TWO-STEP EYEBROW MAKEUP PROCESS WITH A PENCIL-TYPE COMPOSITION AND A COMPOSITION WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, AND A SILICONE GUM

Abstract

TITLE: TWO-STEP EYEBROW MAKEUP METHOD WITH A PENCIL-TYPE COMPOSITION AND A COMPOSITION WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, AND A SILICONE GUM. The present invention relates to a coating method, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours, comprising at least the following steps: 1) the application of a first composition (A) "Base Coat" 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 pigment, 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. ;b) at least one glycerol-based silicone resin; c) at least one silicone gum; d) at least one oily phase comprising at least one volatile hydrocarbon oil.

Description

Title of the invention: TWO-STEP EYEBROW MAKEUP METHOD WITH A COMPOSITION PENCIL TYPE AND A COMPOSITION WITH A NON-GLYCEROLATED SILICONE RESIN, A GLYCEROLATED SILICONE RESIN, A SILICONE GUM

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

[0002] In the field of eyebrow makeup, consumers have access to several types of solutions:

[0003] - eyebrow pencils such as the commercial product MICRO BROW PENCIL® NYX lipsticks are easy to use but only last a day. They often have a pigmented base that transfers color onto the skin.

[0004] - pens, which are also easy to use but only last a day. They are often composed of aqueous formulas containing dyes.

[0005] - tattoo parlor services, which are very painful, but hold several month.

[0006] - anhydrous gels such as the commercial products Inked Waterproof Brow Gel® Urban Decay's (Mintel ID 7578707) and Maybelline's Up to 3 Day Styling Gel® (Mintel ID 10361806) include isododecane and the combination of an MQ resin: TRIMETHYLSILOXYSILICATE and a silicone polyamide: NYLON-611 / DIMETHICONE COPOLYMER.

[0007] Users of makeup formulations of keratinous materials such as eyebrows and skin around the eye and eyebrows seek products with longer lasting power, which is reflected in particular by better resistance of the film deposited to oily substances, such as sebum and makeup remover oils.

[0008] There remains a need to find new compositions for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, which make it possible to obtain makeup with better retention of the deposit over time, in particular better resistance to oily substances such as sebum and makeup-removing oils.

[0009] Unexpectedly, the inventors found that it is possible to achieve these objectives by using a coating process, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including the hairs of eyebrow, the skin where said hairs are implanted and their contours, including at least the following steps:

[0010] 1) the application of a first composition (A) “Base Coat” of the lead type for pencil including, in particular in a physiologically acceptable environment:

[0011] i) at least one wax,

[0012] ii) at least one non-volatile oil,

[0013] iii) at least one coloring matter,

[0014] 2) the application of a second layer to the layer formed by composition (A). formed by a composition (B) “Top Coat” comprising, in particular in a physiologically acceptable environment:

[0015] a) at least one non-glycerol silicone resin;

[0016] b) at least one glycerol-coated silicone resin;

[0017] c) at least silicone gum;

[0018] d) at least one oily phase comprising at least one hydrocarbon oil volatile.

[0019] This discovery is the basis of the invention.

[0020] Thus, a first object of the present invention is a coating method, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours, comprising at least the following steps:

[0021] 1) the application of a first composition (A) “Base Coat” of the lead type for pencil including, in particular in a physiologically acceptable environment:

[0022] i) at least one wax,

[0023] ii) at least one non-volatile oil,

[0024] iii) at least one coloring matter,

[0025] 2) the application of a second layer to the layer formed by composition (A) formed by a composition (B) “Top Coat” comprising, in particular in a physiologically acceptable environment:

[0026] a) at least one non-glycerol silicone resin;

[0027] b) at least one glycerol-coated silicone resin;

[0028] c) at least one silicone rubber;

[0029] d) at least one oily phase comprising at least one volatile hydrocarbon oil.

[0030] A second object of the present invention is a coating assembly or kit, in particular for the care and / or makeup of keratinous materials, in particular eyebrows and the skin around the eye and eyebrows, comprising at least:

[0031] 1) a composition (A) as defined above;

[0032] 2) a composition (B) as defined above; said compositions (A) and (B) being conditioned separately. DEFINITIONS

[0033] In the context of the present invention, "keratinous materials" shall mean, in particular, eyebrows, including eyebrow hairs, the skin in which said hairs are implanted, and their contours. The term "keratinous materials," as used in the present invention, also extends to synthetic false eyebrows.

[0034] By "physiologically acceptable" is meant compatible with said keratinous materials, which has a pleasant color, odor and feel and which does not generate unacceptable discomforts (tingling, pulling), likely to deter the consumer from using this composition.

[0035] By "glycerolated silicone resin", we mean any silicone resin comprising at least one organosiloxane motif comprising one or more monoglycerol(s) or polyglycerol(s) group(s) in its chemical structure.

[0036] In particular, the glycerol silicone resin contains at least one organosiloxane motif of the type RR'R”SiOi / 2 in which R, R' and R'”, identical or different, designate hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerol silicone resin contains at least one dimethylsiloxane motif R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

[0037] By “hydrocarbon radical”, we mean a radical containing predominantly hydrogen and carbon atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether and carboxylic functions.

[0038] By “monoglycerol group” is meant any group comprising in its chemical structure a -O-CH2-CHOH-CH2OH group

[0039] By "polyglycerol group" is meant any group comprising in its chemical structure a chain comprising a repetition of at least 2 glycerol motifs -(O-CH2 -CHOH-CH2)m-.

[0040] COMPOSITION (A) PENCIL-TYPE BASE COAT

[0041] The composition (A) Base Coat of the type for pencil lead according to the invention comprises, in particular in a physiologically acceptable medium:

[0042] i) at least one wax,

[0043] ii) at least one non-volatile oil, and

[0044] iii) at least one coloring matter. WAXES

[0045] For the purposes of this invention, "wax" means a solid and rigid lipophilic compound at room temperature (25°C) with a solid-state change of state. reversible liquid, having a melting temperature above 30°C and up to 120°C, a hardness above 0.05 MPa and exhibiting anisotropic crystalline organization in the solid state.

[0046] By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture and to obtain crystallization of this wax in the oils of the mixture when said mixture is brought back to room temperature.

[0047] According to the invention, the composition more specifically comprises at least one hard wax. By "hard wax" for the purposes of the present invention, we mean a wax having a melting temperature ranging from 65 to 120°C, more preferably between 70 and 100°C.

[0048] Advantageously, by "hard" wax in the sense of the present invention, we mean a wax having at 20°C, a hardness greater than 5 MPa, in particular ranging from 5 to 30 MPa, preferably greater than 6 MPa, better still ranging from 6 to 25 MPa.

[0049] To perform these hardness measurements, the wax is melted at a temperature equal to the melting point of the wax + 20°C. For this, 30g of wax is placed in a 100ml beaker with a diameter of 50mm, itself positioned on a heated magnetic stirring plate. Approximately 15g of melted wax is poured into a stainless steel container 80mm in diameter and 15mm deep, which has been preheated to 45°C in an oven. The wax is then left to recrystallize in a room at 20°C for 24 hours before measurement. The mechanical properties of the wax or wax mixture are determined in a room thermostated at 20°C using the texture tester sold under the name TA-XT2i by the company Swantech, equipped with a stainless steel cylinder with a diameter of 2 mm. The measure involves 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 stage 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 third stage called withdrawal where the mobile returns to its initial position at a speed of 1 mm / s and we note the withdrawal energy of the probe (negative force). The hardness value corresponds to the maximum compressive force, measured in Newtons, divided by the surface area of ​​the texture tester cylinder, expressed in mm², in contact with the wax. The resulting hardness value is expressed in megapascals, or MPa.

[0050] 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. The measurement protocol is as follows:

[0051] A 15 mg sample of wax placed in a crucible is subjected to a first temperature increase from 0°C to 120°C, at a heating rate of 10°C / minute, then is cooled from 120°C to 0°C at a cooling rate of 10°C / minute and finally subjected to a second temperature increase 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 is measured as a function of temperature. The melting point of the compound is the temperature value corresponding to the peak of the curve representing the variation of the difference in absorbed power as a function of temperature.

[0052] The waxes that can be used in the compositions according to the invention can be chosen from solid and rigid waxes at room temperature, of animal, vegetable, mineral, synthetic origin, and their mixtures.

[0053] Generally speaking, waxes of vegetable or mineral origin will be preferred. Animal or synthetic waxes may also be suitable for the invention.

[0054] Examples of hard waxes include Camauba wax, candelilla wax, BIS-PEG-12 DIMETHICONE CANDELILLATE wax such as, for example, SILICONYL CANDELLILA WAX® marketed by KOSTER KEUNEN, hydrogenated Jojoba wax such as, for example, that marketed by DESERT WHALE, hydrogenated palm oil such as that marketed by SIO, rice bran wax, Sumac wax, ceresin waxes, laurel wax, Chinese insect wax, Shellac wax, hydrogenated olive oil such as Waxolive® from SOLIANCE, waxes obtained by hydrogenation of esterified olive oil with C12 to C18 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 esterified castor oil with cetyl or behenic alcohol, such as those sold under the names Phytowax Ricin 16 L 64® and Phytowax Ricin 22 L 73® by 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 PARAMELT, hydrogenated coconut oil with the INCI name: HYDROGENATED COCOGLYCERIDES such as, for example, that sold under the trade names Softisan 100® or Softisan 142 by SASOL, polyethylene waxes such as, for example, that sold under the trade name Cirebelle 303® by 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 New Phase 27 Technologies, alcohol-polyethylene waxes such as, for example, that marketed under the name Performacol 425 Alcohol® by BARECO, the ethylene / acrylic acid 95 / 5 copolymer sold under the trade name Cire AC 540® by Honeywell company, hydroxyoctacosanyl hydroxystearate 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 dibehenyl adipate, dioctadecyl adipate and dieicosanyl 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: Cl8-22 dialkyl sebacate), the mixture of dioctadecyl octadecanedioate,didocosyl octanedioate and dieicosyl octanedioate (INCI name: dialkyl octanedioate Cl8-22), such as those marketed by COGNIS; pentaerythrityl tetrastearate, such as Liponate PS-4® from Lipo Chemicals; tetracontanyl stearate, such as Kester Wax K76 H® from KOSTER KEUNEN; stearyl benzoate, such as Finsolv 116® from FINETEX; behenyl fumarate, such as Marrix 222® from AKZO BERNEL; and di-(trimethyloi-1,1,1-propane) tetrastearate, such as 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 motifs (PEG-4) such as, for example, that which is sold under the trade name Clariant Licowax KST1®,hexanediol disalyticol 28 such as, for example, Betawax RX-13750® marketed by CP Hall, dipentaerythritol hexastearate such as, for example, that which is sold, under the trade name Hest 2P-6S® by HETERENE, ditrimethylolpropane tetrabehenate such as, for example, that sold under the trade name Hest 2T-4B® by HETERENE, jojoba esters such as, for example, that sold under the trade name Floraester HIP® by FLORATECH, mixtures of linear carboxylic acid (C20-40) / saturated hydrocarbons (INCI name: C20-40 Acid polyethylene) such as, for example, Performacid 350 Acid® by NEW PHASE TECHNOLOGIES, Fischer-Tropsch type synthetic wax such as that marketed under the reference Rosswax 100® by ROSS, stearic alcohol, behenic alcohol, dioctadecyl carbonate such as, for example, Cutina KE 3737®, sucrose polybehenate such as, by For example, Crodaderm B® from the company CRODA, and their mixtures.

[0055] 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) from Nucera Solutions; KOSTER KPC-56® (Mixture of cetyl stearate, behenic alcohol and palm kernel glycerides), KPC-60® (Mixture of stearyl stearate, behenic alcohol and palm kernel glycerides), KPC-63® (Mixture of behenyl stearate, behenic alcohol and palm kernel glycerides) and KPC-80® (Mixture of synthetic beeswax, hydrogenated vegetable oil and behenic alcohol) from KOSTER KEUNEN.

[0056] According to a particular embodiment of the invention, the composition (A) comprises at least one hard wax selected from Candellila wax of INCI name EUPHORBIA CERIFERA (CANDELILLA) WAX / CANDELILLA CERA, rice bran wax of INCI name ORYZA SATIVA (RICE) BRAN WAX / ORYZA SATIVA CERA, a microcrystalline wax of INCI name: MICROCRYSTALLINE WAX / CERA MICROCRISTALLINA, a polyethylene wax, a mixture of waxes of INCI name: C20-40 ALCOHOLS (and) POLYETHYLENE, hydrogenated coconut oil of INCI name: HYDROGENATED COCO GLYCERIDES, and mixtures thereof.

[0057] According to a particular embodiment of the invention, the composition (A) comprises a wax content of 20 to 50% by weight and preferably 25 to 45% by weight, relative to the total weight of the composition (A). NON-VOLATILE OILS

[0058] The composition of the invention comprises at least one non-volatile oil.

[0059] The term "oil" refers to any fatty substance in liquid form at ambient temperature (20-25°C) and atmospheric pressure (1.013 x 10⁵ Pa). These oils may be of vegetable, mineral, or synthetic origin.

[0060] The non-volatile oil or oils may be chosen from the group consisting of hydrocarbon oils, silicone oils and their mixtures.

[0061] The non-volatile oil or oils is / are present in the composition of the invention, preferably at a content of 5 to 30% by weight, preferably 7 to 20% by weight, even more preferably 10 to 15% by weight, relative to the total weight of the composition.

[0062] For the purposes of the present invention, "siliconized oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group, and more particularly an organopolysiloxane.

[0063] The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly one or more functions selected from among the hydroxyl, ester, ether, carboxylic functions.

[0064] By "non-volatile oil" is meant an oil remaining on the keratin material at ambient temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 2.66 Pa, preferably less than 0.13 Pa. By way of example, the vapor pressure can be measured according to the static method or by the isothermal thermogravimetric effusion method, according to the vapor pressure (OECD standard 104). Non-volatile hydrocarbon oils

[0065] By way of example of a non-volatile hydrocarbon oil that can be used in the invention, one may cite:

[0066] - vegetable-derived hydrocarbon oils, such as phytostearyl esters,such as phytostearyl oleate, phytostearyl isostearate and lauroyl / octyldodecyl / phytostearyl glutamate; triglycerides consisting of fatty acid esters and glycerol, in particular, whose fatty acids may have chain lengths ranging from C4 to C36, and, in particular, from Cl8 to C36, these oils being linear or branched, saturated or unsaturated; These oils may include, in particular, heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, the liquid fraction of shea butter, aloe vera oil, sweet almond oil, peach kernel oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, carrot oil, safflower oil, hemp oil, rapeseed oil, cottonseed oil, coconut oil,pumpkin seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grapeseed oil, oil, pistachio oil, butternut squash oil, pumpkin oil, quinoa oil, rosehip oil, sesame oil, soybean oil, sunflower oil, castor oil, and watermelon oil, and mixtures thereof, or triglycerides of fatty acids in C4 to Cl8, in particular caprylic / capric acid triglycerides, notably those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel,

[0067] - linear or branched hydrocarbons, of mineral, synthetic or vegetable origin, such as paraffin oils, polydecenes, hydrogenated or not, polybutenes, hydrogenated polyisobutene such as Parleam, squalane;

[0068] - synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether;

[0069] - synthetic esters, such as oils of formula R1COOR2, in which RI represents a remnant of at least one linear or branched fatty acid containing from 1 to 40 carbon atoms, and R2 represents a hydrocarbon chain, particularly a branched one, containing from 1 to 40 carbon atoms, provided that RI + R2 is greater than or equal to 10. Esters may be selected, in particular, from esters of alcohol and fatty acids, such as cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, octyldodecyl stearoyl stearate, and hydroxylated esters, such as... isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate,tridecyl octanoate, ethyl 2-hexyl 4-diheptanoate and palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol diethyl 2-hexanoate and mixtures thereof, C12-C15 alcohol benzoates, C12-C15 alkyl ethylhexanoate such as the commercial product ACTIVEMOL EH-25® from Innospec Active Chemicals, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isononanoate isotridecyl, octyl isononanoate, hydroxylated esters such as isostearyl lactate, di-isostearyl malate; ,

[0070] - pentaerythritol esters, such as tetrahydroxystearate / tetraisostearate of dipentaerythritol, pentaerythritol tetrahydroxystearate, pentaerythritol tetraisostearate;

[0071] - the esters of diol dimers and diacid dimers,

[0072] - diol dimer and diacid dimer copolymers and their esters, such as dilinoleyl diol / dilinoleic dimer copolymers and their esters,

[0073] - copolymers of polyols and diacid dimers, and their esters,

[0074] - liquid fatty alcohols at room temperature with a branched carbon chain and / or unsaturated having 12 to 26 carbon atoms such as octyldodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, oleic alcohol;

[0075] - higher fatty acids such as oleic acid, linoleic acid, acid linolenic;

[0076] - carbonates such as dicapryl carbonate;

[0077] - acetates;

[0078] - citrates;

[0079] - their mixtures. Non-volatile silicone oils

[0080] The composition may also include at least one silicone oil, other than silicone gum c).

[0081] Examples of non-volatile silicone oils include:

[0082] - polydimethylsiloxanes (INCI name: Dimethicone) in particular, of viscosity ranging from 50 to 500 mm2 / s (est), including 350 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 350® by WACKER, XIAMETER PMX-200 SILICONE FLUID® 350CS by DOW CORNING; polydimethylsiloxanes with viscosities ranging from 50 to 150 mm2 / s (est), including 100 mm2 / s (est) such as the commercial products sold under the names BELSIL DM 100® by WACKER, XIAMETER PMX-200 SILICONE FLUID 100CS® by DOW CORNING.

[0083] - phenylated silicone oils such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethyl-siloxysilicates.

[0084] According to a preferred method, the non-volatile oil or oils is / are chosen from synthetic esters, C4 to C18 fatty acid triglycerides, and mixtures thereof.

[0085] The quantity of non-volatile oil(s)(c) is generally adjusted to control the texture and mechanical properties of the composition (A) according to the invention, in particular in terms of application comfort and lead retention.

[0086] In particular, the non-volatile oil or oil(s) may be present at a rate of 5 to 30% by weight, and in particular 10 to 20% by weight, relative to the total weight of the composition. COLORING MATERIALS

[0087] The composition (A) according to the invention comprises at least one coloring material.

[0088] The coloring materials may be chosen from mineral pigments, organic pigments, mother-of-pearl, liposoluble colorants, and mixtures thereof. Pigments

[0089] 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. Mineral pigments

[0090] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0091] By "mineral pigment" is meant any pigment which meets the definition in the Ullmann encyclopedia in the chapter on inorganic pigment.

[0092] Among the mineral pigments useful in the present invention, one can cite zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric aluminum ferrocyanide, titanium dioxide, and metallic powders such as aluminum powder and copper powder. The following mineral pigments can also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 in mixtures with TiO2, ZrO2, Nb2O5, CeO2, and ZnS.

[0093] The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can go up to 100 µm, preferably from 200 nm to 5 µm, and more preferably from 300 nm to 1 µm.

[0094] According to a particular embodiment of the invention, the pigments have a size characterized by a D

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

[0095] The sizes are measured by static light scattering using a commercial particle size analyzer, the Malvern Master Sizer 3000®, which allows for the determination of the particle size distribution over a wide range from 0.01 µm to 1000 µm. The data are processed based on the classical Mie scattering theory. This theory is best suited for size distributions ranging from submicron to multimicron and allows for the determination of an "effective" particle diameter. This theory is notably described in Van de Hulst, HC, “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957.

[0096] D

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

[0097] According to a particular embodiment of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, the latter preferably being present in the oily phase of the composition according to the invention.

[0098] According to a particular embodiment of the invention, the pigments can be coated according to the invention by at least one compound selected from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

[0099] According to a particular mode, the pigments can be coated according to the invention with an N-acylated amino acid or one of its salts which can comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

[0100] The amino acid may be, for example, lysine, glutamic acid, or alanine. The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zinc, sodium, or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylated amino acid derivative, which may be, in particular, a glutamic acid derivative and / or one of its salts, and more specifically a stearoyl glutamate, such as aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include the black iron oxide pigments CI77499, red CI77491, and yellow CI77492, sold under the trade name NAI® by MIYOSHI KASEI.

[0101] According to a preferred embodiment, the pigments according to the invention can be coated with isopropyl titanium triisostearyl titanate. Examples of pigments treated with isopropyl titanium triisostearate (ITT) include titanium dioxide pigments and black, red, and yellow iron oxide pigments sold under the trade names BWB0-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWY0-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate), and BWRO-12® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by KOBO.

[0102] Among mineral pigments, nacres can also be mentioned. These can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with, in particular, ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. Organic pigments

[0103] The pigments that can be used according to the invention can also be organic pigments.

[0104] By "organic pigment" is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on organic pigment. The organic pigment may in particular be chosen from among the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0105] The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the Color Index under references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments coded in the Color Index under references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under references CI 61565, 61570, 74260, the orange pigments coded in the Color Index under the references CI 1725, 15510, 45370, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and pigments obtained by oxidative polymerization of indole derivatives,phenolic compounds as described in patent FR2 679 771.

[0106] These pigments can also be in the form of composite pigments as described in patent EPI 184426. These composite pigments can be composed in particular of particles comprising an inorganic core covered at least partially with an organic pigment and at least one binder ensuring the fixation of the organic pigments on the core.

[0107] The pigment can also be a lacquer. By lacquer, we mean insolubilized dyes adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0108] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0109] Among organic colorants, cochineal carmine may be mentioned. Other products known by 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 Red33 (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 Bine 1 (CI 42 090).

[0110] As examples of lacquers, we can cite the product known under the name D&C Red 7 (CI 15 850 :1). Fat-soluble coloring agents

[0111] By "liposoluble colouring material", in the sense of the invention, is meant any compound generally organic, natural or synthetic, soluble in an oily phase or solvents miscible with a fat and capable of colouring.

[0112] Fat-soluble colorants suitable for the invention may include, in particular, synthetic or natural fat-soluble colorants such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red, carotenes ([3-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan Brown, quinoline yellow, annatto, curcumin.

[0113] Preferably, the colouring material(s) is / are present in the composition at 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.

[0114] Preferably, the composition (A) according to the invention comprises at least one powdered colouring material of the mineral pigment type, in particular selected from titanium dioxides, black, red or yellow iron oxides, coated or uncoated, ferric aluminium ferrocyanide, and mixtures thereof. SURFACTANTS

[0115] The composition (A) according to the invention may also include at least one surfactant.

[0116] More particularly suitable for the invention are C4-C24 fatty acid esters, especially C8-C18, linear or branched, saturated or unsaturated (palmitate, stearate, oleate) (poly)oxyethylenated; C4-C24 fatty acid esters, especially C8-C18, linear or branched, saturated or unsaturated (palmitate, stearate, oleate) of (poly)oxyethylenated or non-polysorbitan; C4-C24 fatty acid esters, especially C8-C18, linear or branched, saturated or unsaturated of sucrose, C4-C24 fatty acid esters, especially C8-C18, linear or branched, saturated or unsaturated of glucose derivatives, alkyl polyglucosides, condensation products of an α-diol, a monoalcohol and mixtures thereof.

[0117] We can also mention fatty acid esters of polyol such as mono-, di-, tri- or sesqui-oleate of sorbitol, mono-, di-, or tri-stearate of sorbitol or mixtures thereof.

[0118] We may also mention partial esters resulting from the reaction of at least one linear or branched fatty acid in C8-C40 and preferably in C8-C22, saturated or unsaturated, in particular of ricinoleic acid or 12-hydroxystearic acid, with at least one polyol such as glycerol, polyglycerol, pentaerythritol, saccharide alcohols such as sorbitol, and in particular polyglycerol esters, and esters resulting from the reaction of sorbitan with at least one linear or branched fatty acid, saturated or unsaturated.

[0119] Representative examples of this type of compound include:

[0120] - POLYGLYCERYL-2 TRIISOSTEARATE as the commercial product sold under the name RISOREX PGIS23® by the company KOKYU ALCOHOL KOGYO;

[0121] - SORBITAN TRISTEARATE such as the commercial product sold under the name SP SPAN 65 MBAL-PW-(MV)® by the company CRODA; and their mixtures.

[0122] Preferably, the composition may comprise from 0.05 to 10% by weight of surfactant(s), relative to the total weight of the composition. More particularly, the surfactant content varies from 2 to 10%, preferably from 3 to 7% by weight, relative to the total weight of the composition. CHARGES

[0123] Composition (A) may further include at least one of the fillers commonly used in the field of cosmetics.

[0124] By "charges" we mean colourless or white particles, mineral or synthetic, lamellar or non-lamellar.

[0125] The fillers may be present at a rate of 0.01 to 60% by weight, more particularly from 3 to 10% by weight, relative to the total weight of the composition.

[0126] The fillers that can be used are generally mineral or synthetic, lamellar or non-lamellar.

[0127] Representative examples of these fillers include talc, natural mica or synthetic mica such as fluorphlogopite, silica, kaolin, nylon and polyethylene powders, Teflon, starch, boron nitride, polymer microspheres such as Expacel® (Nouryon), silicone resin microbeads, precipitated calcium carbonate, magnesium carbonate or hydrocarbonate, bismuth oxychloride and mixtures thereof. ADDITIVES

[0128] Composition (A) may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners like zinc stearate, trace elements, softeners, sequestrants, UV filters and mixtures thereof.

[0129] Finally, the composition (A) may also contain other additives, in particular to control its viscosity, adjust its colour or its reflective effect.

[0130] Propylene carbonate can be used in particular as a useful agent for controlling viscosity.

[0131] Of course, a person skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or substantially not, altered by the envisaged addition.

[0132] According to a particularly preferred form, the composition (A) of the invention is anhydrous.

[0133] For the purposes of the invention, the expression "anhydrous composition" means 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 the total weight of the composition, and in particular a water-free composition.

[0134] According to one embodiment, the composition (A) of the invention may comprise an aqueous phase comprising water and water-soluble or water-miscible organic solvents such as lower monoalcohols having 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes.

[0135] The composition (A) according to the invention is formulated in a conventional manner in the form of a pencil lead.

[0136] According to a particular embodiment of the invention, the pencil lead can be in retractable form.

[0137] Generally, wax-type compounds are melted and combined with the other liquid components. Various other compounds, including solids such as pigments and fillers, are then added to this mixture, and the whole is homogenized again. The resulting matrix is ​​then formulated as pencil lead using conventional processes. COMPOSITION (B) TOP COAT

[0138] Composition (B) “Top Coat” according to the invention comprises, in particular in a physiologically acceptable medium:

[0139] a) at least one non-glycerol silicone resin;

[0140] b) at least one glycerol-coated silicone resin;

[0141] c) at least one silicone rubber;

[0142] d) at least one oily phase comprising at least one volatile hydrocarbon oil. NON-GLYCEROLATED SILICONE RESINS

[0143] The composition (B) according to the invention comprises at least one non-glycerol silicone resin a).

[0144] More generally, the term "resin" refers to a compound with a three-dimensional structure. Silicone resins are also called silicone resins or "siloxane resins." Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

[0145] The nomenclature of silicone resins is known as MDTQ, the resin being described according to the different siloxane monomeric units it comprises, each of the letters MDTQ characterizing a type of unit.

[0146] The letter M represents the Monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being bonded to a single oxygen atom in the polymer comprising this unit.

[0147] The letter "D" signifies a Difunctional unit R1 R2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.

[0148] The letter T represents a Trifunctional RlSiO3 / 2 unit.

[0149] 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.

[0150] In the motifs M, D, T defined above, R, namely RI, R2 and R3, represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0151] Finally, the letter Q signifies a tetrafunctional SiO4 / 2 unit in which the silicon atom is bonded to four oxygen atoms which are themselves bonded to the rest of the polymer.

[0152] Various silicone resins of different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the dangling chains.

[0153] As examples of silicone resins that can be used in the compositions according to the invention, MQ type silicone resins, T type silicone resins, MQT type silicone resins, and mixtures thereof may be used. MQ Resins

[0154] As an example of MQ-type silicone resins, alkylsiloxysilicates of formula [(Rl)3SiOi / 2]x(SiO4 / 2)y (MQ units) may be cited, in which x and y are integers from 50 to 80, and such that the RI group represents a radical as defined previously, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0155] Examples of MQ silicone resins of the Trimethylsiloxysilicate type include those marketed under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker, under the name "KF-7312J®" by Shin-Etsu, and "DC 749®" and "DC 593®" by Dow Corning. T Resins

[0156] By way of example of T-type silicone resins, we may cite polysilsesquioxanes of formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

[0157] Preferably, polymethylsilsesquioxane resins in which R represents a methyl group may be used, such as, for example, those commercially available:

[0158] - by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating CH3SiO3 / 2 units (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2 units (D units) and having an average molecular weight of about 10000 g / mol, or

[0159] - by the company SHIN-ETSU under the references KR-220L® which are composed of T units with the formula CH3SiO3 / 2 and have Si-OH (silanol) terminal groups, under the reference KR-242A® which comprise 98% T units and 2% dimethyl D units and have Si-OH terminal groups, or under the reference KR-251® comprising 88% T units and 12% dimethyl D units and have Si-OH terminal groups. MQT Resins

[0160] As a resin comprising MQT motifs, those cited in US document 5 110 890 are known in particular.

[0161] A preferred form of MQT-type resins is MQT-propyl resin (also called MQTPr). Such resins usable in the compositions according to the invention include, in particular, those described and prepared in application WO 2005 / 075542.

[0162] The MQ-T-propyl resin preferably comprises the following units: (i) ((Rl)3SiO1 / 2)a (ii) ((R2)2SiO2 / 2)b (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with RI, R2 and R3 independently represent a hydrocarbon radical (especially alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d=l, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0163] Preferably, the siloxane resin comprises the following units: (i) ((Rl)3SiO1 / 2)a (ii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with RI and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, RI being preferably a methyl group and R3 being preferably a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55, a + b + c + d = l, eta, b, cetd being mole fractions, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0164] The siloxane resins usable according to the invention can be obtained by a process comprising the reaction of A) a resin MQ comprising at least 80 mole percent of ((Rl)3SiO1 / 2)a and (SiO4 / 2)d units RI representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, a and d being greater than zero, the a / d ratio being between 0.5 and 1.5; and of B) a propyl T resin comprising at least 80 mole percent of (R3SiO3 / 2)c units, R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, provided that at least 40% by mole 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.

[0165] Advantageously, the mass ratio A / B is between 95.5 and 15.85. Preferably, the A / B ratio is less than or equal to 70:30. These preferred ratios have been shown to allow comfortable deposition.

[0166] Preferably, the composition (B) according to the invention comprises, as a silicone resin, at least one MQ type resin, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker, under the name KF-7312J® by Shin-Etsu, DC 749®, DC 593® by Dow Corning, under the reference SILSOFT 74 FLUID® by MOMENTIVE PERFORMANCE MATERIALS.

[0167] A Trimethylsiloxysilicate type resin in solution in isododecane will be used in particular, in particular in a solution of 75% by weight of active matter in isododecane such as the commercial product sold under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS.

[0168] According to a particular embodiment of the invention, the non-glycerol silicone resin(s) is / are present in the composition (B) in a content, expressed as active matter, ranging from 4 to 35% by weight, preferably ranging from 6 to 30% by weight, and more preferably from 8 to 25% by weight, relative to the total weight of the composition (B). Glycerol-based silicone resin

[0169] The composition (B) according to the invention comprises at least one glycerol silicone resin b).

[0170] The glycerol-based silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol groups.*

[0171] According to a particular embodiment of the invention, the glycerol silicone resin(s) is / are present in a content, expressed as active matter, ranging from 0.1 to 40% by weight, preferably ranging from 0.2 to 30% by weight, and more preferably from 0.5 to 15% by weight, relative to the total weight of the composition (B).

[0172] The glycerol-siliconized resin(s) according to the invention are preferably chosen from those of the following formula (1). (Rl3SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(Rl2SiO2 / 2)d(RlSiO3 / 2)e(SiO4 / 2)f (1) in which - each RI, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - each R2 is a mono- or poly-glycerol group with the following general formula (2) -(CH2)2-C1H21-O-(CH2CH(OH)CH2O)iR4 (2) in which - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, and - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is an identical or different group of general formula (3), general formula (4), general formula (5) or general formula (6) below: -(CH2)2-CmH2m-(SiORl2)j-SiRl3 (3) -(CH2)2-CmH2m-SiRlkl-(OSiRl3)3 kl (4) -(CH2)2-CmH2m-SiRlkl-(OSiRlk2(OSiRl3)3_k2)kl (5) -(CH2)2-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiRl3)3_k3)3_k2)3_kl (6) where - each RI, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - the indices m, j and kl to k3 are integers that satisfy the conditions 0< m < 5, 0 < j < 500, 0< kl < 2, 0 < k2 < 2 and 0 < k3 < 2; - the indices a, b, c, d, e and f are numbers that satisfy the conditions 0 < a < 400, 0

[0173] Glycerol-coated silicone resins according to the invention are described in Shin Etsu's US patent application US20200332065A1.

[0174] According to a particular method, the glycerol-coated silicone resin(s) of formula (1) as defined above are chosen from those of which - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; - the index i in the general formula (2) of the monoglycerol or polyglycerol group R2 is an integer which satisfies the condition 0 < i < 3. ​

[0175] According to a particular mode, the glycerol silicone resin(s) of formula (1) are in solid form at 25 °C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

[0176] According to a particular mode, the glycerol-siliconized resin(s) have an average molecular weight by weight ranging from 1000 to 100000.

[0177] The glycerol-coated silicone resin(s) according to the invention are amphiphilic, that is, they have two parts with different polarities. Generally, one is lipophilic (soluble or dispersible in an oil phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by their HLB (Hydrophilic-Lipophilic Balance) value, the HLB being the ratio between the hydrophilic and lipophilic parts in the molecule. The term HLB is well known to those skilled in the art and is described, for example, in "The HLB System: A Time-Saving Guide to Emulsifier Selection," published by ICI Americas Inc., 1984. The HLB value of the glycerol-coated silicone resin(s) according to the invention preferably varies from 0.1 to 15 according to Griffin's method.

[0178] The glycerol-coated silicone resin(s) according to the invention can be obtained by a preparation process comprising the hydrosilylation step A) of a silicone resin containing a hydrosilyl group of formula (7) below (Rl3SiO1 / 2)JInRl3_nSiO1 / 2)b+c(Rl2SiO2^ (7) in which: - each RI, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0 < d < 320, 0 < e < 320, 0 < f < 1000 and 0.5 < (a+b+c) / f < 1.5; - n is an integer that satisfies the condition 1 < n < 3, with B) one or more compounds that are chosen from the compounds ending with an alkenyl group of general formulas (8), (9), (10), (11) and (12) below: CH2=CH-CiH2i-O-(CH2CH(OH)CH2O)iR4 (8) CH2=CH-CmH2m-(SiORl2)j-SiRl3 (9) CH2=CH-CmH2m-SiRlkl-(OSiRl3)3 kl (10) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRl3)3 k2)3 kl (11) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiRl3)3 k3)3 k2)3 kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 <l<15, 0<i<5; - the indices m, j and kl to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said silicone resin containing a hydrosilyl group of formula (7) reacting with at least one compound of formula (8).

[0179] The hydrosilylation reaction is carried out in the presence, for example, of a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R4,1, m, i, j and kl to k3 are as defined above.

[0180] Silicone resin containing a hydrosilyl group used as a starting material

[0181] The silicone resin containing a hydrosilyl group of formula (7) can be in solid or liquid form at 25°C, although, in terms of film-forming ability, it is preferably solid. From a utility standpoint, the resin is preferably diluted with an organic solvent. The use of a solvent whose boiling point is above the reflux temperature during hydrolysis is preferred.

[0182] 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 decamethylcyclopentasiloxane are preferred.

[0183] The silicone resin containing a hydrosilyl group of formula (7) is prepared: (i) by hydrolyzing, in the presence of an acid catalyst, a mixture of one or more compounds selected from the organosilicon compounds of general formulas (13) and (14) below, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) below and one or more compounds selected from the hydrolyzable silanes of general formula (17) below, the partial hydrolytic condensates of these hydrolyzable silanes and the metallic salts of these hydrolyzable silanes: Rl3SiOSiRl3 (13) Rl3SiXl (14) HnRl(3 n)SiOSiRl(3 n)Hn (15) HnRl(3 n)SiX2 (16) Or - each RI, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - XI and X2 are hydrolyzable functional groups; and - n satisfies the condition 1 < n < 3 SiX34(17) where X3 is a hydrolyzable functional group), ii) by neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acid catalyst, and iii) by then carrying out a condensation.

[0184] In general formulas (13), (14), (15) and (16), the examples and preferred range for RI are the same as those mentioned above.

[0185] In the general formula (14), XI is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the point of view of availability and rate of hydrolysis, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0186] In the general formula (16), X2 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the standpoint of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0187] In the general formula (17), X3 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, an alkoxy group is preferred; from the standpoint of availability and hydrolysis rate, a methoxy or ethoxy group is preferred. The hydrolyzable X3 groups on the molecule may be similar or different groups.

[0188] Examples of organosilicon compounds of general formula (13) include 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,1,3,3-pentavinylmethyldisiloxane, 1,1,1,3,3-n- octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Among these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

[0189] Examples of organosilicon compounds of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane. Of these, trimethylchlorosilane and trimethylethoxysilane are preferred.

[0190] 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.

[0191] Furthermore, in general formulas (15) and (16), n satisfies the condition 1 < n < 3. In general formula (15), the "n" associated with the H and RI bonded to one silicone atom and the "n" associated with the H and RI bonded to the other silicone atom can be identical or different.

[0192] Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0193] Examples of hydrolyzable silane of general formula (17) include tetrachlorosilane, tetramethoxysilane, and tetraethoxysilane. Examples of partially hydrolyzed condensates of hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silane include soluble glass, sodium silicate, and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0194] In this invention, to a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metallic salts of these hydrolyzable silanes may be added prior to hydrolysis under an acid catalyst, or a mixture of one or more compounds selected from organosilicon compounds of general formula (17) (18) or general formula (19) can be added after such hydrolysis and before the rehydrolysis described later. RlSiX43 (18) Rl2SiX52(19) where - each RI is an alkyl, aryl or aralkyl group identical or different from 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - X4 and X5 are hydrolyzable functional groups.

[0195] In general formulas (18) and 19), the examples and preferred ranges for RI are the same as those mentioned above.

[0196] In the general formula (18), X4 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the standpoint of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred. The X4 hydrolyzable groups on the same molecule may be similar or different.

[0197] In the general formula (19), X5 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the standpoint of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred. The X5 hydrolyzable groups on the same molecule may be similar or different.

[0198] Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, rethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane, and methyltrichlorosilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, and methyltrichlorosilane are preferred.

[0199] Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane and dimethyldichlorosilane. Of these, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane are preferred.

[0200] A specific example of a process for preparing the silicone resin containing a hydrosilyl group used as a raw material in the present invention is described. A solvent (in particular, an organic solvent) and a hydrolysis raw material (a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), the condensates of partial hydrolysis of these hydrolyzable silanes, and the metal salts of these hydrolyzable silanes) are loaded into a reactor, an acid is added as a catalyst, and water is added dropwise while stirring. It is also possible in this case to add the organic solvent after the dropwise addition of water has been completed.Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0201] [The temperature during the dropwise addition of water is preferably between 0 and 80°C, and more preferably between 0 and 50°C. By maintaining the temperature within this range, the heat of reaction of the hydrolysis reaction on the hydrolysis starting product in the system can be kept low. The amount of water added dropwise, expressed as a molar ratio per mole of hydrolyzable functional groups (alkoxy groups, etc.), is between 0.6 and 2, and preferably between 1.0 and 1.8. By maintaining the amount of water added within this range, it is possible to further suppress the deactivation of hydrosilyl groups.

[0202] In order to eliminate a decrease in the reaction rate due to retention and an increase in the viscosity of the uniform reaction system during the hydrolysis reaction, it is preferable to use an organic solvent as the solvent in the hydrolysis reaction. It is also desirable to use a solvent whose boiling point is higher than the reflux temperature during hydrolysis.

[0203] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methylethyl ketone, diethyl ketone and methylisobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane.

[0204] 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- 2-methylpropanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Because alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol, and 2-propanol are particularly preferred.

[0205] The solvent used is included in an amount, relative to the overall reaction system, of 1 to 80% (here and below, "%" refers to the percentage by weight), and in particular from 5 to 50%. Within this range, the reaction system remains uniform and the reaction proceeds efficiently.

[0206] Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. The acid catalyst may be used in small amounts, with an amount on the order of 0.001 to 10% of the overall reaction system being preferred.

[0207] After adding water dropwise as mentioned above, the hydrolysis reaction is carried out by heating the system to a temperature between 50 and 150°C, preferably between 80 and 120°C, for approximately 2 to 8 hours. During this time, by carrying out the reaction at a temperature below the boiling point of the organic compound containing hydrosilyl groups used, the deactivation of the hydrosilyl groups can be further suppressed.

[0208] After carrying out the hydrolysis in this manner on the starting product of the above hydrolysis in the presence of an acid catalyst, the system is cooled to a temperature between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably at 25°C.

[0209] After the above hydrolysis, the system is neutralized between 10 and 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this point, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is prevented and the condensation reaction of the organosilicon resin is further favored. 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. With regard to the combinations of a strong basic catalyst with a weak basic catalyst, from the point of view of the ease of obtaining a weight For high molecular weight resins, a combination of sodium hydroxide and calcium carbonate is desirable. This combination increases the molecular weight sufficiently, making it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

[0210] The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. Performing the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, resulting in an increase in molecular weight and yielding a high molecular weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the amount added within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, thus yielding a resin of the target molecular weight.

[0211] After neutralization, the alcohols formed, the solvent, and excess water can be removed by heating between 95 and 120°C under normal or reduced pressure. Then, after confirming that the alcohols formed, the solvent, and excess water have been removed, the condensation reaction is carried out by heating between 120 and 150°C for approximately 2 to 5 hours. This yields an organosilicon resin containing a hydrosilyl group.

[0212] In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio between the combined molar quantity of the compounds of general formulas (13), (14), (15) and (16) and the molar quantity of SiO4 / 2 units in the compound of general formula (17), expressed as the molar ratio ((13)+(14)+(15)+(16)) :(19), is preferably from 0.3:1 to 2:1, and more preferably from 0.6:1 to 1.3:1.

[0213] Furthermore, the ratio between the combined molar quantity of compounds of general formulas (13) and (14) and the combined molar quantity of compounds of general formulas (15) and (16), expressed as the molar ratio ((13)+(14)) :((15)+(16)), is preferably from 0.3:1.0 to 2.0:1.0, and more preferably from 0.6:1.0 to 1.3:1.0. By setting the values ​​within these ranges, the amount of hydrosilyl groups included in the organosilicon resin containing hydrosilyl groups can be varied quantitatively more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulas (15) and (16) are loaded, it is possible to quantitatively vary the amount of hydrosilyl groups included on the organosilicon resin.

[0214] In the process described above for preparing a silicone resin containing hydrosilyl groups, after carrying out hydrolysis, in the presence of an acid catalyst, from a mixture of one or more compounds chosen from the organosilicon compounds of general formulas (13) and (14) with one or more compounds chosen from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes and metallic salts of these hydrolyzable silanes, it is also possible to add gradually, drop by drop, one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group, of general formulas (15) and (16).

[0215] Next, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably performed by heating at a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example, preferably between 40 and 150°C, and more preferably between 40 and 120°C, for about 2 to 8 hours. When the reaction is carried out within this temperature range, the deactivation of the hydrosilyl groups can be further suppressed.

[0216] In the process of preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups are deactivated, can occur. [Chem 1] SiCS , / M ...........O...... fï' JI, , / D m.sho where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

[0217] However, by appropriately determining the order in which the raw materials are added, i.e., by hydrolyzing a mixture of one or more compounds selected from the organosilicon compounds of general formulas (13) and (14) with one or more compounds selected from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes, and metallic salts of these hydrolyzable silanes, and then adding one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) and carrying out a rehydrolysis, the above reaction (20) can be kept to a minimum. This reaction can be further suppressed by cleverly modifying the quantities in which the raw materials are added and the type of catalyst used.

[0218] The quantity of hydrosilyl groups included in the organosilicon resin thus obtained is easily adjustable, and it is even possible to introduce a large quantity of hydrosilyl groups by varying the amount of the organosilicon compound containing hydrosilyl groups that is loaded. Furthermore, by varying the quantity of hydrolysis starting materials used, the type and the The amount of acid catalyst added, the temperature and reaction time, the amount of solvent added and the method of addition, the molecular weight range, the shape and other characteristics of the organosilicon resin can be adjusted, making it possible to prepare an organosilicon resin containing hydrosilyl groups for the intended application.

[0219] The silicone resin containing a hydrosilyl group obtained as described above has the average formula (7) above and is composed of Q units (SiO4 / 2) and M units (Rl3SiO1 / 2) and (HnRl3nSiO1 / 2) as essential constituents, and also of D units (Rl2SiO2 / 2) and T units (RlSiO3 / 2) as optional constituents. It may be in the form of a solid or a liquid at 25°C, although from the point of view of film formability, it is preferably a solid. Examples include MQ resins, MTQ resins, MDQ resins, and MDTQ resins. The average molecular weight is preferably between 2,000 and 30,000, although the range of 3,000 to 15,000 is more preferred from the point of view of performance and ease of performing operations such as filtration.The weight-average molecular mass can be determined as the weight-average molecular mass equivalent to polystyrene in gel permeation chromatography (GC).

[0220] Process for preparing glycerol-coated silicone resin

[0221] A specific example of a process for preparing the glycerol-siliconized resin according to the invention is described below.

[0222] As mentioned above, the glycerol-coated silicone resin according to the invention can be obtained by the hydrosilylation step (A) of a silicone resin containing a hydrosilyl group of average formula (7) below: (R13SiOl / 2)a(HnR13-nSiOl / 2)b+c(R12SiO2 / 2)d(RlSiO3 / 2)e(SiO4 / 2)f (7) in which - each RI is an alkyl, aryl or aralkyl group identical or different from 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0 < d < 320, 0 < e < 320, 0 < f < 1000 and 0.5 < (a+b+c) / f < 1.5; - n is an integer that satisfies the condition 1 < n < 3 with (B) one or more compounds which are chosen from the compounds ending with an alkenyl group of general formulas (8), (9), (10), (11) and (12) below CH2=CH-ClH21-O-(CH2CH(OH)CH2O)iR4(8) CH2=CH-CmH2m-(SiOR12)j-SiR13 (9) CH2=CH-CmH2m-SiRlkl-(OSiR13)3-kl (10) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiR13)3-k2)3-kl (11) CH2=CH-CmH2m-SiRlkl-(OSiRlk2(OSiRlk3(OSiR13)3-k3)3-k2)3-kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15, and 0 < i < 5; - the indices m, j and kl to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said includes a compound of general formula (8).

[0223] The organosilicon resin containing hydrosilyl groups of average composition formula (7) and the compound having terminal alkenyl groups of general formula (8), (9), (10), (11) or (12) are mixed in a molar ratio, expressed in hydrosilyl groups / terminal unsaturated groups, which is preferably from 0.5 to 2.0, and more preferably from 0.8 to 1.2.

[0224] The addition reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinyl siloxane complexes. When an excessive amount of the catalyst is included, discoloration of the sample occurs, and therefore the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0225] Furthermore, if necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane. and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol.From a reactivity standpoint, ethanol, 1-propanol, and 2-propanol are preferred.

[0226] The amount of solvent used is preferably from 1 to 80%, and more preferably from 5 to 50%, of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0227] The conditions of the addition reaction are not particularly limited, although reflux heating at a temperature between 50 and 150°C, in particular between 80 and 120°C, for about 1 to 10 hours is preferred.

[0228] After the addition reaction, the step of removing the rhodium or platinum catalyst used with the activated carbon may be included. The amount of activated carbon used is preferably from 0.001 to 5.0%, and in particular from 0.01 to 1.0%, of the overall system. By fixing the amount of activated carbon within this range, the discoloration of the sample can be better suppressed.

[0229] After the addition reaction, if necessary, a step to remove the remaining hydrosilyl groups may be included. Particularly in cases where use in applications such as cosmetic preparations is planned, there is a possibility that these hydrosilyl groups may become deactivated over time due to dehydrogenation reactions, which poses a safety concern. Therefore, it is preferable to include a step to maintain the hydrosilyl groups.

[0230] An example of a step for removing hydrosilyl groups is the process of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, followed by neutralization through the addition of an amount of acidic catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the perspective of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being especially preferred.Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. Generally, instead of using the acid or base alone, it is preferable to use them with water and heat them to a temperature no higher than the boiling point of water.

[0231] After the addition reaction, if necessary, a deodorization step to reduce the odor may be included. When use in applications such as cosmetic preparations is planned, in particular, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common silicones modified with polyethers can be explained as follows. When an addition reaction occurs between a polyether The allyl group-etherification of a hydrogen-polyorganosiloxane is carried out in the presence of a platinum catalyst. The allyl groups rearrange internally through side reactions, forming a polyether ethered with propenyl groups. This propenyl-etherified polyether has no reactivity with the hydrogen-polyorganosiloxane and therefore remains in the system as an impurity. It is thought that when water reacts with this propenyl-etherized polyether, the propenyl ether hydrolyzes, giving propionaldehyde, which emits an unpleasant odor. The above hydrolysis reaction is known to be further favored in the presence of an acid catalyst.Therefore, when polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and causing an unpleasant odor.

[0232] Typical examples of the deodorization step include two approaches. The first is that in which, by adding an acid catalyst to the solution after the addition reaction, all the propenyl ether remaining in the system is hydrolyzed and the propionaldehyde that forms is removed by band purification (JP No. 2137062).

[0233] Specific examples of the acid catalyst used in the first approach include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. These acids are used in combination with water. In cases where it is necessary to remove the acid that has been used, it is preferable to use a low-boiling-point acid, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Similarly, from the point of view of treatment effectiveness, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

[0234] The processing temperature is preferably set at 80°C or less to avoid oxidation of the hydrophilic groups. The amount of acidic aqueous solution added is preferably set at 0.1 to 100% relative to the organosilicon resin modified with organic groups. The use of 5 to 30% is more preferred.

[0235] From a productivity standpoint, the preferred method is to add an aqueous solution to the post-reaction solution to adjust the pH to 7 or less and to perform strip purification after stirring under heating. Strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to efficiently purify the strip under these temperature conditions, it is preferable to carry out this operation under reduced pressure; when carried out at At normal pressure, the operation is preferably carried out under a flow of inert gas such as nitrogen or argon.

[0236] 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).

[0237] Hydrogenation reactions include methods involving the use of hydrogen and methods involving the use of metal hydrides, and there are also homogeneous and heterogeneous reactions. These methods can be used alone, but it is also possible to use them in combination. However, given the advantage that there is no trace of the catalyst used in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is preferred.

[0238] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron, and others, either in uncombined form or as a compound. In this case, a catalyst support is not required. However, when a catalyst support is used, it can be, for example, activated carbon, silica, silica-alumina, alumina, or zeolite. These catalysts can be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. Furthermore, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0239] It is preferable to carry out the hydrogenation reaction at a pressure generally between 1 and 100 MPa and between 50 and 200°C. The hydrogenation reaction can be carried out in batches or continuously. When it is a batch process, the reaction time depends, for example, on the amount of catalyst and the temperature, but it is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to a suitable fixed pressure. The endpoint of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing, and it can therefore be determined by carefully monitoring a pressure gauge.

[0240] The amount of aldehyde included in the glycerol-siliconized resin that has been purified by this acid treatment and this hydrogenation treatment can be fixed at 70 ppm or less, preferably at 20 ppm or less, and more preferably at 10 ppm or less.

[0241] It is also possible to combine the two types of deodorization steps mentioned above. In the approach that involves acid treatment, the Decomposition and removal of the aldehyde compound is possible, but because there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehyde cannot be completely eliminated. In the approach involving a hydrogenation reaction, removing the unsaturated double bonds reduces the amount of aldehyde compound formed. However, the aldehyde condensate that forms from the condensation of some of the aldehyde remains in the system even after such treatment, and removal by band washing is also difficult. Therefore, by alkylating the remaining unsaturated double bonds when the solution following the addition reaction is hydrogenated, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible (WO2002 / 05588).

[0242] The average molecular weight by weight of the glycerol-siliconized resin of average formula (1) varies, preferably, from 1000 to 100000; from the point of view of performance and ease of operations such as filtration, the average molecular weight by weight varies preferably from 3000 to 50000. Here and below, the average molecular weight by weight can be determined as the average molecular weight by weight equivalent to polystyrene in gel permeation chromatography (GC).

[0243] The glycerol-siliconized resin according to the invention is in a form at 25°C which can be solid or liquid; from the point of view of the formability of the film, it is preferably solid.

[0244] In particular, the glycerol-coated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b<30et0<c< 30, l'indice i dans la formule générale (2) est un nombre entier qui satisfait à la condition 0 < i < 3 et l'indice j dans la formule générale (3) satisfait à la condition 0 < j < 10 est sous la forme d'un solide à 25°C et présente, de préférence une masse moléculaire moyenne en poids qui varie de préférence comprise de 1000 à 100000 et plus préférentiellement, de 3000 à 50000.

[0245] The glycerol-coated silicone resins according to the invention have a hydrophilic-lipophilic equilibrium (HLB), as determined by Griffin's formula, preferably from 0.1 to 15, and more preferably from 1.0 to 8.0.

[0246] According to a preferred embodiment, the composition of the invention comprises at least one glycerol-coated silicone resin of formula (1) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate corresponding to the following formula (21): [(CH3)3SiO1 / 2]a [R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - R designates the 3-glyceroxypropyl group with structure -C3H6OCH2-CH(OH)CH2OH ; - the indices a, b and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.5.

[0247] According to a particularly preferred form, the glycerol silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution in at least one volatile oil.

[0248] For the purposes of this invention, "volatile oil" means any oil capable of evaporating upon contact with the skin in less than one hour at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1,300 Pa.

[0249] The volatile oil according to the invention can be chosen from the group consisting of hydrocarbon oils, silicone oils, and their mixtures.

[0250] By "hydrocarbon oil" is meant an oil containing predominantly hydrogen and carbon atoms and possibly one or more functions selected from among the hydroxyl, ester, ether and carboxylic functions.

[0251] For the purposes of the present invention, the term "siliconized oil" means an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.

[0252] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0253] Examples include C8-C16 isoalkanes (also called isoparaffins) such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and, for example, oils sold under the trade names Isopar® or Permetyl®. Isododecane is preferred.

[0254] By way of example of volatile silicone oils usable in the invention, one may cite volatile silicone oils, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 centistokes (2 x 10⁶ to 8 x 10⁶ m² / s), and containing in particular 2 to 7 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups containing 1 to 10 carbon atoms. Examples of volatile silicone oils usable in the invention include, in particular, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctytrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane. xane and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) is preferred.

[0255] According to a particularly preferred form, the glycerol silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in solution form at about 49-50% by weight in active matter in isododecane and has a weight average molecular mass of 11000. VOLATILE HYDROCARBONATE OILS

[0256] Composition (B) according to the invention comprises an oily phase comprising at least one volatile hydrocarbon oil.

[0257] Oil means any fatty substance in liquid form at room temperature (25°C) and atmospheric pressure (760 mm Hg or 1.013.105 Pa).

[0258] The term "oil phase" means an organic liquid phase at room temperature (25°C) and atmospheric pressure that is immiscible in water. It comprises at least one oil and any ingredient soluble or miscible in said phase.

[0259] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0260] Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopar® or Permetyl®.

[0261] C8-C16 branched esters such as isohexyl neopentanoate can also be mentioned. Other volatile hydrocarbon oils such as petroleum distillates, particularly those sold under the name Shell Soit® by the Shell company, can also be used.

[0262] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the volatile linear alkanes comprising from 6 to 14 carbon atoms.

[0263] As an example of linear alkanes suitable for the invention, mention may be made of the alkanes described in Cognis patent applications WO 2007 / 068371, or WO2008 / 155059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from coconut or palm oil.

[0264] By way of example of linear C6-C14 alkanes suitable for the invention, n-hexane (C6); n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), and mixtures thereof.

[0265] Notable examples include n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references PARAFOL 12 97® and PARAFOL 14 97® respectively, as well as their mixtures.

[0266] According to another embodiment, a mixture of n-dodecane and n-tetradecane is used. In particular, the dodecane / tetradecane mixture in the weight ratio 85 / 15 marketed by BIOSYNTHIS under the reference VEGELIGHT 1214® may be used.

[0267] According to yet another embodiment, a mixture of volatile linear alkanes in C9-C12 with INCI name: C9-12 ALKANE is used, such as the product marketed by the company BIOSYNTHIS under the reference VEGELIGHT SILK®.

[0268] According to yet another embodiment, a mixture of n-undecane (Cl 1) and n-tridecane (Cl3) is used, such as those obtained in examples 1 and 2 of application WO2008 / 155059 from Cognis and such as that sold under the trade name CETIOL ULTIMATE® by BASF.

[0269] According to a particularly preferred embodiment, the volatile hydrocarbon oil is selected from C8-C16 branched alkanes, and more particularly isododecane, the mixture of C9-C12 volatile linear alkanes and the mixture of n-undecane (C11) and n-tridecane (Cl3).

[0270] According to a particularly preferred embodiment, the composition (B) of the invention comprises at least one volatile oil selected from the C8-C16 isoalkanes (also called isoparaffins), alone or in mixtures, in particular isododecane.

[0271] The volatile hydrocarbon oil or oils are preferably present in the composition at levels less than or equal to 80% by weight, preferably from 40 to 70% by weight, relative to the total weight of the composition (B). SILICONE GUM

[0272] The composition according to the present invention comprises at least one silicone gum (c).

[0273] By silicone gum, we mean more particularly non-crosslinked linear polyorganosiloxanes, in particular polydimethylsiloxanes, optionally hydroxylated, phenylated, or vinylized, or combinations thereof. It should be noted that the silicone gums used according to the invention are not silicone elastomers.

[0274] According to the present invention, a silicone gum is also not considered to be a silicone oil.

[0275] More particularly, the silicone gum (c) is selected from polyorganosiloxanes with a weight-average molecular mass greater than or equal to 180,000 g / mol. Advantageously, the silicone gum is selected from polyorganosiloxanes with a weight-average molecular mass greater than or equal to 400,000 g / mol.

[0276] Molecular weight masses are measured in a conventional way in the field, for example using gel permeation chromatography coupled with static light scattering (GPC-MALLS).

[0277] Preferably, the viscosity of the silicone gum is greater than or equal to 300,000 cSt, advantageously greater than or equal to 400,000 cSt, more particularly greater than or equal to 800,000 cSt, more particularly less than or equal to 10,000,000 cSt (at 25°C, measured according to ASTM D-445). More particularly, between 800,000 and 5,000,000 cSt (at 25°C, measured according to ASTM D-445).

[0278] It is preferable that the silicone gum (c) not have a functional group such as an amino group.

[0279] The silicone gum (c) may be selected in particular from silicones of formula:

[0280] [Chem 2] in which: RI, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, R3 and R4 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, a vinyl radical, an aryl radical, or a hydroxyl radical. X is an alkyl radical containing 1 to 6 carbon atoms, a hydroxyl radical, an alkoxy radical containing 1 to 6 carbon atoms, and n and p being integers chosen such that the molecular mass of silicone gum is greater than or equal to 180,000 g / mol, advantageously greater than or equal to 400,000 g / mol.

[0281] In general, n and p can each take values ​​from 0 to 5000, more particularly from 0 to 3000, knowing that n and p are not naught simultaneously.

[0282] According to a particular embodiment, the silicone gum (c) is selected from polydimethylsiloxane gums, in particular those of INCI name Dimethicone, polydimethylsiloxane gums comprising at least one aryl radical, in particular those of INCI name: Diphenyl Dimethicone, gums of INCI name Dimethiconol, or mixtures thereof, and preferably gums of INCI name Dimethicone, alone or in mixtures.

[0283] The silicone gum(s) can be used alone or in mixture, in particular with one or more volatile or non-volatile oils.

[0284] According to a particular embodiment of the invention, the silicone gum (c) is in the form of a solution in one or more volatile or non-volatile oils.

[0285] Preferably, the volatile or non-volatile oil, identical or different from those mentioned above, is selected from volatile silicones; non-volatile polydimethylsiloxane oils; polyphenylmethylsiloxane oils; isoparaffins, in particular C8-C16 such as isododecane; methylene chloride; pentane; dodecane; tridecane; tetradecane; or mixtures thereof. Most preferably, the oil is selected from C8-C16 isoparaffins, alone or in mixtures, in particular isododecane.

[0286] When the silicone gum (c) of the invention is used in the form of a mixture, more particularly a solution, in one or more oils as described above, the proportion of silicone gum represents, preferably, 5 to 40% by weight, and more preferably 10 to 30% by weight relative to the total weight of said mixture (or solution).

[0287] Preferably, the composition (B) comprises a silicone gum(s) (c) content, expressed as active material, ranging from 2 to 35% by weight, and more particularly from 5 to 25% by weight, relative to the total weight of the composition (B).

[0288] Among the silicone gums that can be used in the context of the present invention, we can mention Dimethicone gums (all the R and X radicals are methyl groups), sold for example under the names Silsoft SE 30, Silsoft B3820 BLEND® (in isododecane) by the company Momentive Performance Materials, Belsil DM 500000 by the company Wacker, KF-9043 (in isododecane) by the company Shin Etsu.

[0289] Among the Dimethiconol gums (the R radicals are methyl groups and the X radicals are hydroxyl groups), we can mention in particular those sold under the names Xiameter® PMX-1401 Fluid (in cyclopentasiloxane), Xiameter PMX-1503 Fluid (in a Dimethicone), Xiameter® PMX-1403 Fluid (in a dimethicone) by the company Dow Corning, the products of the Mirasil D-DML-LV range marketed by the company Elkem Silicones, Silsoft 1215 (in cyclopentasiloxane) by the company Momentive Performance Materials.

[0290] With regard to Diphenyl dimethicone type gums (R3 and R4 representing an aryl group, the other radicals R and X representing methyl groups) one can cite for example Mirasil C-DPDM (in cyclopentasiloxane) marketed by the company Elkem Silicones.

[0291] Among dimethicones of the (polydimethylsiloxane) (methylvinylsiloxane) type, such as SE63® sold by GE Bayer Silicones, poly(dimethylsiloxane) (diphenyl) (methylvinylsiloxane) copolymers and mixtures thereof. LIPOPHILIC THICKENER

[0292] According to a preferred form, the composition (B) according to the invention further comprises at least one lipophilic thickener.

[0293] The term “lipophilic thickener” means any lipophilic or lipophilicly soluble molecule in the oily phase of the composition capable of increasing the viscosity of the composition.

[0294] As a lipophilic thickener, at least one lipophilic clay will preferably be used.

[0295] Clay refers to a material based on hydrated silicates and / or aluminosilicates with a lamellar structure.

[0296] Clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as a C22 C1O ammonium chloride, in particular steralkonium chloride or di-stearyl di-methyl ammonium chloride.

[0297] They can be chosen from among bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

[0298] Preferably, they are chosen from among the hectorites and the bentonites.

[0299] According to a particularly preferred form, a lipophilic clay selected from hydrophobic modified bentonites and hydrophobic modified hectorites, in particular by a quaternary ammonium chloride in C22 C1O, will be used, such as: - a bentonite modified by stearalkonium chloride such as the commercial products sold under the name CLAYTONE AF®, GARAMITE VT®, TIXOGEL® LG-M, TIXOGEL® MP 250 TIXOGEL® VZ, TIXOGEL® VZ-V XR, by 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 STEARINERIE DUBOIS FILS, MYGLYOL GEL T® from Cremer Oleo, TIXOGEL® CGT 6030, TIXOGEL® DBA 6060, TIXOGEL® FTN, TIXOGEL® FTN 1564, TIXOGEL® IPM, TIXOGEL® LAN, TIXOGEL® LAN 1563 by BYK Additives Inc; - a hectorite modified by distearyl dimethyl ammonium chloride (INCI name: DISTEARDIMONIUM HECTORITE) such as, for example, that marketed under the name BENTONE® 38VCG RHEOLOGICAL ADDITIVE by the company Elementis Specialities; - a hectorite modified by distearyl dimethyl ammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil such as the commercial products sold under the name BENTONE® GEL DOA V, BENTONE® GEL EUG V, BENTONE® GEL IHD V, BENTONE® GEL ISD V, BENTONE® GEL MIO V® BENTONE® GEL PTM V® BENTONE® SS-71 V, BENTONE® VS-5 PC V, BENTONE® VS-5® by the company Elementis Specialities; the commercial products sold under the name CREAGEL BENTONE CPS / HECTONE CPS®, CREAGEL BENTONE ID / HECTONE ID® by the company Créations Couleurs; the commercial products sold under the name NS GEL DM1®, NS GEL PTIS®, NS MGEL 1152® by the company Next Step Laboratories Stop.

[0300] In particular, a hectorite modified by distearyl dimethyl ammonium chloride (INCI name: DISTEARDIMONIUM HECTORITE) will be used, such as, for example, that marketed under the name BENTONE® 38VCG RHEOLOGICAL ADDITIVE by the company Elementis Specialities.

[0301] The lipophilic thickener(s) may be present in the composition at concentrations ranging, preferably, from 0.5 to 10% by weight, and more preferably from 1 to 6% by weight, relative to the total weight of the composition (B). COSMETIC ADDITIVES

[0302] Composition (B) may contain conventional cosmetic additives, preservatives, perfumes, antioxidants, moisturizing agents, lipophilic actives such as vitamins, lipophilic UV filters, fillers.

[0303] Of course, a person skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or substantially not, altered by the envisaged addition.

[0304] The composition (B) used according to the invention may be a care and / or makeup composition for keratinous materials, in particular for eyebrows including eyebrow hairs, the skin in which said hairs are implanted and their contours.

[0305] According to a particularly preferred form, the composition (B) of the invention is anhydrous.

[0306] For the purposes of the invention, the expression "anhydrous composition" means respectively a composition which contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water by weight of its total weight, and in particular a composition free of water.

[0307] Such compositions are in particular prepared according to the general knowledge of the person skilled in the art.

[0308] Composition (B) of the invention may be in the form of an assembly or kit for conditioning and applying a coating composition for keratinous materials, comprising: - a conditioning device comprising said composition (B) as previously described, - an applicator of said composition.

[0309] The container may delimit one or more compartment(s). The container may, for example, be in the form of a tube.

[0310] Such an applicator may be attached to a cap mounted reversibly on said container between a closing position of said container and a makeup position.

[0311] Alternatively, such an applicator can be irreversibly mounted on said container. Examples of such applicators include felt-tip pens and brushes, which may be made of synthetic fibers.

[0312] It is understood that within the framework of the present invention, the weight percentages given for a compound or a family of compounds are always expressed in weight relative to the total weight of the composition.

[0313] Throughout the application, the expression "includes a" or "comprises a" should be understood as meaning "containing at least one" or "comprising at least one", unless otherwise specified.

[0314] It is understood that the following examples are provided for illustrative purposes only and are in no way limiting the scope of protection conferred by this application. EXAMPLES OF PREPARATION

[0315] Example 1: Preparation of a 60 wt% isododecane solution of a silicone resin modified by 3-glyceroxypropyl groups

[0316] A reactor was loaded with 1300 g of a 50% isododecane solution of a powdered organosilicon resin containing a hydrosilyl group, of average composition formula (E4) (weight average molecular weight, 4480; amount of hydrogen gas evolution, 8.0 mL / g), 30.7 g of glycerol monoallyl ether of formula (E5), 1300 g of 2-propanol and 0.7 g of a 0.5% chloroplatinic acid solution in 2-propanol, and the reaction was carried out by heating for 6 hours at 100°C. The solvent was then removed by heating under reduced pressure. Next, 325 g of ethanol were added, followed by 6.5 g of a 5% aqueous sodium hydroxide solution, hydrolyzing the unreacted hydrosilyl groups. Neutralization was then carried out by adding 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of hydrochloric acid...

[0317]

[0318]

[0319] Aqueous 0.01 N sodium bicarbonate was added, hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene, and neutralization was carried out with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was then heated under reduced pressure to drive off the solvent and filtered, yielding an isododecane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). (Me3SiO 1 / 2)27.8(HMe2SiO 1 / 2) 1.6(SiO4 / 2)35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiO 1 / 2)27.8(R2Me2SiO 1 / 2) 1.6(SiO4 / 2)35.3 (E6) R2= -CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H. Examples of eyebrow makeup compositions The following (Al) Base Coat composition for pencil lead was prepared. [Table 1] Phase Ingredients (INCI name) Composition (A 1) A OZOKERITE 7 EUPHORBIA CERIFERA (CANDELIL LA) WAX 3 MICROCRYSTALLINE WAX 1 HYDROGENATED COCO-GLYCERI DES 10 POLYETHYLENE 22 C20-40 ALCOHOLS (and) POLYETHY LENE 3 B C12-15 ALKYL ETHYLHEXANOATE qs 100 POLYGLYCERYL-2 TRIISOSTEARA TE 5 GLYCERYL CAPRYLATE 0.05 TOCOPHERYL ACETATE 0.1 C ZINC STEARATE 3 MICA (and) DIMETHICONE 7 IRON OXIDES / CI 77499 6.3 IRON OXIDES / CI 77491 2.0 IRON OXIDES / CI 77492 5.8 TITANIUM DIOXIDE / CI 77891 12 Composition preparation protocol (Al)

[0320] Phase A of waxes was melted and combined with the oily phase B. The various solid compounds of phase C, such as zinc stearate, pigments, and silicone-coated mica, were then added to this mixture, and the whole was homogenized again. The resulting matrix was then formulated as a pencil lead using a conventional process.

[0321] The following Top Coat compositions (Bl) and (B2) were prepared.

[0322] Contents are indicated as % by weight of raw material, unless otherwise stated opposite.

[0323] [Tables2] Ingredients (INCI name) Composition B1 (comparative) Composition B2 (invention) Glycerol-based silicone resin: (3-GLYCEROXYPROPYL)DIMETHYLSIL OXY TRIMETHYLSILOXYSILICATE - Formula (21) in 50% solution in isododecane obtained in Example 1 9,1 9,1 TRIMETHYLSILOXYSILICATE (in solution in isododecane; 75% by weight of resin; Silsoft 74 Fluid® from Momentive Performance Materials) 18 18 NYLON-611 / DIMETHICONE COPOLYMER (Dowsil 2-8179 Gellant® from Dow Corning) 12% MA (*) 0 Silicone gum: Dimethicone blend in isododecane (Silsoft B3820 Blend from Momentive Performance Materials) 0 12% MA (*) Disteardimonium Hectorite (Bentone 38 VCG® Rheological Additive from E lementis) 5 5 Propylene Carbonate 1.65 1.65 Isododecane Qsp 100 Qsp 100

[0324] (*) MA = active ingredient Composition preparation protocol

[0325] 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).

[0326] Tests to measure durability: Resistance to makeup remover oil: A layer of pencil was deposited on Supplale® in a 4 x 5 cm rectangle. If necessary, a layer of top coat (50mg) was applied evenly over the layer of pencil with a beveled brush. The deposit was left to dry for 24 hours. Five colorimetric data measurements were taken on each spot (T0) at the four corners and the center of the Supplale® using a CM 700d® spectrophotometer (Minolta). Three drops of cleansing oil (Shu Uemura - Ultime 8 Cleansing Oil®) were applied to the spot. The deposit to be evaluated was rubbed in a circular motion 4 times. We rinsed it with water. We dabbed with a tissue to remove the excess water. We repeated the operation 5 times on each deposit. The deposit was left to dry for 24 hours. We performed 5 colorimetric data measurements (T5) on each deposit. The variation of the AE color between T0 and T5 was measured in the CIE L*a*b* system, using the CM 700d Spectrophotometer (illuminant D65, angle 10°, specular component excluded). The value of AE is calculated according to the following equation: AE = [(L* - L*0)2 + (a* - a0*)2 + (b* - b0*)2]1 / 2 where L*a*b* represent the values ​​of the coordinates in the CIE Lab 76 color space, measured after the test, and Lo*, a0*b0* represent the values ​​measured before the test. Results

[0327] The results obtained are shown in the table below:

[0328] [Tables3] Comparative Al Comparative Al + Bl Invention Al + B2 AE 10.52 2.06 0.78 Standard deviation AE 0.25 0.46 0.37

[0329] The results of comparative tests showed that the two-step makeup process comprising the application of the pencil (A1) followed by the application of the composition (B2) according to the invention comprising the association of a silicone resin non-glycerolized, of a glycerolized silicone resin, of a silicone gum and of a volatile oil led to a makeup with excellent resistance to cleansing oil unlike the one-step makeup process using the pencil (Al) or followed by a top coat outside the invention because it lacks silicone gum and includes a silicone polyamide.

Claims

Demands

1. A coating method, in particular for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin of implantation of said hairs and their contours, comprising at least the following steps: 1) the application of a first composition (A) “Base Coat” of the type of pencil lead comprising, in particular in a physiologically acceptable medium: i) at least one wax, ii) at least one non-volatile oil, iii) at least one coloring matter, 2) the application on the layer formed by composition (A), of a second layer formed by a composition (B) “Top Coat” comprising, in particular in a physiologically acceptable medium: a) at least one non-glycerol silicone resin; b) at least one glycerol silicone resin; c) at least one silicone gum; d) at least one oily phase comprising at least one volatile hydrocarbon oil.

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

3. The process according to claim 2, characterized in that the composition (A) comprises at least one hard wax selected from Candelilla wax, INCI name Euphorbia Cerifera (Candelilla) Wax; rice bran wax, INCI name Oryza Sativa (Rice) Bran Wax; a microcrystalline wax, INCI name Microcrystalline Wax; a polyethylene wax; a mixture of waxes, INCI name C20-40 Alcohols (and) Polyethylene; hydrogenated coconut oil, INCI name Hydrogenated Cocoglycerides; and mixtures thereof.

4. A method according to any one of the preceding claims, characterized in that the composition (A) comprises a content of wax(s) ranging from 20 to 50% by weight, and preferably from 25 to 45% by weight, relative to the total weight of the composition.

5. A process according to any one of the preceding claims, characterized in that, in composition (A), the non-volatile oil or oils is / are selected hydrocarbon oils, silicone oils or mixtures thereof, and preferably from oils of formula R1COOR2, in which RI represents a remainder of at least one linear or branched fatty acid comprising from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular, branched containing from 1 to 40 carbon atoms provided that RI + R2 is greater than or equal to 10, C4 to Cl8 fatty acid triglycerides, and mixtures thereof.

6. A process according to any one of the preceding claims, characterized in that the composition (A) comprises a content of non-volatile oil(s) ranging from 5 to 30% by weight, preferably from 7 to 20% by weight, relative to the total weight of the composition.

7. A process according to any one of the preceding claims, characterized in that the composition (A) comprises a content of colouring matter(s) 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. A method according to any one of the preceding claims, characterized in that the composition (A) comprises at least one powdered colouring material of the mineral pigment type, in particular selected from titanium dioxides, black, red or yellow iron oxides, coated or uncoated, ferric aluminium ferrocyanide, and mixtures thereof.

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

10. A method according to any one of claims 1 to 8, characterized in that composition (A) comprises an aqueous phase.

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

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

13. A process according to claim 12, characterized in that the Trimethylsiloxysilicate type resin is in solution in isododecane.

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

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

16. A process according to any one of the preceding claims, characterized in that, in composition (B), the glycerol-siliconized resin contains at least one organosiloxane motif 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. A process according to claim 16, characterized in that in composition (B), the glycerol silicone resin contains at least one dimethylsiloxane motif R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

18. A method according to any one of the preceding claims, characterized in that, in composition (B), the glycerol-coated silicone resin(s) are selected from those of the following formula (1): (R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2) KD, wherein each R1, identical or different, is an alkyl, aryl, or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a

19. halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - each R2 is a mono- or poly-glycerol group with the following general formula (2) —(CH2)2—C^—O—(CH2CH(OH)CH2O);R4(2) in which - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, and - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is a group identical or different from general formula (3), general formula (4), general formula (5) or general formula (6) below —(CH2)2—CmH2m—(SiOR'2)j—SiR1, (3) —(CH2)2—CmH2m—SiR*kl—(OSiR*3)3_kl) (4) —(CH2)2—CmH2m—SiR'kl—(OSiR^COSiR1^ k2)3 k[ (5) —(CH2)2—CmH2m—SiR'kl—(OSiRUOSiR^OSiR1,), (6) Or - each R1, whether identical or different, is an alkyl, aryl, or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino, or a group substituted by a carboxyl group thereof - the indices m, j and ki to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; - the indices a, b, c, d, e and f are numbers that satisfy the conditions 0 < a < 400, 0 ​0.5 < (a+b+c) / f < 1.

5. A process according to claim 18, characterized in that, in composition (B), the glycerol-coated silicone resin(s) of formula (1) are selected from those of which - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; - the index i in the general formula (2) of the polyglycerol group R2 is an integer that satisfies the condition 0 < i < 3.

20. A method according to any one of claims 18 or 19, characterized in that, in composition (B), the glycerol-siliconized resin(s) of average formula (1) are in solid form at 25 °C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

21. A method according to any one of claims 18 to 20, characterized in that, in composition (B), the glycerol-siliconized resin(s) has (have) a hydrophilic-lipophilic equilibrium (HLB), as determined by Griffin's formula, ranging from 0.1 to 15, and more preferably from 1.0 to 8.

0.

22. A process according to any one of claims 18 to 21, characterized in that the composition (B) comprises at least one glycerolated silicone resin of formula (1) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate corresponding to the following formula (21): [(CH3)3SiO1 / 2]a[R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - R denotes the 3-glyceroxypropyl group of structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers which satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.

5.

23. A process according to claim 22, characterized in that the glycerol-coated silicone resin of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in solution in at least one volatile oil.

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

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

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

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

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

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

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

31. A process according to claim 30, characterized in that the composition (B) comprises a content of lipophilic thickener(s) ranging from 0.5 to 10% by weight, and more preferably from 1 to 6% by weight, relative to the total weight of the composition (B).

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

33. A set or kit for coating, in particular for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, comprising at least 1) a composition (A) as defined in any one of claims 1 to 11; and 2) a composition (B) as defined in any one of claims 12 to 32; said compositions (A) and (B) being packaged separately.