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,in particular 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 process with a first composition of pencil lead type and a second composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone polyamide

[0001] The present application relates to the field of makeup of keratin materials, in particular eyebrows, including eyebrow hairs, the skin where 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 commercial product MICRO BROW PENCIL® from NYX, which are easy to use but only last one day. They often have a pigmented tip that transfers color to the skin. - pens, which are also easy to use but only last a day. They are often made from water-based formulas containing dyes - tattoo services in salons, which are very painful, but last for several months. - anhydrous gels such as the commercial products Inked Waterproof Brow Gel® from Urban Decay (Mintel ID 7578707) and Up to 3 Day Styling Gel® from Maybelline (Mintel ID 10361806) comprising isododecane and the combination of an MQ resin: TRIMETHYLSILOXYSILICATE and a silicone polyamide: NYLON-611 / DIMETHICONE COPOLYMER.

[0003] Users of makeup formulations for keratin materials such as eyebrows and the skin around the eye and eyebrows are looking for products with longer hold over time, which is reflected in particular by better resistance of the film deposited to fatty substances such as sebum and makeup remover oils.

[0004] There remains a need to find new compositions for caring for and / or making up keratin materials, in particular for the eyebrows and the skin around the eye and eyebrows, which make it possible to obtain make-up with better retention of the deposit over time, in particular better resistance to fatty substances such as sebum and make-up removing oils.

[0005] Unexpectedly, the inventors have found that it is possible to achieve these objectives by using a method for coating, in particular for caring for and / or making up keratin materials, in particular eyebrows including eyebrow hairs, the skin where 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 pencil lead type 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-glycerolated 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.

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

[0007] Thus, a first object of the present invention is a method for coating, in particular for caring for and / or making up keratin materials, in particular eyebrows including eyebrow hairs, the skin where 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 pencil lead type 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-glycerolated silicone resin; and (b) at least one glycerol 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 set or kit for covering, in particular for caring for and / or making up keratin materials, in particular the eyebrows and the skin around the eye and the eyebrows, comprising at least 1) a composition (A) as defined above; and 2) a composition (B) as defined previously; said compositions (A) and (B) being packaged separately. Definitions

[0009] In the context of the present invention, the term "keratin materials" is understood to mean in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours. This term "keratin materials", within the meaning of the present invention, also extends to synthetic false eyebrows.

[0010] By "physiologically acceptable" is meant compatible with said keratin materials, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness), likely to deter the consumer from using this composition.

[0011] By "glycerolated silicone resin" is meant any silicone resin comprising at least one organosiloxane unit comprising one or more monoglycerol or polyglycerol group(s) in its chemical structure.

[0012] In particular, the glycerolated silicone resin contains at least one organosiloxane unit of the type RR'R”SiOi / 2 in which R, R' and R'”, which may be identical or different, denote hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerolated silicone resin contains at least one dimethylsiloxane unit R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

[0013] By "hydrocarbon radical" is meant a radical containing mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

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

[0015] By “polyglycerol group” is meant any group comprising in its chemical structure a chain comprising a repetition of at least 2 glycerol units -(O-CH2 -CHOH-CH2)m.

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

[0017] The composition (A) Base Coat of the pencil lead type 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 matter. Wax(s)

[0018] For the purposes of the present invention, the term "wax" is intended to denote a lipophilic compound that is solid and rigid at room temperature (25°C) with a reversible solid / liquid state change, having a melting point greater than 30°C and up to 120°C, a hardness greater than 0.05 MPa and having in the solid state an organo- anisotropic crystallization.

[0019] By bringing the wax to its melting temperature, it is possible to make it miscible with the oils and to form a microscopically homogeneous mixture and to obtain a 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. For the purposes of the present invention, the term "hard wax" means a wax having a melting temperature ranging from 65 to 120°C, more preferably between 70 and 100°C.

[0021] Advantageously, by “hard” wax in the sense of the present invention, is meant 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 carry out these hardness measurements, the wax is melted at a temperature equal to the melting point of the wax + 20 °C. To do this, 30g of wax is placed in a 100ml beaker with a diameter of 50mm, itself positioned on a heated magnetic stirring plate. A quantity of approximately 15g of molten wax is poured into a stainless steel container with a diameter of 80mm and a depth of 15mm, previously heated to 45°C in an oven. The wax is then left to recrystallize in a room thermostatically 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 thermostatically controlled at 20°C using the texturometer sold under the name TA-XT2i by the company Swantech, equipped with a stainless steel cylinder with a diameter of 2mm.The measurement consists of 3 steps: a first step after automatic detection of the sample surface where the mobile moves at the measurement speed of 0.1 mm / s, and penetrates the wax to a penetration depth of 0.3 mm, the software notes the value of the maximum force reached; a second step called relaxation where the mobile remains in this position for one second and where the force is noted after 1 second of relaxation; finally a 3rd step called withdrawal where the mobile returns to its initial position at the speed of 1 mm / s and the withdrawal energy of the probe (negative force) is noted. The hardness value corresponds to the maximum compression force measured in Newton divided by the surface area of ​​the texturometer cylinder expressed in mm2 in contact with the wax. The hardness value obtained is expressed in mega-pascals or 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 temperature rise from 0°C to 120°C, at a heating rate of 10°C / minute, then cooled from 120°C to 0°C at a cooling rate of 10 °C / minute and finally subjected to a second temperature rise from 0 °C to 120 °C at a heating rate of 5 °C / minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the wax sample as a function of temperature is measured. The melting point of the compound is the temperature value corresponding to the top of 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 waxes that are solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin, and their mixtures.

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

[0027] Examples of hard wax that may be mentioned 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 olive oil esterified with C12 to C18 chain fatty alcohols such as those sold by SOPHIM under the trade names Phytowax Olive 12L44®, 14L48®, 16L55® and 18L57®,waxes obtained by hydrogenation of castor oil esterified with cetyl or behenic alcohol, such as those sold under the names Phytowax Ricin 16 L 64® and Phytowax Ricin 22 L 73® by the company SOPHIM, hydrogenated Camelina wax, Ouricury wax, Montan wax, ozokerite waxes such as, for example, Wax SP 1020 P® ​​marketed by the company Strahl & Pitsch, microcrystalline waxes such as, for example, that sold under the trade name Microwax HW® by the company PARAMELT, hydrogenated coconut oil with the INCI name: HYDROGENATED COCOGLYCERIDES, such as, for example, that sold under the trade name Softisan 100® or Softisan 142 by the company SASOL, polymethylene waxes such as, for example, example, 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 95 / 5 ethylene / acrylic acid 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 mixture of adipate of dibehenyl, dioctadecyl adipate and di-eicosanyl adipate (INCI name C18-22 dialkyl adipate),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: C18-22 dialkyl sebacate), the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyl octanedioate (INCI name: C18-22 dialkyl octanedioate) such as, for example, those marketed by the company COGNIS, pentaerythrityl tetrastearate such as, for example, Liponate PS-4® from the company Lipo Chemicals, tetracontanyl stearate such as, for example, Kester Wax K76 H® from the company KOSTER KEUNEN, stearyl benzoate such as, for example, Finsolv 116® from the company FINETEX, behenyl fumarate such as, for example, Marrix 222® from the company AKZO BERNEL, di-(trimethyloi-1,1,1-propane) tetrastearate such as, for example, that offered under the name “HEST 2T-4S®” by the company HETERENE,didotriacontanyl distearate such as, for example, Kester Wax K82D® from the company KOSTER KEUNEN, polyethylene glycol montanate with 4 oxyethylene units (PEG-4) such as, for example, that sold under the trade name Clariant Licowax KST1®, hexanediol disalycilate 28 such as, for example, Betawax RX-13750® marketed by the company CP Hall, dipentaerythritol hexastearate such as, for example, that sold under the trade name Hest 2P-6S® by the company HETERENE, ditrimethylolpropane tetrabehenate such as, for example, that sold under the trade name Hest 2T-4B® by the company HETERENE, Jojoba esters such as, for example, that sold under the trade name Floraester HIP® by the company FLORATECH, mixtures of linear carboxylic acid (C20-40) / saturated hydrocarbons (INCI name: C20-40 Acid polyethylene) such as, for example,Performacid 350 Acid® from NEW PHASE TECHNOLOGIES, the synthetic Fischer-Tropsch type wax such as that marketed under the , reference Rosswax 100® by the company ROSS, stearic alcohol, behenic alcohol, dioctadecyl carbonate such as, for example, Cutina KE 3737®, sucrose polybehenate such as, for example, Crodaderm B® from the company CRODA, and their mixtures.

[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 of cetyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides), KPC-60® (Mixture of 87.5% by weight of stearyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides), KPC-63® (Mixture of 87.5% by weight of behenyl stearate, 7.5% by weight of behenyl alcohol and 5% by weight of palm kernel glycerides) and KPC-80® (Mixture of 86% by weight of synthetic beeswax, 7.5% hydrogenated vegetable oil and 6.5% by weight of behenyl alcohol) from KOSTER KEUNEN.

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

[0030] According to a particular form of the invention, the composition (A) comprises the wax or wax(es), in a concentration ranging from 20 to 50% by weight and preferably from 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] Oil means any fatty substance in liquid form at room temperature. (20-25°C) and at atmospheric pressure (760mm Hg 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 mixtures thereof.

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

[0035] For the purposes of the present invention, the term “silicone 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 optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

[0037] By "non-volatile oil" is meant an oil remaining on the keratin material at room 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. For example, the vapor pressure can be measured according to the static method or by the isothermal effusion method, as a function of the vapor pressure (OECD standard 104). Non-volatile hydrocarbon oils

[0038] As an example of non-volatile hydrocarbon oil that can be used in the invention, mention may be made of: - hydrocarbon oils of vegetable origin, such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl / octyldodecyl / phytostearyl glutamate; triglycerides consisting of esters of fatty acids and glycerol, in particular, the fatty acids of which may have chain lengths varying from C4 to C36, and, in particular, from C18 to C36, these oils being able to be linear or branched, saturated or unsaturated; these oils may, in particular, be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe oil, sweet almond oil, peach almond 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, pumpkin oil, pumpkin oil, quinoa oil, rosehip oil, sesame oil, soybean oil, sunflower oil, castor oil, and watermelon oil, and mixtures thereof, or triglycerides of C4 to C10 fatty acids, in particular triglycerides of caprylic / capric acids, in particular those sold by the company Stéarineries Dubois or in particular those sold under the names, 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 of formula R1COOR2, in which RI represents a residue 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 chain containing from 1 to 40 carbon atoms provided that RI + R2 is greater than or equal to 10. The esters may be, in particular, chosen from alcohol and fatty acid esters, such as for example 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, benzoates of C12-C15 alcohols, C12-C15 alkyl ethylhexanoate such as the commercial product ACTIVEMOL EH-25® from Innospec Active Chemicals hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, neopentanoate isotridecyl, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters, such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters such as isostearyl lactate, di-isostearyl malate; , - pentaerythritol esters, such as dipen-taerythritol tetrahydroxystearate / tetraisostearate, - esters of dimer diols and dimer diacids, - copolymers of dimer diol and dimer diacid and their esters, such as copolymers of dilinoleyl diol / dimer dilinoleic dimer and their esters, - copolymers of polyols and dimer diacids, and their esters, - fatty alcohols which are liquid at room temperature with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, oleyl alcohol; - higher fatty acids such as oleic acid, linoleic acid, li- nolenic; - carbonates such as dicaprylyl carbonate; - acetates; - citrates; - their mixtures. Non-volatile silicone oils

[0039] As non-volatile silicone oils, we can cite: - polydimethylsiloxanes (INCI name: Dimethicone) in particular, with a viscosity ranging from 50 to 500 mm2 / s (est), in particular 350 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 350® from WACKER, XIAMETER PMX-200 SILICONE FLUID® 350CS by DOW CORNING; polydimethylsiloxanes with a viscosity ranging from 50 to 150 mm2 / s (est), in particular 100 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 100® from WACKER, XIAMETER PMX-200 SILICONE FLUID 100CS® by DOW CORNING. - phenyl silicone oils such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethylsiloxysilicates.

[0040] According to a preferred embodiment, the non-volatile oil or oils is (are) chosen from synthetic esters, C4 to C18 fatty acid triglycerides, and mixtures thereof.

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

[0042] In particular, the non-volatile oil or oils may be present in an amount of 5 to 30% by weight and in particular 10 to 20% by weight of the total weight of the composition. Coloring matter

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

[0044] The coloring matters can be chosen from mineral pigments, organic pigments, nacres, fat-soluble 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] By "mineral pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric aluminum ferrocyanide, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments may also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 in mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

[0048] The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can range up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1 μm.

[0049] According to a particular form of the invention, the pigments have a size characterized by a D

[50] greater than 100 nm and which can range up to 100 nm, 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 granulometer of the Master Sizer 3000® type from Malvern, making it possible to understand the particle size distribution of all the particles over a wide range from 0.01 pm to 1000 pm. The data are processed on the basis of the classical Mie scattering theory. This theory is the most suitable for size distributions ranging from submicron to multimicron, it makes it possible to determine an “effective” particle diameter. This theory is notably described in the work of Van de Hulst, HC, “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957.

[0051] D

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

[0052] According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, the latter being preferably present in the oily phase of the composition according to the invention.

[0053] According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

[0054] According to a particular embodiment, the pigments may be coated according to the invention with an N-acylated amino acid or one of its salts which may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

[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 in particular be a glutamic acid derivative and / or one of its salts, and more particularly a stearoyl glutamate, such as, for example, aluminum stearoyl glutamate. As examples of pigments treated with aluminum stearoyl glutamate, mention may be made of the black iron oxide pigments CI77499, red CI77491 and yellow CI77492 sold under the commercial reference NAI® by the company MIYOSHI KASEI.

[0056] According to a preferred embodiment, the pigments according to the invention may be coated with isopropyl triisostearyl titanate. As examples of pigments treated with isopropyl titanium triisostearate (ITT), mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference BWB0-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWY0-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-12® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company KOBO.

[0057] Among the mineral pigments, mention may also be made of nacres. They may be chosen from white nacreous pigments such as mica coated with titanium or bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as nacreous pigments based on bismuth oxychloride.

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

[0059] By "organic pigment" is meant any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type compounds, 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 codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cil 1725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and the pigments obtained by oxidative polymerization of indolic, 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 fixing of the organic pigments on the core.

[0062] The pigment may also be a lake. By lake is meant insolubilized dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

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

[0064] Among the organic dyes, we can cite cochineal carmine. Other products known under the following names may also be mentioned: 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] Examples of lacquers include the product known under the name D&C Red 7 (CI 15850:1). Fat-soluble coloring matters

[0066] By "liposoluble coloring matter", within the meaning of the invention, is meant any generally organic, natural or synthetic compound, soluble in an oily phase or solvents miscible with a fatty substance and capable of coloring.

[0067] As liposoluble dyes suitable for the invention, mention may in particular be made of liposoluble dyes, synthetic or natural, such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes ([3-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto, curcumin.

[0068] Preferably, the coloring material(s) is / are present, preferably, in the composition in a content less than or equal to 50% by weight, preferably 25 to 40% by weight, more particularly 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 pulverulent coloring material of mineral pigment type, in particular chosen from titanium dioxides, black, red or yellow iron oxides, coated or not, ferric aluminum iron cyanide, and mixtures thereof. Surfactants

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

[0071] More particularly suitable for the invention are glycol fatty acid esters, C4-C24 fatty acid esters, especially C8-C18 fatty acid esters, linear or branched, saturated or unsaturated (palmitate, stearate, oleate), oxyethylenated or non-oxyethylenated sorbitan, sucrose fatty acid esters, polyethylene glycol fatty acid esters (polyethylene glycol monostearates or monolaurates), fatty acid esters of glucose derivatives, alkyl polyglucosides, condensation products of an α-diol, of a monoalcohol and mixtures thereof.

[0072] Mention may also be made of polyol fatty acid esters such as sorbitol mono-, di-, tri- or sesquioleate, sorbitol mono-, di-, or tristearate or

[0073] Mention may also be made of partial esters resulting from the reaction of at least one linear or branched C8-C40 and better still C8-C22 fatty acid, 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, saturated or unsaturated fatty acid.

[0074] As a representative of this type of compound, we can particularly cite: - 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 those skilled in the art.

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

[0077] As regards more particularly the dispersing agent, it may be present in an amount 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 usually used in the field of cosmetics.

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

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

[0081] As representatives of these fillers, mention may be made of talc, natural mica or synthetic mica such as fluorphlogopite, silica, kaolin, nylon and polyethylene powders, Teflon, starch, boron nitride, polymer microspheres such as Expancel® (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 such as 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 reflection effect.

[0084] As a useful agent for controlling viscosity, propylene carbonate can more particularly be used.

[0085] Of course, those skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, 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” denotes 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 relative to its total weight, and in particular a composition free of water.

[0088] According to a variant, the composition (A) of the invention may additionally comprise an aqueous phase comprising water and water-soluble organic solvents or miscible in water such as lower monohydric alcohols 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 pencil lead.

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

[0091] Generally speaking, the wax-type compounds are melted and combined with the other liquid components. The various compounds, particularly solid-type compounds, such as pigments and fillers, are then added to this mixture, and the whole is homogenized again. The matrix thus obtained is then formulated into pencil lead using conventional methods. Composition (B) Top Coat

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

[0093] The composition (B) according to the invention comprises at least one non-glycerolated silicone resin.

[0094] More generally, the term resin means a compound whose structure is three-dimensional. Silicone resins are also called silicone resins or "siloxane resins". Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

[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 that 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 linked to a single oxygen atom in the polymer comprising this unit.

[0097] The letter “D” means a Difunctional unit RiR2SiO2 / 2 in which the silicon atom is linked to two oxygen atoms.

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

[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 M, D, T units 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 unit SiO4 / 2 in which the silicon atom is linked to four oxygen atoms themselves linked to the rest of the polymer.

[0102] Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the pendant chains.

[0103] As silicone resins which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of type MQ, silicone resins of type T, silicone resins of type MQT, and mixtures thereof. MQ resins:

[0104] As an example of silicone resins of MQ type, mention may be made of alkylsiloxy-silicates of formula [(Ri)3SiOi / 2]x(SiO4 / 2)y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group Ri represents a radical as defined previously, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0105] As an example of MQ silicone resins of the Trimethylsiloxysilicate type, we can cite those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name “KF-7312J®” by the company Shin-Etsu, “DC 749®”, “DC 593®” by the company Dow Corning. T resins:

[0106] As an example of T-type silicone resins, mention may be made of polysilsesquioxanes of formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

[0107] Preferably, polymethylsilsesquioxane resins in which R represents a methyl group can be used, such as those sold: - by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating units CH3SiO3 / 2 (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 about 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 (silanol) end groups, under the reference KR-242A® which comprise 98% of T units and 2% of dimethyl D units and have Si-OH end groups or under the reference KR-251® comprising 88% of T units and 12% of Dimethyl D units and have Si-OH end groups. MQT Resins:

[0108] As a resin comprising MQT units, those cited in document US 5,110,890 are known in particular.

[0109] A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins which can be used in the compositions according to the invention are in particular those described and prepared in the application WO 2005 / 075542.

[0110] The MQ-T-propyl resin preferably comprises the 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 representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being molar fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d = 1, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

[0111] Preferably, the siloxane resin comprises the units: (i) ((R1)3SiO1 / 2)a (ii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with R1 and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, R1 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 molar fractions, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

[0112] The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of A) an MQ resin comprising at least 80 mol% of ((Ri)3SiOi / 2)a and (SiO 4 / 2)d units Ri representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the ratio a / d being between 0.5 and 1.5; and B) a propyl resin T comprising at least 80 mol% 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 mol% 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 ratio A / B is less than or equal to 70:30. These preferred ratios have proven to allow comfortable deposits.

[0114] Preferably, the composition (B) according to the invention comprises, as silicone resin, at least one resin of MQ type, more particularly of Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name KF-7312J® by the company Shin-Etsu, DC 749®, DC 593® by the company Dow Corning, under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS.

[0115] A resin of the Trimethylsiloxysilicate type will be used in particular in solution in isododecane, in particular in a solution of 75% by weight of active material 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-glycerolated 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). Glycerolated silicone resin

[0117] The composition (B) according to the invention comprises at least one glycerolated silicone resin.

[0118] The glycerolated silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol group(s).*

[0119] According to a particular embodiment of the invention, the glycerolated 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 glycerolated silicone 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 thereof; - 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 substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and - the indices 1 and i are integers which satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is an identical or different group of general formula (3), 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, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof - the indices m, j and ki to k3 are integers which satisfy the 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] The glycerolated silicone resins according to the invention are described in patent application US20200332065A1 by SHIN ETSU.

[0123] According to a particular embodiment, the glycerolated 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 which satisfies the condition 0 < i < 3.

[0124] According to a particular embodiment, the glycerolated silicone resin(s) of formula (1) are in solid form at 25°C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

[0125] According to a particular embodiment, the glycerolated silicone resin(s) have a weight-average molecular weight ranging from 1000 to 100000.

[0126] The glycerolated silicone resin(s) according to the invention are amphiphilic, i.e. they have two parts of different polarity. In general, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (Hydrophilic Lipophilicity Balance), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and is described for example in "The HLB System. A time-saving guide to Emulsifier Selection” published by ICI Americas Inc; 1984). The HLB value of the glycerolated silicone resins according to the invention preferably varies from 0.1 to 15 according to the GRIFFIN method.

[0127] The glycerolated 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 thereof; - the indices a, b, c, d, e and f are integers which 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 terminated by 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 substituted or unsubstituted monovalent hydrocarbon group 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 of, for example, 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 starting material.

[0130] The hydrosilyl group-containing silicone resin of formula (7) may be in a solid or liquid form at 25°C, although in terms of film-forming ability, it is preferably solid. From the point of view of utility, the resin is preferably diluted with an organic solvent. The use of a solvent whose boiling point is higher than the reflux temperature during hydrolysis is preferred.

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

[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 chosen from the organosilicon compounds of general formulas (13) and (14) below, one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) below and one or more compounds chosen from the hydrolyzable silanes of general formula (17) below, the partial hydrolytic condensates of these hydrolyzable silanes and the metal salts of these hydrolyzable silanes.

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

[0136] In general formula (16), X2 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred.

[0137] In 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. Among these, an alkoxy group is preferred; from the viewpoints of availability and hydrolysis rate, a methoxy group or an ethoxy group is preferred. The hydrolyzable groups X3 on the molecule may be the same or different groups.

[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. Of 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, dimethylphenyl-chlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane and tri-phenylethoxysilane. 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 general formulas (15) and (16), n satisfies the condition 1< n < 3. In general formula (15), the "n" associated with H and R1 bonded to one silicone atom and the "n" associated with H and R1 bonded to the other silicone atom may be the same 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 partial hydrolysis condensates of hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silane include water glass, sodium silicate and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0144] In this invention, to a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes 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 identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - 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 general formula (18), X4 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X4 on the same molecule may be similar or different.

[0148] In general formula (19), X5 is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X5 on the same molecule may be similar or different.

[0149] Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane and methyltrichlorosilane. Among these, methyltrimethoxysilane, methyltriethoxysilane and methyltrichlorosilane are preferred.

[0150] Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropro-pyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane and dimethyldichlorosilane. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane are preferred.

[0151] A specific example of a method for preparing the 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 organosilicon compounds of general formulae (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes) are charged into a reactor, an acid is added as a catalyst, and water is added dropwise with stirring. It is also possible in this case to add the organic solvent after completing the dropwise addition of water. Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

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

[0153] In order to suppress a decrease in the reaction rate due to retention and increase in viscosity of the uniform reaction system during the hydrolysis reaction, it is preferable to use an organic solvent as the solvent in the hydrolysis reaction. It is also desirable to use a solvent whose boiling point is higher than the reflux temperature during the hydrolysis.

[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. Since alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol and 2-propanol are particularly preferred.

[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 of 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 in the range of 0.001 to 10% of the overall reaction system being preferred.

[0158] After adding the water dropwise as mentioned above, the hydrolysis reaction is carried out by heating the system at a temperature between 50 and 150°C, preferably between 80 and 120°C, for about 2 to 8 hours. Meanwhile, by carrying out the reaction at a temperature lower than 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 of between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably to 25°C.

[0160] After the above hydrolysis, the system is neutralized at 10 to 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this time, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is suppressed, and the condensation reaction of the organosilicon resin is further promoted. Examples of such strongly basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate.Regarding the combinations of a strong base catalyst with a weak base catalyst, from the point of view of ease of obtaining a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, which makes it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

[0161] The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. Carrying out the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, resulting in an increase in molecular weight and obtaining a high-molecular-weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the addition amount within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, thereby obtaining a resin of target molecular weight.

[0162] After neutralization, the formed alcohols, the solvent and the excess water can be removed by heating between 95 and 120°C under normal or reduced pressure. Then, after confirming that the formed alcohols, the solvent and the excess water have been removed, the condensation reaction is carried out by heating between 120 and 150°C for about 2 to 5 hours. An organosilicon resin containing a hydrosilyl group is thus obtained.

[0163] In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio of the combined molar amount of the compounds of general formulas (13), (14), (15) and (16) to the molar amount of SiO4 / 2 units in the compound of general formula (17), expressed as the molar ratio ((13)+(14)+(15)+(16)):(19), is preferably 0.3:1 to 2:1, and more preferably 0.6:1 to 1.3:1.

[0164] Furthermore, the ratio of the combined molar amount of the compounds of general formulae (13) and (14) to the combined molar amount of the compounds of general formulae (15) and (16), expressed as the molar ratio ((13)+(14)):((15)+(16)), is preferably 0.3:1.0 to 2.0:1.0, and more preferably 0.6:1.0 to 1.3:1.0. By setting the values ​​within these ranges, the amount of hydrosilyl groups included in the hydrosilyl group-containing organosilicon resin can be quantitatively varied more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulae (15) and (16) are charged, it is possible to quantitatively vary the amount of hydrosilyl groups included on the organosilicon resin.

[0165] In the process described above for preparing a silicone resin containing hydrosilyl groups, after having carried out the hydrolysis, in the presence of an acid catalyst, of a mixture of one or more compounds chosen from organosilicon compounds of general formulas (13) and (14) with one or more compounds chosen from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, it is also possible to gradually add, drop by drop, one or more compounds chosen from organosilicon compounds containing a hydrosilyl group, general formulas (15) and (16).

[0166] Next, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably carried out by heating at a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example at a temperature preferably between 40 and 150°C, and more preferably between 40 and 120°C, for about 2 to 8 hours. When the reaction is carried out in this temperature range, deactivation of the hydrosilyl groups can be further suppressed.

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

[0169] The amount of hydrosilyl groups included in the thus obtained hydrosilyl group-containing organosilicon resin is easily adjustable, and it is even possible to introduce a large amount of hydrosilyl groups, by varying the amount of the hydrosilyl group-containing organosilicon compound that is charged. Furthermore, by varying the amount of hydrolysis starting materials used, the type and amount of added acid catalyst, the reaction temperature and time, the amount of added solvent and the addition method, the molecular weight range, shape and other characteristics of the organosilicon resin can be adjusted, thereby preparing a hydrosilyl group-containing organosilicon resin for the intended application.

[0170] The silicone resin containing a hydrosilyl group obtained as described above has the average formula (7) above and is composed of Q units (SiO4 / 2) and M units (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 weight average molecular weight is preferably between 2,000 and 30,000, although the range of 3,000 to 15,000 is more preferred from the point of view of performance and ease of carrying out operations such as filtration. The weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GC).

[0171] Process for the preparation of glycerol silicone resin

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

[0173] As mentioned above, the glycerolated silicone resin according to the invention can be obtained by the hydrosilylation step (A) of a silicone resin containing a hydrosilyl group of average formula (7) below: (R13SiO1 / 2)a(HnR13nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (7) in which - each R1 is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 < 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 alkenyl-terminated compounds 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 substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, - the indices 1 and i are integers which satisfy the conditions 0 < 1 < 15, and 0 < i < 5; - the indices m, j and ki to k3 are integers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < ki < 2, 0 < k2 < 2 and 0 < k3 < 2; said comprises 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 as hydrosilyl groups / terminal unsaturated groups, which is preferably 0.5 to 2.0, and more preferably 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 thus 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 the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type solvents such as acetone, methylethylketone, diethylketone and methylisobutylketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol.From the point of view of reactivity, ethanol, 1-propanol and 2-propanol are preferred.

[0177] The amount of solvent used is preferably 1 to 80%, and more preferably 5 to 50%, of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0178] The conditions of the addition reaction are not particularly limited, although refluxing at a temperature between 50 and 150°C, particularly 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 0.001 to 5.0%, and especially 0.01 to 1.0%, of the system overall. By setting the amount of activated carbon within this range, sample discoloration can be better suppressed.

[0180] After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups can be included. Especially in cases where use in applications such as cosmetic preparations is intended, there is a possibility that these hydrosilyl groups will deactivate over time due to dehydrogenation reactions, which is a problem from a safety point of view. It is therefore preferable to include a step of maintaining the hydrosilyl groups.

[0181] An example of a step for removing hydrosilyl groups is the method of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, and then neutralizing by adding an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of the basic catalyst include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the viewpoint of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being particularly preferred.Acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. In general, instead of using the acid or base alone, it is better to use them with water and heat them to a temperature not higher than the boiling point of water.

[0182] After the addition reaction, if necessary, a deodorization step to reduce the odor can be included. When use in applications such as cosmetic preparations in particular is intended, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common polyether-modified silicones can be explained as follows. When an addition reaction between an allyl-etherified polyether and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as side reactions, forming a propenyl-etherified polyether. This propenyl-etherified polyether has no reactivity with the polyorganosiloxane hydrogen, and therefore remains in the system as an impurity.It is believed that when water acts on this propenyl etherified polyether, the propenyl ether hydrolyzes, giving rise to . propionaldehyde, which gives off an unpleasant odor. It is known that the above hydrolysis reaction is further promoted in the presence of an acid catalyst. Therefore, when polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and causing the appearance of an unpleasant odor.

[0183] Typical examples of the deodorization step include two approaches. The first is that, by adding an acid catalyst to the solution after the addition reaction, all the propenyl ether remaining in the system is hydrolyzed and the propionaldehyde that forms is removed by strip purification (JP No. 2137062).

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

[0185] The treatment temperature is preferably set at 80°C or lower in order to avoid oxidation of hydrophilic groups. The amount of acidic aqueous solution added is preferably set at 0.1 to 100% relative to the organosilicon resin modified with organic groups. The use of 5 to 30% is more preferred.

[0186] From the productivity point of view, the method of adding to the post-reaction solution an aqueous solution so as to adjust the pH to 7 or less and performing strip purification after stirring under heating is preferred. The strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to effectively purify the strip under these temperature conditions, it is preferable to carry out this operation under reduced pressure; when carried out at normal pressure, the operation is preferably carried out under a flow of inert gas such as nitrogen or argon.

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

[0189] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron and the like, in uncombined form or in compound form. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support may be, for example, activated carbon, silica, silica-alumina, alumina or zeolite. These catalysts may be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. In addition, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[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 batchwise or continuously. When it is a batch process, the reaction time depends, for example, on the amount of catalyst and the temperature, but is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to a suitable fixed pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing, and it can therefore be determined by carefully monitoring a pressure gauge.

[0191] The amount of aldehyde included in the glycerol silicone resin which has been purified by this acid treatment and this hydrogenation treatment can be set at 70 ppm or less, preferably at 20 ppm or less, and more preferably at 10 ppm or less.

[0192] It is also possible to combine the two types of deodorization steps mentioned above. In the approach that involves acid treatment, decomposition and removal of the aldehyde compound is possible, but since there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehyde from this cannot be completely suppressed. In the approach that involves a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound that is formed due to this. However, the aldehyde condensate that forms with the condensation of a portion of the aldehyde remains in the system even after such treatment has been carried out, and removal by strip purification is also difficult. Therefore, by alkylating the unsaturated double bonds that remain when the solution following the addition reaction is subjected to hydrogenation, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible (WO2002 / 05588).

[0193] The weight average molecular weight of the glycerolated silicone resin of average formula (1) preferably ranges from 1000 to 100000; from the viewpoint of performance and ease of operations such as filtration, the weight average molecular weight preferably ranges from 3000 to 50000. Here and below, the weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GPC).

[0194] The glycerolated silicone resin according to the invention is in a form at 25°C which can be solid or liquid, from the point of view of the formability of the film, it is preferably solid.

[0195] In particular, the glycerolated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b<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 glycerolated silicone resins according to the invention have a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, preferably from 0.1 to 15, and more preferably from 1.0 to 8.0.

[0197] According to a preferred form, the composition of the invention comprises at least one glycerolated silicone resin of formula (1) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type corresponding to the following formula (21):

[0198] [Chem 21] [(CH3)3SiO1 / 2]a [R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - R denotes the 3-glyceroxypropyl group of structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers which satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.5.

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

[0200] For the purposes of the invention, the term "volatile oil" means any oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1,300 Pa.

[0201] The volatile oil in accordance with the invention may be chosen from the group consisting of hydrocarbon oils, silicone oils, and mixtures thereof.

[0202] By “hydrocarbon oil” is meant an oil containing mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

[0203] For the purposes of the present invention, the term "silicone oil" designates an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.

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

[0205] Mention may be made in particular of C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopar® or Permetyl®. Isododecane will be used more preferably.

[0206] As an example of volatile silicone oil that can be used in the invention, mention may be made of volatile silicone oils, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 centistokes. (2.106 to 8.106 m2 / s), and containing in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils which can be used in the invention, mention may in particular be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, deca-methyltetrasiloxane and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) will be used more preferably.

[0207] According to a particularly preferred form, the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution at 49.5% by weight of active material in isododecane such as product manufactured under the trade name X-25-9138A® by SHIN ETSU with a weight average molecular weight 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 which is immiscible in water. It comprises at least one oil and any ingredient soluble or miscible in said phase.

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

[0212] Mention may in particular be made of C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopar® or Permetyl®.

[0213] Mention may also be made of branched C8-C16 esters such as isohexyl neopentanoate. Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Soit® by the company SHELL, may also be used.

[0214] The volatile hydrocarbon oils that can be used in the compositions according to the invention can be chosen from 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 the patent applications of the company Cognis 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 copra or palm oil.

[0216] As examples of linear C6-C14 alkanes suitable for the invention, mention may be made of 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] Mention may in particular be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12 97® and PARAFOL 14 97®, 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 the company BIOSYNTHIS under the reference can be used. VEGELIGHT 1214®.

[0219] According to yet another embodiment, a mixture of volatile linear C9-C12 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 the company Cognis and such as that sold under the trade name CETIOL ULTIMATE® by the company BASF.

[0221] According to a particularly preferred embodiment, the volatile hydrocarbon oil is chosen from branched C8-C16 alkanes, and more particularly isododecane, the mixture of volatile linear C9-C12 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 chosen from C8-C16 isoalkanes of petroleum origin (also called isoparaffins), in particular isododecane.

[0223] The volatile hydrocarbon oil or oils are preferably present in the composition of the invention at contents 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 the invention, the term “polymer” means a compound having at least 2 repeating units, preferably at least 3 repeating units and better still 10 repeating units.

[0227] The silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type 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 units capable of establishing hydrogen interactions are arranged in the polymer chain.

[0229] The silicone polymers may more particularly be polymers comprising at least one unit corresponding 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, identical or different, represent a group chosen from: - linear, branched or cyclic hydrocarbon groups, C1 to C40, saturated or unsaturated, which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, and which may be substituted in part or completely by fluorine atoms, - C6 to C10 aryl groups, optionally substituted by one or more C1 to C4 alkyl groups, - polyorganosiloxane chains containing or not one or more oxygen, sulfur and / or nitrogen atoms, the X, identical or different, represent a linear or branched alkylene di-yl group in C1 to C30, which may contain in its chain one or more oxygen and / or nitrogen atoms, Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, saturated or unsaturated, C1 to C50, which may contain one or more oxygen, sulfur and / or nitrogen atoms, and / or may carry as a substituent one of the following atoms or groups of atoms: fluorine, hydroxy, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted by 1 to 3 C1 to C3 alkyl, C1 to C3 hydroxyalkyl and C1 to C6 amino alkyl groups, or Y represents a group corresponding to the formula (23): [Chem 23] (23) in which T represents a trivalent or tetravalent, linear or branched, saturated or unsaturated, C3 to C24 hydrocarbon group optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms chosen from O, N and S, or T re- exhibits a trivalent atony selected from N, P and Al, and R8 represents a linear or branched C1 to C50 alkyl group, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups which may or may not be linked to another chain of the polymer, n is an integer ranging from 2 to 500, preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200. Preferably, m is an integer ranging from 50 to 150.

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

[0232] According to the invention, Y may represent various divalent groups, optionally also comprising one or two free valences to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from: - linear alkylene groups from C1 to C20, preferably from C1 to C10, - branched alkylene groups which may contain rings and non-conjugated unsaturations, in C30 to C56, - C5-C6 cycloalkylene groups, - phenylene groups optionally substituted by one or more C1 to C40 alkyl groups, - C1 to C20 alkylene groups, comprising 1 to 5 amide groups, - C1 to C20 alkylene groups, comprising one or more substituents, chosen from hydroxyl, C3 to C8 cycloalkane, C1 to C3 hydroxyalkyl and C1 to C6 alkylamine groups, - polyorganosiloxane chains of formula (24) or (25): [Chem 24] [Chem 86] If O (25) If______ wherein R4, R5, R6, R7, T and m are as defined above.

[0233] According to the second variant, the polyorganosiloxanes may be polymers comprising at least one unit corresponding to formula (II): [Chem 26] A: (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 linear, branched or cyclic, saturated or unsaturated hydrocarbon group, C1 to C50, optionally comprising in its chain one or more atoms chosen from O, S and N, optionally substituted by one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more C1 to C4 alkyl groups, R11 represents the group of formula -XG-R12 in which X, G and R12 are as defined above, mi is an integer 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 may be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (I) or formula (II).

[0235] According to another particular embodiment of the invention, it is also possible to use a silicone polyamide consisting of a copolymer comprising several different units of formula (I), i.e. a polymer in which at least one of R4, R5, R6, R7, X, G, Y, m and n is different in one of the units. The copolymer can also be formed from several units of formula (II), in which at least one of R4, R6, R10, R11, mi and m2 is different in at least one of the units.

[0236] It is also possible to use a polymer comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical or different from each other.

[0237] According to a variant of the invention, it is also possible to use a polymer further comprising at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof.

[0238] These copolymers can be block polymers, sequenced polymers or graft 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 unit of formula (III) or (IV): [Chem 27] 3 iv C.........X...............SiO............Si...............X................... 0 R" R / 0 (HD Or [Chem 28] A: "$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 in particular from 50 to 200 and n ranges in particular from 1 to 500, preferably from 1 to 100. and better still 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, in particular 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 which may contain cycles and / or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and better still from 2 to 6 carbon atoms, in particular 6 carbon atoms.

[0242] In formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements: - 1 to 5 amide, urea, urethane, or carbamate groups, - a C5 or C6 cycloalkyl group, e - a phenylene group optionally substituted by 1 to 3 identical or different C1 to C3 alkyl groups.

[0243] In formulas (III) and (IV), the alkylene groups may also be substituted by at least one element selected from the group consisting of: - a hydroxy group, - a C3 to C8 cycloalkyl group, - one to three C1 to C40 alkyl groups, - a phenyl group optionally substituted by one to three C1 to C3 alkyl groups, - a C1 to C3 hydroxyalkyl group, and - a C1 to C6 aminoalkyl group.

[0244] In these formulas (III) and (IV), Y can also represent represents 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 ranging from 1 to 10, and R13 is a hydrogen atom or a group as 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 C1 to C40 alkyl group, 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 unit of formula (III) and / or (IV).

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

[0248] Thus, the polymer can be a polyamide containing several units of formula (III) or (IV) of different lengths, or a polyamide corresponding 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 from 1 to 1000, and p is an integer from 2 to 300. ,In this formula, the units 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 Ys. In this case, the polymer can correspond to the 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 units 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 unit of formula (VII): [Chem 33] (VII) wherein X1 and X2 which are the same 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 selected from the same group as R4 to R7, m5 and m6 are numbers in the range 1 to 1000, and p is an integer from 2 to 500. In formula (VII), it is preferred that: p ranges from 1 to 25, better still from 1 to 7, R14 to R21 are methyl groups, T meets one of the following formulas: [Chem 34] _____________R33;............AS_______________R' '____________ in which R22 is a hydrogen atom or a group selected from the groups defined for R4 to R7, and R23, R24 and R25 are independently alkylene groups, linear or branched, more preferably, with the formula: [Chem 35] -------- _______„N ..._______R24 ._______ R25 in particular with R23, R24 and R25 representing -CH2-CH2-, mi and m2 range from 15 to 500, and better still from 15 to 45, X1 and X2 represent -(CH2)i0-, and Y represents -CH2-.

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

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

[0254] According to an alternative embodiment of the invention, it is possible to use a copolymer of silicone polyamide and hydrocarbon polyamide, i.e. a copolymer comprising units of formula (III) or (IV) and hydrocarbon polyamide units. In this case, the

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

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] in which R4, R5, R6 and R7 independently represent a linear or branched C1 to C40 alkyl group, 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 in particular from 1 to 500, preferably from 1 to 100 and better still from 4 to 25. Preferably, according to this embodiment, the groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents an alkylene group of 6 carbon atoms and the other an alkylene group of 11 carbon atoms, 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 value approximately 100. The index m corresponds to the degree of polymerization of the silicone part of the polymer. More preferably, the composition according to the invention comprises at least one polymer comprising at least one unit of formula (III) where m ranges from 50 to 200, in particular from 75 to 150, and preferably of the order of 100. As an example of a silicone polymer that can be used, mention may be made of one of the silicone polyamides, obtained in accordance with examples 1 to 3 of document US-A-5,981,680. According to a preferred embodiment, a silicone polyamide polymer with the INCI name: NYLON-611 / DIMETHICONE COPOLYMER marketed by the company Dow Corning under the name DOWSIL 2-8179 GELLANT® (DP 100) and DOWSIL 2-8178 GELLANT® (DP 15) is used. The polymers and / or copolymers used in the composition of the invention have advantageously a transition temperature from the solid state to the liquid state ranging from 45 to 190°C. Preferably, they have a transition temperature from the solid state to the liquid state ranging from 70 to 130°C and better still from 80 to 105°C.

[0263] The silicone polyamide content, expressed as active material, preferably 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 composition (B). Lipophilic thickener

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

[0265] The term “lipophilic thickener” means any liposoluble or lipodispersible molecule in the oily phase of the composition capable of increasing the viscosity of the composition.

[0266] As 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] The clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as a C10 to C22 ammonium chloride, particularly steralkonium chloride or di-stearyl di-methyl ammonium chloride.

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

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

[0271] According to a particularly preferred form, a lipophilic clay chosen from hydrophobic modified bentonites and hydrophobic modified hectorites will be used, in particular by a C10 to C22 quaternary ammonium chloride, 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 with distearyl dimethyl ammonium chloride (INCI name: DISTEARDIMONIUM HECTORITE) such as, for example, that marketed under the name BENTONE® 38VCG RHEOLOGICAL ADDITIVE by the company Elementis Specialities; - a hectorite modified with distearyl dimethyl ammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil such as the commercial products sold under the name BENTONE® GEL DOA V, BENTONE® GEL EUG V, BENTONE® GEL IHD V, BENTONE® GEL ISD V, BENTONE® GEL MIO V® BENTONE® GEL PTM V® BENTONE® SS-71 V, BENTONE® VS-5 PC V, BENTONE® VS-5® by the company Elementis Specialities; the commercial products sold under the name CREAGEL BENTONE CPS / HECTONE CPS®, CREAGEL BENTONE ID / HECTONE ID® by the company Créations Couleurs; the commercial products sold under the name NS GEL DM1®, NS GEL PTIS®, NS MGEL 1152® by the company Next Step Laboratories Stop.

[0272] More particularly, a hectorite modified with 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 active ingredients such as vitamins, lipophilic UV filters, fillers.

[0275] Of course, those skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the envisaged addition.

[0276] The composition (B) used according to the invention may be a composition for caring for and / or making up keratin materials, in particular eyebrows including eyebrow hairs, the skin where 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” denotes 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 relative to its total weight, and including a water-free composition.

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

[0280] Composition (B) of the invention may be in the form of a set or kit for packaging and applying a composition for coating keratin materials comprising: - a packaging 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 integral with a cap mounted reversibly on said container between a position for closing said container and a makeup position.

[0283] Alternatively, such an applicator may be irreversibly mounted on said container. Examples of applicators include those of the felt or brush type 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 by weight relative to the total weight of the composition.

[0285] Throughout the application, the expression "has a" or "includes a" must be understood as meaning "having at least one" or "comprising at least one", unless otherwise specified.

[0286] It is understood that the following examples are provided for illustrative purposes and are in no way limiting of the scope of the protection conferred by the present application. Preparation examples

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

[0288] A reactor was charged 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 the 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. Then 325 g of ethanol was added, after which 6.5 g of 5% aqueous sodium hydroxide solution was added, thereby 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 was added, thereby 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 remove the solvent and filtration was carried out, giving a decamethylcyclopentasiloxane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). The solution had a clear and colorless appearance.

[0289] The decamethylcyclopentasiloxane solution of this silicone resin modified with 3-glyceroxypropyl groups was heated to 120 to 130°C under reduced pressure to remove the decamethylcyclopentasiloxane. The product thus obtained was a solid powder which had 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% by weight solution of isododecane of a silicone resin modified with 3-glyceroxypropyl groups

[0291] A reactor was charged 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 the 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. Then, 325 g of ethanol was added, after which 6.5 g of 5% aqueous sodium hydroxide solution was added, thereby 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 was added, thereby 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 remove the solvent and filtration was carried out, thus giving an isododecane solution of the 3-glyceroxypropyl-modified silicone resin 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 Base Coat composition (Al) 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 Protocol for the preparation of the composition (Al)

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

[0296] The following Top Coat compositions (B1) and (B2) were prepared.

[0297] [Tables2] Ingredients Example (Bl) (not included in the invention) Example (B2) (invention) SILICONE RESIN (3-GLYCEROXYPROPYL) DIMETHYLSILOXY TRL METHYLSILOXYSILICAT E OF FORMULA (21) IN 50% SOLUTION IN LTSODODECANE (X-25-9138A® BY SHIN ETSU) 0 9.1 (4.5% as active matter) TRIMETHYLSILOXYSILIC ATE IN 75% SOLUTION IN LTSODODECANE (SILSOFT 74 FLUID® -MOMENTIVE PERFORMANCE MATERIALS) 18.0 (13.5% as active matter) 18.0 (13.5% as active matter) 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 Protocol for preparing compositions

[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] Resistance measurement tests: 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 pencil layer. The deposit was left to dry for 1 hour. 5 colorimetric data measurements were performed on each deposit (To) with a Konica CM 700d® spectrophotometer (Minolta). We placed 3 drops of cleansing oil (Shu Uemura - Ultime 8 Huile Démaquillante®) on the deposit. The deposit to be evaluated was rubbed in a circular motion 4 times. We rinsed with water. We dabbed with a tissue to remove excess water. The operation was repeated 5 times on each deposit. 5 colorimetric data measurements (T5) were performed on each deposit. The variation in AE color between To and T5 was measured.

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

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

[0303] The results of the 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 combination of the non-glycerolated silicone resin TRIMETHYLSILOXYSILICATE, the glycerolated silicone resin 3-(GLYCEROXYPROPYL) DIMETHYLSILOXY TRIMETHYLSILOXYSILICATE, the silicone polyamide NYLON-611 / DIMETHICONE COPOLYMER and isododecane led to a makeup having excellent resistance to makeup remover 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 glycerolated silicone resin.

Claims

Claims

1. Process for coating, in particular for caring for and / or making up keratin materials, in particular eyebrows including eyebrow hairs, the skin where 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 lead type 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 to the layer formed by the 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-glycerolated silicone resin; and b) at least one glycerolated silicone resin; and c) at least one silicone polyamide; and d) at least one oily phase comprising at least one volatile hydrocarbon oil.

2. Method according to claim 1, where the composition (A) comprises at least one hard wax having a melting temperature ranging from 65 to 120°C, and preferably 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.

3. Method according to claim 2, wherein the composition (A) comprises at least one hard wax selected from Candellila wax with the INCI name EUPHORBIA CERIFERA (CANDELILLA) WAX / CANDELILLA CERA, rice bran wax with the INCI name ORYZA SATIVA (RICE) BRAN WAX / ORYZA SATIVA CERA, a microcrystalline wax with the INCI name MICROCRYSTALLINE WAX / CERA MICRO-CRISTALLINA, a polyethylene wax, a mixture of waxes with the INCI name: C20-40 ALCOHOLS (and) POLYETHYLENE, hydrogenated coconut oil with the 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 waxes, in a concentration ranging from 20 to 50% by weight and preferably from 25 to 45% by weight per relative to the total weight of the composition.

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

6. Process according to any one of the preceding claims, where in composition (A), the non-volatile oil or oils is (are) present in an amount of 5 to 30% by weight and in particular 10 to 20% by weight of the total weight of the composition.

7. Process according to any one of the preceding claims, where in composition (A), the coloring matter(s) is (are) present, preferably, in the composition in a content less than or equal to 50% by weight, preferably 25 to 40% by weight, more particularly 3 to 15% by weight relative to the total weight of the composition.

8. Method according to any one of the preceding claims, wherein the composition (A) comprises at least one powdery coloring matter of mineral pigment type, in particular chosen from titanium dioxides, black, red or yellow iron oxides, coated or not, ferric aluminum iron cyanide, and mixtures thereof.

9. A method according to any preceding claim, wherein composition (A) is anhydrous.

10. A method according to any preceding claim, wherein composition (A) further comprises an aqueous phase.

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

12. Method according to any one of the preceding claims, where the composition (B) comprises at least one non-glycerolated silicone resin chosen from silicone resins of MQ type, in particular of Trimethylsiloxysilicate type.

13. Process according to claim 12, wherein the Trimethylsiloxysilicate resin is in solution in isododecane, in particular in solution at 75% by weight of active material in isododecane.

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

15. Method according to any one of the preceding claims, where in composition (B), the glycerolated 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.

16. Method according to any one of the preceding claims, where in composition (B), the glycerolated silicone resin contains at least one organosiloxane unit of the type RR'R”SiOi / 2 in which R, R' and R”', identical or different, denote hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group.

17. Method according to claim 16, where in composition (B), the glycerolated silicone resin contains at least one dimethylsiloxane unit R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

18. Process according to any one of the preceding claims, where in composition (B), the glycerolated silicone resin(s) are chosen from those of the following formula (1).(R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f(l) in which - each R1, the same or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof; - each R2 is a mono- or poly-glycerol group of the following general formula (2) —(CH2)2—QH21—O—(CH2CH(OH)CH2O);R4 (2) in which - R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and - the indices 1 and i are integers which satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is an identical or different group of general formula (3), general formula (4), general formula (5) or general formula (6) below —(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, the same or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof - the indices m, j and ki to k3 are integers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; - the indices a, b, c, d, e and f are numbers which 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. Process according to claim 18, where in composition (B), the glycerolated silicone resin(s) of formula (1) 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 polyglycerol group R2 is an integer which satisfies the condition 0 < i < 3.

20. Process according to claim 18 or 19, where in composition (B), the glycerolated silicone 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. Process according to any one of claims 18 to 20, where in composition (B), the glycerolated silicone 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 glycerolated silicone resin(s) has (have) a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, ranging from 0.1 to 15, and more preferably from 1.0 to 8.

0.

23. Process according to any one of claims 18 to 22, wherein the composition (B) comprises at least one glycerolated silicone resin of formula (1) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsi- 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 of structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers which satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.

5.

24. The method of claim 23, wherein the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

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

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

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

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

29. Process according to any one of the preceding claims, where 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. Method according to any one of the preceding claims, wherein the composition (B) additionally comprises at least one lipophilic thickener, preferably a lipophilic clay, and more particularly a hectorite modified with distearyl dimethyl ammonium chloride with the 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 composition (B).

32. A method according to any preceding claim, wherein composition (B) is anhydrous.

33. Set or kit for coating, in particular for caring for and / or making up keratin materials, in particular the eyebrows and the skin around the eye and the 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.