consist of a grafted copolymer. Thus, the polyamide with silicone units may be grafted and optionally crosslinked by silicone chains with amide groups. Such polymers may be synthesized with trifunctional amines. In this case, the polymer may comprise at least one motif of formula (VII): [Chem 33] (VII) in which X1 and X2, which are identical or different, have the meaning given for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), R14 to R21 are groups chosen from the same group as R4 to R7, m5 and m6 are numbers in the range from 1 to 1000, and p is an integer from 2 to 500. In formula (VII), it is preferred that: p can range from 1 to 25, or even better, from 1 to 7. R14 to R21 are methyl groups, T meets one of the following criteria: [Chem 34] _____________R33;............AS_______________R' '____________ in which R22 is a hydrogen atom or a group chosen from the groups defined for R4 to R7, and R23, R24 and R25 are independently alkylene groups, linear or branched, preferably still, to the formula: [Chem 35] -------- _______„N ..._______R24 ._______ R25 in particular with R23, R24 and R25 representing -CH2-CH2-, mi and m2 go from 15 to 500, and better still from 15 to 45, X1 and X2 represent -(CH2)i0-, and Y represents -CH2-.

[0252] These silicone-grafted polyamides of formula (VII) can be copolymerized with silicone polyamides of formula (II) to form block copolymers, alternating copolymers, or random copolymers. The weight percentage of silicone-grafted (VII) motifs in the copolymer can range from 0.5 to 30% by weight.

[0253] According to the invention, as previously stated, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or dangling chains. In the main chain, the siloxane units may be in the form of segments as described above. In the dangling or grafted chains, the siloxane units may appear individually or in segments.

[0254] According to one embodiment of the invention, a copolymer of silicone polyamide and hydrocarbon polyamide may be used, namely a copolymer comprising formula units (III) or (IV) and hydrocarbon polyamide units. In this case, the

[0255] Polyamide silicone patterns can be arranged at the ends of the hydrocarbon polyamide. According to a preferred embodiment, the silicone polyamide comprises formula motifs (III).

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] in which R4, R5, R6 and R7 independently represent an alkyl group in Cl to C40, linear or branched, preferably a CH3, C2H5, nC3H7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups, and m ranges from 1 to 700, in particular from 15 to 500 and especially from 50 to 200 and n ranges particularly from 1 to 500, preferably from 1 to 100 and better still from 4 to 25. Preferably, according to this embodiment, groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents a 6-carbon alkylene group and the other a 11-carbon alkylene group, n representing the degree of polymerization (DP) of the polymer. Advantageously, the composition (B) according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) having an index m of a value of about 100. The index m corresponds to the degree of polymerization of the silicone part of the polymer. Preferably, the composition according to the invention comprises at least one polymer comprising at least one motif of formula (III) where m ranges from 50 to 200, in particular from 75 to 150, and preferably in the order of 100. As an example of a usable silicone polymer, one can cite one of the silicone polyamides, obtained in accordance with examples 1 to 3 of document US-A-5 981 680. According to a preferred method, a silicone polyamide polymer with INCI name: NYLON-611 / DIMETHICONE COPOLYMER is used, marketed by Dow Corning under the name DOWSIL 2-8179 GELLANT® (DP 100) and DOWSIL 2-8178 GELLANT® (DP 15). The polymers and / or copolymers used in the composition of the invention have advantageously a solid-to-liquid transition temperature ranging from 45 to 190 °C. Preferably, they have a solid-to-liquid transition temperature ranging from 70 to 130 °C and better from 80 to 105 °C.

[0263] The content of silicone polyamide, expressed as active material, varies, preferably, from 5 to 30% by weight, more preferably from 10 to 25% by weight, more particularly from 8 to 15% by weight relative to the weight of the composition (B). Lipophilic thickener

[0264] According to a preferred form, the composition (B) according to the invention further comprises at least one lipophilic thickener.

[0265] 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.

[0266] As a lipophilic thickener, at least one lipophilic clay will preferably be used.

[0267] Clay refers to a material based on hydrated silicates and / or aluminosilicates with a lamellar structure.

[0268] Clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as a C22 C1O ammonium chloride, in particular steralkonium chloride or di-stearyl di-methyl ammonium chloride.

[0269] They can be chosen from among the bentonites in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

[0270] Preferably, they are chosen from among the hectorites and the bentonites.

[0271] 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 C22CIO, 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 the company BYK Additives Inc; the commercial products sold under the name VISCOGEL® B3, VISCOGEL® B4, VISCOGEL® B7, VISCOGEL® B8, VISCOGEL® ED, VISCOGEL® GM, VISCOGEL® S4, VISCOGEL® SD by the company Bentec SPA; - a bentonite modified by stearalkonium chloride in the presence of at least propylene carbonate and at least one oil such as the commercial products DUB VELVET GUM® from the company STEARINERIE DUBOIS FILS, MYGLYOL GEL T® from the company Cremer Oleo, TIXOGEL® CGT 6030, TIXOGEL® DBA 6060, TIXOGEL® FTN, TIXOGEL® FTN 1564, TIXOGEL® IPM, TIXOGEL® LAN, TIXOGEL® LAN 1563 by 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.

[0272] 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.

[0273] The lipophilic thickener or thickeners may be present in the composition at concentrations ranging, preferably from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition (B). Cosmetic additives

[0274] Composition (B) may contain conventional cosmetic additives, preservatives, perfumes, antioxidants, moisturizing agents, lipophilic actives such as vitamins, lipophilic UV filters, fillers.

[0275] 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.

[0276] 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.

[0277] According to a particularly preferred form, the composition (B) of the invention is anhydrous.

[0278] For the purposes of the invention, the expression "anhydrous composition" designates 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 including a water-free composition.

[0279] Such compositions are notably prepared according to the general knowledge of the person skilled in the art.

[0280] 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.

[0281] The container may delimit one or more compartment(s). The container may, for example, be in the form of a tube.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] 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. Preparation examples

[0287] Example 1: Preparation of a 60% decamethylcyclopenta-siloxane solution of silicone resin modified by 3-glyceroxypropyl groups

[0288] A reactor was loaded with 1300 g of a 50% decamethylcyclopenta-siloxane solution of a powdered organosilicon resin containing hydrosilyl groups, of average composition formula (E4) (weight average molecular weight, 4480; amount of hydrogen gas evolution, 8.0 mL / g), 30.7 g of glycerol mono-allyl 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, followed by 6.5 g of a 5% aqueous sodium hydroxide solution, hydrolyzing the unreacted hydrosilyl groups, after which neutralization was carried out by 0.8 g of concentrated hydrochloric acid was added. 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 heated under reduced pressure to drive off the solvent, and filtration was performed, yielding a decamethylcyclopentasiloxane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). The solution was clear and colorless.

[0289] The decamethylcyclopentasiloxane solution of this silicone resin modified with 3-glyceroxypropyl groups was heated to 120–130°C under reduced pressure to remove the decamethylcyclopentasiloxane. The product thus obtained was a solid powder with an HLB of 0.9. (Me3SiO 1 / 2)27.s(HMe2SiO 1 / 2) 1.0(8^4 / 2)35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiO 1 / 2)27.s(R2Me2SiO 1 / 2) 1.0(8^4 / 2)35.3 (E6) R2= -CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H

[0290] Example 2: Preparation of a 60 wt% isododecane solution of a silicone resin modified by 3-glyceroxypropyl groups

[0291] 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, giving an isododecane solution of the silicone resin modified by 3-glyceroxypropyl groups of formula (E6). (Me3SiO 1 / 2)27.s(HMe2SiO 1 / 2) 1.0(8^4 / 2)35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiO 1 / 2)27.s(R2Me2SiO 1 / 2) 1.0(8^4 / 2)35.3 (E6) R2=-CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H.

[0292] Examples of eyebrow makeup composition

[0293] The following pencil lead type (Al) Base Coat composition was prepared.

[0294] [Tables 1] Phase Ingredients Composition (Al) A OZOKERITE 7 EUPHORBIA CERIFERA (CANDELILLA) WAX / CANDELILLA CERA 3 MICROCRYSTALLINE WAX / CERA MICROCRISTALLINE A 1 HYDROGENATED COCO-GLYCERIDES 10 POLYETHYLENE 22 C20-40 ALCOHOLS (and) POLYETHYLENE 3 B C12-15 ALKYL ETHYLHEXANOATE qs 100 POLYGLYCERYL-2 TRIL SOSTEARATE 5 GLYCERYL CAPRYLATE 0.05 TOCOPHERYL ACETATE 0.1 C ZINC STEARATE 3 MICA (and) DIMETHICONE 7 IRON OXIDES / CI 77499 6.3 IRON OXIDES / CI 77491 2.0 IRON OXIDES / CI 77492 5.8 TITANIUM DIOXIDE / CI 77891 12 Composition preparation protocol (Al)

[0295] Phase A of waxes was melted and combined with the oily phase B. The various solid compounds of phase C, such as zinc, were then added to this mixture. Stearate, pigments, and silicone-coated mica were combined and homogenized again. The resulting matrix was then formulated into pencil lead using a conventional process.

[0296] The following Top Coat compositions (Bl) and (B2) were prepared.

[0297] [Tables2] Ingredients Example (B1) (not part of the invention) Example (B2) (invention) SILICONE RESIN (3-GLYCEROXYPROPYL) DIMETHYLSILOXY TRIMETHYLSILOXY ATE OF FORMULA (21) IN 50% SOLUTION IN LTSODODECANE (X-25-9138A® BY SHIN ETSU) 0 9.1 (4.5% active ingredient) TRIMETHYLSILOXYSILIC ATE IN 75% SOLUTION IN LTSODODECANE (SILSOFT 74 FLUID® - MOMENTIVE PERFORMANCE MATERIALS) 18.0 (13.5% active ingredient) 18.0 (13.5% active ingredient) NYLON-611 / DIMETHICON E COPOLYMER (DOWSIL 2-8179 GELLANT® - DOW CORNING) 12.0 12.0 DISTEARDIMONIUM HECTORITE (BENTONE 38 VCG® RHEOLOGICAL ADDITIVE -ELEMENTIS) 5.0 5.0 PROPYLENE CARBONATE 1.65 1.65 ISODODECANE qs 100 qs 100 Composition preparation protocol

[0298] 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).

[0299] Tests to measure durability: resistance to makeup remover oil

[0300] A layer of pencil was deposited on Supplale® in a 1x2 cm rectangle. A layer of top coat was applied over the layer of pencil. The deposit was left to dry for 1 hour. We performed 5 colorimetric data measurements on each deposit (To) with a Konica CM 700d® spectrophotometer (Minolta). 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. We performed 5 colorimetric data measurements (T5) on each deposit. The variation in AE color was measured between To and T5.

[0301] The results obtained are shown in the table below

[0302] [Tables3] Outfit (A1) alone outside invention (A1) + (B1) outside invention (A1) + (B2) invention AE 43.8 20.6 0.7 Standard deviation AE 0.27 3.0 0.4

[0303] The results of comparative tests showed that the two-step makeup process comprising the application of the pencil (Al) followed by the application of the composition (B2) according to the invention comprising the association of the non-glycerol silicone resin TRIMETHYLSILOXYSILICATE, the glycerol silicone resin 3-(GLYCEROXYPROPYL) DIMETHYLSILOXY TRIMETHYLSILOXYSILICATE, the silicone polyamide NYLON-611 / DIMETHICONE COPOLYMER and isododecane resulted in makeup having excellent resistance to cleansing oil unlike the one-step makeup process using the pencil (Al) alone and unlike the two-step process comprising the application of the Base Coat pencil (Al) followed by the application of the Top Coat composition (Bl) outside the invention not containing glycerol silicone resin.

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 of implantation of said hairs and their contours, comprising at least the following steps: 1) the application of a first composition (A) “Base Coat” of the type of pencil lead comprising, in particular in a physiologically acceptable medium: i) at least one wax, ii) at least one non-volatile oil, and iii) at least one coloring matter, and 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; and b) at least one glycerol silicone resin; and c) at least one silicone polyamide; and d) at least one oily phase comprising at least one volatile hydrocarbon oil.

2. A method according to claim 1, wherein the composition (A) comprises at least one hard wax having a melting temperature of 65 to 120°C, and preferably having at 20°C a hardness greater than 5 MPa, in particular from 5 to 30 MPa, preferably greater than 6 MPa, even better from 6 to 25 MPa.

3. A process according to claim 2, wherein the composition (A) comprises at least one hard wax selected from Candelilla wax of INCI name EUPHORBIA CERIFERA (CANDELILLA) WAX / CANDELILLA CERA, rice bran wax of INCI name ORYZA SATIVA (RICE) BRAN WAX / ORYZA SATIVA CERA, a microcrystalline wax of INCI name MICROCRYSTALLINE WAX / CERA MICRO-CRISTALLINA, a polyethylene wax, a mixture of waxes of INCI name: C20-40 ALCOHOLS (and) POLYETHYLENE, hydrogenated coconut oil of INCI name: HYDROGENATED COCO-GLYCERIDES, and mixtures thereof.

4. A method according to any one of the preceding claims, wherein the composition (A) comprises the wax or wax(s), in a concentration of 20 to 50% by weight and preferably 25 to 45% by weight per relative to the total weight of the composition.

5. A process according to any one of the preceding claims, wherein in composition (A), the non-volatile oil or oils is / are selected from synthetic esters, C4-C18 fatty acid triglycerides, and mixtures thereof.

6. A method according to any one of the preceding claims, wherein in composition (A) the non-volatile oil or oil(s) is / are present at a rate of 5 to 30% by weight and in particular 10 to 20% by weight of the total weight of the composition.

7. A method according to any one of the preceding claims, wherein in composition (A), the colouring material(s) is / are present, preferably in the composition at a content less than or equal to 50% by weight, preferably from 25 to 40% by weight, more particularly from 3 to 15% by weight relative to the total weight of the composition.

8. A method according to any one of the preceding claims, wherein the composition (A) comprises at least one powdered colouring material of the mineral pigment type, in particular selected from titanium dioxides, black, red or yellow iron oxides, coated or uncoated, ferric aluminium iron rocyanide, and mixtures thereof.

9. A process according to any one of the preceding claims, wherein the composition (A) is anhydrous.

10. A method according to any one of the preceding claims, wherein the composition (A) further comprises an aqueous phase.

11. A method according to any one of the preceding claims, wherein the pencil lead is in retractable form.

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

13. A process according to claim 12, wherein the Trimethylsiloxysilicate type resin is in solution in isododecane, in particular in solution at 75% by weight of active matter in isododecane.

14. A process according to any one of the preceding claims, wherein in composition (B), the non-glycerol silicone resin(s) is / are present in an active material content of 4 to 35% by weight, preferably of 6 to 30% by weight and more preferably of 8 to 25% by weight relative to the total weight of composition (B).

15. A process according to any one of the preceding claims, wherein in composition (B), the glycerol silicone resin(s) is / are present in an active material content of 0.1 to 40% by weight relative to the total weight of the composition, preferably of 0.2 to 30% by weight and more preferably of 0.5 to 15% by weight relative to the total weight of the composition.

16. A method according to any one of the preceding claims, wherein 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 contains a monoglycerol group or a polyglycerol group

17. A method according to claim 16, wherein 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.

18. 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).(R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f(l) 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 poly-glycerol group of the following general formula (2) —(CH2)2—QH21—O—(CH2CH(OH)CH2O);R4 (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 the following general formula (3), general formula (4), general formula (5) or general formula (6) —(CH2)2—CmH2m—(SiORyj—SiR>3 (3). —(CH2)2—CmH2m—SiR'kl—(OSiR'3)3 kl) (4) —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (5) —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 kl (6) where - each R1, identical or different, is an alkyl, aryl, or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino, or a group substituted by a carboxyl group - the indices m, j, and k1 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 <b < 200, 0 < c < 400, < d < 320, < e < f < 1000 et 0,5 < (a+b+c) f < 1,5.

19. A method according to claim 18, wherein in composition (B), the glycerol silicone resin(s) of formula (1) are selected 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 polyglycerol group R2 is an integer which satisfies the condition 0 < i < 3.

20. A process according to claim 18 or 19, wherein in composition (B), the glycerol-siliconized resin(s) of formula (1) have a weight average molecular mass which preferably varies from 1000 to 100,000 and more preferably from 3000 to 50,000.

21. A method according to any one of claims 18 to 20, wherein 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.

22. A method according to any one of claims 18 to 21, wherein 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.

23. A method according to any one of claims 18 to 22, wherein composition (B) comprises at least one glycerol-coated silicone resin of formula (1) of the type (3-Glyceroxypropyl)DimethylsiloxyTrimethylsi- loxy silicate 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 with 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.

24. A method according to claim 23, wherein the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in solution in at least one volatile oil.

25. A process according to claim 24, wherein the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution at 49.5% by weight of active matter in isododecane.

26. A process according to any one of the preceding claims, wherein the composition (B) comprises at least one volatile oil selected from petroleum-derived C8-C16 isoalkanes, in particular isododecane.

27. ​​A process according to any one of the preceding claims, wherein in composition (B), the volatile hydrocarbon oil or oils are present in contents less than or equal to 80% by weight, preferably from 40 to 70% by weight relative to the total weight of said composition.

28. A process according to any one of the preceding claims, wherein in composition (B), the silicone polyamide polymer has the INCI name: NYLON-611 / DIMETHICONE COPOLYMER.

29. A method according to any one of the preceding claims, wherein in composition (B) the content of silicone polyamide, expressed as active material, varies from 5 to 30% by weight, more preferably from 10 to 25% by weight, more particularly from 8 to 15% by weight relative to the weight of the composition.

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

31. A method according to claim 30, wherein the thickener or thickeners lipophilic are present at concentrations ranging, preferably from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition (B).

32. A process according to any one of the preceding claims, wherein the composition (B) is anhydrous.

33. 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 11; and 2) a composition (B) as defined in any one of claims 12 to 32; said compositions (A) and (B) being packaged separately.