Eyebrow makeup composition with a non-glycerol silicone resin, a glycerol silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener

Abstract

Eyebrow makeup composition with a non-glycerol silicone resin, a glycerol silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener. The present invention relates to an anhydrous composition for the care and / or makeup of keratinous materials, in particular of the eyebrows and the skin around the eye and eyebrows, comprising, in particular in a physiologically acceptable medium: (a) at least one non-glycerol silicone resin; and (b) at least one glycerol silicone resin; and (c) at least one silicone gum; and (d) at least one oily phase comprising at least one volatile hydrocarbon oil; and (e) a lipophilic thickener.It also relates to a process of coating keratinous materials, in particular eyebrows and skin around the eye and eyebrows, and more particularly a process of making up said keratinous materials, including the application to them of the composition as defined above.

Description

Title of the invention: Eyebrow makeup composition with a non-glycerol silicone resin, a glycerol silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener

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

[0002] In the field of eyebrow makeup, consumers have access to several types of solutions: - Eyebrow pencils, which are easy to use but only last a day. They are often based on a pigmented lead that colors by transferring material onto the skin. - Pens, which are also easy to use but only last a day. They are often made with water-based formulas containing dyes. - Tattoo parlor services, which are very painful, but last for several months. - anhydrous gels such as the commercial products Semi-Permanent Brow Ink by Revlon (Mintel ID 9314122), Jason Wu-Brow Everlasting Love Eyebrow Gel® by JW Beauty (Mintel ID 9811090), L'Oréal Paris Unbelievabrow Longwear Brow Gel® (Mintel ID 10352772) containing an MQ resin: TRIMETHYLSILOXYSILICATE and the commercial products Inked Waterproof Brow Gel® by Urban Decay (Mintel ID 7578707) and Up to 3 Day Styling Gel® by Maybelline (Mintel ID 10361806) containing isododecane and the combination of an MQ resin: TRIMETHYLSILOXYSILICATE and a silicone polyamide: NYLON-611 / DIMETHICONE COPOLYMER.

[0003] Users of makeup formulations containing keratinous materials, such as eyebrows and the skin around the eyes and eyebrows, seek products with longer-lasting wear, which is reflected in particular by better resistance of the film to makeup-removing oils. When this film is present on the skin around the eyes and eyebrows, it tends to make it difficult to maintain eyebrow makeup.

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

[0005] Unexpectedly, the inventors found that it is possible to achieve these objectives using a composition, preferably for the care and / or makeup of keratinous materials, in particular eyebrows including eyebrow hairs, the skin on which said hairs are implanted and their contours, including, in particular in a physiologically acceptable environment: (a) at least one non-glycerol silicone resin; and (b) at least one glycerol-based silicone resin; and (c) at least one silicone eraser; and (d) at least one oily phase comprising at least one volatile hydrocarbon oil; and (e) a lipophilic thickener.

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

[0007] Thus, a first object of the present invention is a composition, preferably 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, in particular in a physiologically acceptable environment: (a) at least one non-glycerol silicone resin; and (b) at least one glycerol-based silicone resin; and (c) at least one silicone eraser; and (d) at least one oily phase comprising at least one volatile hydrocarbon oil; and (e) a lipophilic thickener.

[0008] A second object of the present invention is a method of coating keratinous materials, in particular eyebrows and skin around the eye and eyebrows, and more particularly a method of making up said keratinous materials, comprising applying to them the composition as defined above. Definitions

[0009] 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.

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

[0011] By "glycerol-based silicone resin", we mean any silicone resin comprising at less an organosiloxane motif comprising one or more monoglycerol or polyglycerol group(s) in its chemical structure.

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

[0013] By “hydrocarbon radical”, we mean a radical containing predominantly hydrogen and carbon atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether and carboxylic functions.

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

[0015] By "polyglycerol group" 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 Non-glycerol silicone resin

[0016] The composition according to the invention comprises at least one non-glycerol silicone resin (a).

[0017] More generally, the term resin refers to a compound with a three-dimensional structure. Silicone resins are also called silicone resins or "siloxane resins." Thus, for the purposes of the present invention, polydimethylsiloxane is not a silicone resin.

[0018] The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known as MDTQ, the resin being described according to the different siloxane monomeric units it comprises, each of the letters MDTQ characterizing a type of unit.

[0019] The letter M represents the Monofunctional unit of formula RiR2R3SiOi / 2, the silicon atom being bonded to a single oxygen atom in the polymer comprising this unit.

[0020] The letter "D" signifies a Difunctional unit RiR2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.

[0021] The letter T represents a RiSiO3 / 2 trifunctional unit.

[0022] 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.

[0023] In the motifs M, D, T defined above, R, namely RB R2 and R3, represents a hydrocarbon radical (especially alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0024] 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.

[0025] 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.

[0026] As examples of non-glycerol silicone resins (a) 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:

[0027] As an example of MQ type silicone resins, alkylsiloxy-silicates of formula [(Ri)3SiOi / 2]x(SiO4 / 2)y (MQ units) may be cited, in which x and y are integers from 50 to 80, and such that the Ri group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0028] As an example of MQ silicone resins of the Trimethylsiloxysilicate type, one can cite 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. T Resins:

[0029] As an example of T-type silicone resins, we can cite polysilses-quioxanes of formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

[0030] Preferably, polymethylsilsesquioxane resins can be used in which R represents a methyl group, such as those commercially available: - by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: a polymer comprising repeating CH3SiO3 / 2 units (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2 units (D units) and having an average molecular weight of approximately 10000 g / mol, or - by the company SHIN-ETSU under the references KR-220L® which are composed of T units of formula CH3SiO3 / 2 and have Si-OH (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®, comprise 88% T units and 12% Dimethyl D units and have Si-OH terminal groups. MQT resins:

[0031] As examples of resins comprising MQT motifs, those cited in US document 5 110 890 are known in particular.

[0032] A preferred form of MQT-type resins is MQT-propyl resin (also called MQTPr). Such resins usable in the compositions according to the invention include, in particular, those described and prepared in the application WO 2005 / 075542.

[0033] The MQ-T-propyl resin preferably comprises the following units: (i) ((Russia) (ii) ((R2)2SiO2 / 2)b (iii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with Ri, R2 and R3 independently represent a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d= 1, provided that more than 40% by mole of the R3 groups of the siloxane resin are propyl groups.

[0034] Preferably, the siloxane resin comprises the following units: (i) ((R1)3SiO1 / 2)a (ii) (R3SiO3 / 2)c and (iv) (SiO4 / 2)d with Ri and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, Ri preferably being a methyl group and R3 preferably being a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or even 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.

[0035] The siloxane resins (a) usable according to the invention can be obtained by a process comprising the reaction of A) an MQ resin comprising at least 80 mole percent of ((Ri)3SiO1 / 2)a and (SiO4 / 2)d units Ri representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the a / d ratio being between 0.5 and 1.5; and of B) a propyl resin T comprising at least 80 mole percent of (R3SiO3 / 2)c units, R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, provided that at least 40 mole percent of the R3 groups are propyl groups, where the mass ratio A / B is between 95:5 and 15:85, preferably the mass ratio A / B is 30:70.

[0036] 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 proven to allow comfortable deposition.

[0037] Preferably, the composition according to the invention comprises, as a non-glycerol silicone resin (a), at least one MQ type resin, more particularly of the Tri-methylsiloxysilicate 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.

[0038] 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.

[0039] According to a particular embodiment of the invention, the non-glycerol silicone resin(s) (a) is (are) present in the composition in an active material content ranging from 4 to 35% by weight relative to the total weight of the composition, preferably ranging from 6 to 30% by weight and more preferably from 8 to 25% by weight relative to the total weight of the composition. Glycerol-based silicone resin

[0040] The composition according to the invention comprises at least one glycerol-coated silicone resin (b).

[0041] The glycerol-coated silicone resin (b) comprises in its chemical structure one or more monoglycerol or polyglycerol groups.*

[0042] According to a particular embodiment of the invention, the glycerol silicone resin(s) (b) is (are) present in an active matter content ranging from 0.1 to 40% by weight relative to the total weight of the composition, preferably ranging from 0.2 to 30% by weight and more preferably from 0.5 to 15% by weight relative to the total weight of the composition.

[0043] The glycerol silicone resin(s) (b) according to the invention are preferably chosen from those of the following formula (1). [Chem 1] (R13SiO1 / 2)a(R2(CH3)2SiO1 / 2)b(R33SiO1 / 2)c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (1) in which - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - each R2 is a mono- or poly-glycerol group of the following general formula (2)

[0044] [Chem 2] —(CH2)2—QHa—O—(CH2CH(OH)CH2O);R4 (2) in which - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, and - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5, - each R3 is a group identical or different from general formula (3), general formula (4), general formula (5) or general formula (6) below [Chem 3] —(CH2)2—CmH2m—(SiORyj—SiR>3 (3) [Chem 4] —(CH2)2—CmH2m—SiR'kl—(OSiR'3)3 kl) (4) [Chem 5] —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (5) [Chem 6] —(CH2)2—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 kl (6) where - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino, or a group substituted by a carboxyl group 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

[0045] Glycerol-coated silicone resins (b) according to the invention are described in SHIN ETSU's US patent application US20200332065A1.

[0046] According to a particular method, the glycerol-coated silicone resin(s) (b) of formula (1) as defined above are chosen from those of which - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; ​- the index i in the general formula (2) of the monoglycerol or polyglycerol group R2 is an integer that satisfies the condition 0 < i < 3.

[0047] According to a particular mode, the glycerol silicone resin(s) (b) of formula (1) are in solid form at 25 °C when the index c satisfies the condition 0 < c < 400 and R 3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

[0048] According to a particular mode, the glycerolized silicone resin(s) (b) have an average molecular weight by weight ranging from 1000 to 100000.

[0049] The glycerol-coated silicone resin(s) (b) according to the invention are amphiphilic, that is, they have two parts of 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 the value of their HLB (Hydrophilic Lipophilic Balance), the HLB being the ratio between the hydrophilic and lipophilic parts in the molecule. The term HLB is well known to those skilled in the art and is described, for example, in "The HLB System: A Time-Saving Guide to Emulsifier Selection," published by ICI Americas Inc., 1984. The HLB value of the glycerol-coated silicone resins according to the invention preferably varies from 0.1 to 15 according to Griffin's method.

[0050] The glycerol-coated silicone resin(s) according to the invention can be obtained by a preparation process comprising the hydrosilylation step A) of a silicone resin containing a hydrosilyl group of formula (7) below. [Chem 7] (R13SiO1 / 2)aHnR13_nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f (7) in which: - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0 < d < 320, 0 < e < 320, 0 < f < 1000 and 0.5 < (a+b+c) / f < 1.5; - n is an integer that satisfies the condition 1 < n < 3, with B) one or more compounds which are chosen from the compounds ending with an alkenyl group of general formulas (8), (9), (10), (11) and (12) below. [Chem 8] CH2=CH-CiH21-O-(CH2CH(OH)CH2O)iR4(8) [Chem 9] CH2=CH-CmH2m-(SiOR12)j-SiR13 (9) [Chem 10] CH2=CH—CmH2m—SiR'kl—(OSiR13)3 kl (10) [Chem 11] CH2=CH—CmH2m—SiR'kl—(OSiR WOSiR'^k2)3kl (11) [Chem 12] CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15, 0 <i<5; - the indices m, j and kl to k3 are integers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said silicone resin containing a hydrosilyl group of formula (7) reacting with at least one compound of formula (8).

[0051] 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.

[0052] Silicone resin containing a hydrosilyl group used as a starting material.

[0053] The silicone resin containing a hydrosilyl group of formula (7) can be in solid or liquid form at 25°C, although, in terms of film-forming ability, it is preferably solid. From a utility standpoint, the resin is preferably diluted with an organic solvent. The use of a solvent whose boiling point is higher than the reflux temperature during hydrolysis is preferred.

[0054] Examples of organic solvents used for dilution include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; and ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the point of view of storage stability and lack of volatility, octamethylcyclotetrasiloxane and decamethylcyclopenta-siloxane are preferred.

[0055] 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.

[0056] [Chem 13] RSSiOSiRS (13) [Chem 14] RSSiX1 (14) [Chem 15] HnR*(3.n)SiOSiR1(3.n)Hn(15) [Chem 16] HnR'(3 n)SiX2 (16) where - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - X1 and X2 are hydrolyzable functional groups; and - n satisfies the condition 1 < n < 3.

[0057] [Chem 17] SiX34(17) where X3 is a hydrolyzable functional group), ii) by neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acidic catalyst, and iii) by then performing a condensation.

[0058] In the general formulas (13), (14), (15) and (16), the examples and the range The preferred ones for R1 are the same as those mentioned above.

[0059] In the general formula (14), X1 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the point of view of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0060] In the general formula (16), X2 is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Of these, from the point of view of availability and hydrolysis rate, a methoxy group, an ethoxy group, or a chlorine atom is preferred.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Examples of organosilicon compounds containing a hydrosilyl group of general formula (15) include 1,1,3,3-tetramethyldisiloxane and the I, IJ ,3,3-pcntamethyldisiloxane. 1,1,3,3-Tetramethyldisiloxane is particularly preferred.

[0065] Furthermore, in the general formulas (15) and (16), n satisfies the condition 1 < n < 3. In the general formula (15), the "n" associated with the H and R1 bonded to one silicone atom and the "n" associated with the H and R1 bonded to the other silicone atom can be identical or different.

[0066] Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0067] 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.

[0068] In this invention, to a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulas (15) and (16) and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metallic salts of these hydrolyzable silanes may be added before hydrolysis under an acid catalyst, or a mixture of one or more compounds selected from organosilicon compounds of general formula (18) or general formula (19) may be added after such hydrolysis and before the rehydrolysis described later.

[0069] [Chem 18] R'SiX43 (18) [Chem 19] R12SiX52 (19) where - each R1 is an alkyl, aryl or aralkyl group identical or different from 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - X4 and X5 are hydrolyzable functional groups

[0070] In general formulas (18) and 19), the examples and preferred ranges for R1 are the same as those mentioned above.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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 salts of The alkaline components of these hydrolyzable silanes are loaded into a reactor, an acid is added as a catalyst, and water is added dropwise while stirring. Alternatively, the organic solvent can be added after the dropwise addition of water is complete. Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0076] 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 the hydrosilyl groups.

[0077] 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.

[0078] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane.

[0079] In some cases, an alcoholic solvent of 1 to 10 carbon atoms may be used concomitantly. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Because alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol, and 2-propanol are particularly preferred.

[0080] 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.

[0081] 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 can be used in small amounts, with an amount on the order of 0.001 to 10% of the overall reaction system being preferred.

[0082] 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.

[0083] 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.

[0084] After the above hydrolysis, the system is neutralized at 10 to 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide. At this point, using a strong basic catalyst and a weak basic catalyst together prevents the deactivation of the hydrosilyl group and further promotes the condensation reaction of the organosilicon resin. Examples of such strongly basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate.Regarding combinations of a strong basic catalyst with a weak basic catalyst, from the perspective of easily achieving a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, making it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

[0085] The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. Performing the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, resulting in an increase in molecular weight and yielding a high molecular weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the amount of addition within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, resulting in a resin of target molecular weight.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] In the process described above for preparing a silicone resin containing hydrosilyl groups, after carrying out the hydrolysis, in the presence of an acid catalyst, of a mixture of one or more compounds selected from the organosilicon compounds of general formulas (13) and (14) with one or more compounds selected from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes and metallic salts of these hydrolyzable silanes, it is possible to add also gradually, drop by drop, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group, of general formulas (15) and (16).

[0090] Next, a rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably carried out by heating to a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example, preferably between 40 and 150°C, and more preferably between 40 and 120°C. for approximately 2 to 8 hours. When the reaction is carried out within this temperature range, the deactivation of the hydrosilyl groups can be further suppressed.

[0091] In the process of preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups are deactivated, can occur. [Chem 20] StQ 1 / 2 (2°) .49 p- T ?.. ? I.) wmùs i where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

[0092] 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.

[0093] 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 amount of hydrolysis starting materials used, the type and quantity of acid catalyst added, the reaction temperature and time, the amount of solvent added and the method of addition, the molecular weight range, shape, and other characteristics of the organosilicon resin can be adjusted, making it possible to prepare an organosilicon resin containing hydrosilyl groups for the intended application.

[0094] 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 ((RSSiO2 / 2) and (HnR'3 nSiO2 / 2)) as essential constituents, and also of D units (R12SiO2 / 2) and T units (R'SiO2 / 2) as optional constituents. It can be in the form of a solid or a liquid at 25°C, although from the point of view of film forming, 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 standpoint of performance and ease of performing operations such as filtration. The average molecular weight can be determined as the equivalent average molecular weight of polystyrene in gel permeation chromatography (GC).

[0095] Process for preparing glycerol-coated silicone resin (b)

[0096] A specific example of a process for preparing the glycerol-siliconized resin (b) according to the invention is described below.

[0097] As mentioned above, the glycerol-siliconized resin (b) according to the invention can be obtained by the hydrosilylation step (A) of a silicone resin containing a hydrosilyl group of average formula (7) below: (R13SiO1 / 2)a(HnR13_nSiO1 / 2)b+c(R12SiO2 / 2)d(R1SiO3 / 2)e(SiO4 / 2)f(7) in which - each R1 is an alkyl, aryl or aralkyl group identical or different from 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl of the latter; - the indices a, b, c, d, e and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0 < d < 320, 0 < e < 320, 0 < f < 1000 and 0.5 < (a+b+c) / f <1.5; - n is an integer that satisfies the condition 1 < n < 3 with (B) one or more compounds which are selected from the compounds ending in an alkenyl group of general formulas (8), (9), (10), (11) and (12) below. CH2=CH-CiH21-O-(CH2CH(OH)CH2O)iR4(8) CH2=CH-CmH2m-(SiOR12)j SiR>3 (9) CH2=CH—CmH2m—SiR'kl—(OSiR'3)3 kl (10) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR13)3 k2)3 kl (11) CH2=CH—CmH2m—SiR'kl—(OSiR1k2(OSiR1k3(OSiR13)3 k3)3 k2)3 kl (12) where - R4 is a monovalent hydrocarbon group, substituted or unsubstituted, or a hydrogen atom, - the indices 1 and i are integers that satisfy the conditions 0 < 1 < 15, and 0 < i < 5; - the indices m, j and ki to k3 are integers that satisfy the conditions 0 < m < 5, 0 < j < 500, 0 < kl < 2, 0 < k2 < 2 and 0 < k3 < 2; said includes a compound of general formula (8).

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups may be included. Particularly in cases where use in applications such as cosmetic preparations is planned, there is a possibility These hydrosilyl groups deactivate over time due to dehydrogenation reactions, which poses a safety concern. Therefore, it is preferable to include a step to maintain the hydrosilyl groups.

[0105] An example of a step for removing hydrosilyl groups is the process of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, followed by neutralization by adding an amount of acidic catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the point of view 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.

[0106] After the addition reaction, if necessary, a deodorization step to reduce the odor may be included. When use in applications such as cosmetic preparations is planned, in particular, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common silicones modified with polyethers can be explained as follows. When an addition reaction between a polyether etherized with allyl groups and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as side reactions, forming a polyether etherized with propenyl groups. This propenyl-etherized polyether has no reactivity with the hydrogen polyorganosiloxane and therefore remains in the system as an impurity.It is believed that when water reacts with this propenyl-etherified polyether, the propenyl ether hydrolyzes, yielding propionaldehyde, which emits an unpleasant odor. The above hydrolysis reaction is known to be further promoted in the presence of an acidic catalyst. Therefore, when polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, further promoting the hydrolysis reaction. described above and causing the appearance of a bad odor.

[0107] 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).

[0108] 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.

[0109] 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.

[0110] From a productivity standpoint, the preferred method is to add an aqueous solution to the post-reaction solution to adjust the pH to 7 or less and to perform strip purification after stirring under heating. Strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. To efficiently purify the strip under these temperature conditions, it is preferable to perform this operation under reduced pressure; when performed at normal pressure, the operation is preferably carried out under a flow of inert gas such as nitrogen or argon.

[0111] 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).

[0112] 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 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.

[0113] 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, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support can be, for example, activated carbon, silica, silica-alumina, alumina, or zeolite. These catalysts can be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. Furthermore, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0114] 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.

[0115] 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.

[0116] It is also possible to combine the two types of deodorization steps mentioned above. In the approach involving acid treatment, the decomposition and removal of the aldehyde compound is possible, but since there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehyde from this cannot be completely eliminated. In the approach involving a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound formed. However, the aldehyde condensate that forms with the condensation of some of the aldehyde remains in the system even after such treatment has been carried out, and removal by strip purification is also difficult.Therefore, by alkylating the unsaturated double bonds that remain when the solution following the addition reaction is subjected to hydrogenation, and then decomposing the . Adding an acid catalyst to the aldehyde condensate in the system allows for complete deodorization. (WO2002 / 05588).

[0117] 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).

[0118] The glycerol silicone resin (b) 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.

[0119] In particular, the glycerol-coated silicone resin (b) according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b<30et0<c< 30, l'indice i dans la formule générale (2) est un nombre entier qui satisfait à condition 0 < i < 3 et j (3) < j < 10 sous forme d'un solide 25° c présente, de préférence une masse moléculaire moyenne en poids varie comprise 1000 100000 plus préférentiellement, 3000 50000.

[0120] The glycerol-siliconized resins (b) 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.

[0121] 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):

[0122] [Chem 21] [(CH3)3SiO1 / 2]a [R(CH3)2SiO1 / 2]b(SiO4 / 2)f (21) where - R designates the 3-glyceroxypropyl group with the structure -C3H6OCH2-CH(OH)CH2OH; - the indices a, b and f are integers that satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a+b) / f < 1.5.

[0123] According to a particularly preferred form, the glycerol silicone resin (b) of the type (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate of formula (21) is in the form of a solution in at least one volatile oil.

[0124] 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 ambient temperature, having in particular a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40000 Pa, in particular ranging from 2.66 Pa to 13000 Pa, and more particularly ranging from 2.66 Pa to 1300 Pa.

[0125] The volatile oil according to the invention can be chosen from the group consisting of hydrocarbon oils, silicone oils, and their mixtures.

[0126] 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.

[0127] 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.

[0128] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0129] Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and, for example, oils sold under the trade names Isopar® or Permetyl®. Isododecane is preferred.

[0130] By way of example of volatile silicone oil usable in the invention, volatile silicone oils may be cited, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 mnf / s (cSt), 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, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) will be used more preferentially.

[0131] 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 at 49.5% by weight of active matter in isododecane as the product manufactured under the trade name X-25-9138A® by SHIN ETSU of average molecular weight of 11000.

[0132] According to a preferred embodiment, in order to improve the resistance of the composition of the invention to sebum, the composition of the invention comprises at least one glycerol-based silicone resin and at least one non-glycerol-based silicone resin in a weight ratio of The quantity of glycerol-coated silicone resin to the quantity of non-glycerol-coated silicone resin greater than or equal to 0.8, and more preferably greater than or equal to 1.0 Volatile hydrocarbon oil

[0133] The composition according to the invention comprises an oily phase (d) comprising at least one volatile hydrocarbon oil.

[0134] Oil means any fatty substance in liquid form at room temperature (25 °C) and atmospheric pressure (760 mm Hg or 105 Pa).

[0135] 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.

[0136] The volatile hydrocarbon oils usable in the compositions according to the invention can be chosen from among the C8-C16 branched alkanes.

[0137] 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®.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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®.

[0144] 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®.

[0145] 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.

[0146] According to a particularly preferred embodiment, the volatile hydrocarbon oil is chosen from among C8-C16 branched alkanes, and more particularly isododecane, the mixture of C9-C12 volatile linear alkanes and the mixture of n-undecane (Cil) and n-tridecane (Cl3).

[0147] According to a particularly preferred embodiment, the composition of the invention comprises at least one volatile oil selected from petroleum-derived C8-C16 isoalkanes (also called isoparaffins), in particular isododecane.

[0148] The volatile hydrocarbon oil or oils are preferably present in the composition of the invention at levels less than or equal to 80% by weight, preferably from 40 to 70% by weight relative to the total weight of said composition. Silicone gum

[0149] The composition according to the present invention comprises at least one silicone gum (c).

[0150] If two or more silicone erasers (c) are used, they may be identical or different.

[0151] 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.

[0152] More particularly, silicone gum (c) is selected from polyorgano-siloxanes with a molecular mass by weight greater than or equal to 180000g / mol.

[0153] 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).

[0154] The silicone rubber (c) preferably has a dynamic viscosity at 25°C and atmospheric pressure of 100 to 1000 mPa.s.

[0155] It may be preferable that the silicone gum (b) does not have a functional group such as an amino group.

[0156] The silicone gum (c) may be chosen in particular from silicones of formula: [Chem 22] R2

[0157] 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 amine radical, or a hydroxyl radical. X is an alkyl radical containing 1 to 6 carbon atoms, a hydroxyl radical, or an amine radical, and n and p being integers chosen such that the molecular mass of silicone gum is greater than or equal to 180000 g / mol.

[0158] In general, n and p can each take values ​​from 0 to 3000, knowing that n and p are not naught simultaneously.

[0159] According to a particular method, the silicone gum(s) (c) can be used alone.

[0160] According to a particular embodiment of the invention, the silicone gum (c) is in the form of a solution in an organic solvent, preferably selected from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular C8-C16 such as isododecane, methylene chloride, pentane, dodecane, tridecane, tetradecane or mixtures thereof.

[0161] In a particularly preferred manner, the solvent for silicone gum (c) is chosen from among the C8-C16 isoparaffins, in particular isododecane.

[0162] When the silicone gum (c) of the invention is in the form of a solution in an organic solvent such as those described above, the proportion of silicone gum represents, preferably, from 5 to 40% by weight, and more preferably from 10 to 30% by weight relative to the total weight of the solution.

[0163] Preferably, the silicone gum(s) (c) according to the invention is (are) present at active material contents ranging from 5 to 30% by weight, and more particularly from 8 to 15% by weight relative to the total weight of the composition.

[0164] As examples of silicone gums (c) that can be used according to the present invention, mention may be made of those for which: - Substituents RI to R6 represent a methyl group, group X represents a methoxy group, and n and p are such that the molecular weight of the polymer is 600 000 g / mol, such as the product sold under the name Mirasil C-DPDM® by the company Bluestar; - Substituents RI to R6 represent a methyl group, group X represents a hydroxyl group, and n and p are such that the molecular weight of the polymer is 600,000 g / mol, such as the product sold under the name SGM 36® by Dow Corning, the product marketed or manufactured under the name XIAMETER® PMX-1401 FLUID® by Dow Corning, as a 13% wt. solution in cyclopentasiloxane, the product marketed or manufactured under the name XIAMETER PMX-1503 FLUID® by Dow Corning, as a 12% wt. solution in polydimethylsiloxane, the product marketed or manufactured under the name XIAMETER® PMX-1403 FLUID by Dow Corning, as a 13% wt. solution in polydimethylsiloxane, - dimethicones of the type (polydimethylsiloxane) (methylvinylsiloxane), such as SE63® sold by GE Bayer Silicones, copolymers of poly(dimethylsiloxane)(diphenyl)(methylvinylsiloxane) and their mixtures.

[0165] According to a particularly preferred form, silicone gum (c) is a polydimethylsiloxane with the INCI name DIMETHICONE and the following formula: [Chem 22] in which n is less than or equal to 3000, and particularly in the form of a solution in isododecane, and more particularly in the form of a 25% by weight solution in isododecane such as the product marketed or manufactured under the name SILSOFT B3820 BLEND® by the company MOMENTIVE PERFORMANCE MATERIALS. Lipophilic thickener

[0166] The composition according to the invention comprises at least (e) a lipophilic thickener.

[0167] A "lipophilic thickener" is understood to mean any lipophilic molecule that is lipophilic or lipophilic dispersible in the oil phase of the composition and capable of increasing the viscosity of the composition.

[0168] As a lipophilic thickener, at least one lipophilic clay will preferably be used.

[0169] Clay refers to a material based on hydrated silicates and / or aluminosilicates of lamellar structure.

[0170] 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.

[0171] They can be chosen from among bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

[0172] Preferably, they are chosen from among the hectorites and the bentonites.

[0173] According to a particularly preferred form, a lipophilic clay selected from hydrophobic modified bentonites and hydrophobic modified hectorites, in particular by a quaternary ammonium chloride in C22CIO, will be used, such as: - a bentonite modified by stearalkonium chloride such as the commercial products sold under the name CLAYTONE AF®, GARAMITE VT®, TIXOGEL® LG-M, TIXOGEL® MP 250 TIXOGEL® VZ, TIXOGEL® VZ-V XR, by the company BYK Additives Inc; the commercial products sold under the name VISCOGEL® B3, VISCOGEL® B4, VISCOGEL® B7, VISCOGEL® B8, VISCOGEL® ED, VISCOGEL® GM, VISCOGEL® S4, VISCOGEL® SD by the company Bentec SPA; - a bentonite modified by stearalkonium chloride in the presence of at least propylene carbonate and at least one oil such as the commercial products DUB VELVET GUM® from the company STEARINERIE DUBOIS FILS, MYGLYOL GEL T® from the company Cremer Oleo, TIXOGEL® CGT 6030, TIXOGEL® DBA 6060, TIXOGEL® FTN, TIXOGEL® FTN 1564, TIXOGEL® IPM, TIXOGEL® LAN, TIXOGEL® LAN 1563 from the company 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.

[0174] 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.

[0175] The lipophilic thickener or thickeners may be present in the composition at concentrations ranging, preferably from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition. Cosmetic additives

[0176] The composition may contain conventional cosmetic additives such as colouring materials, preservatives, perfumes, antioxidants, moisturizing agents, lipophilic actives such as vitamins, lipophilic UV filters, fillers.

[0177] 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. Coloring agents

[0178] The composition according to the invention may in addition include at least one coloring material.

[0179] According to a particular embodiment of the invention, the coloring matter can be chosen from powdered coloring materials, liposoluble dyes, and mixtures thereof. a. Powdered coloring agents

[0180] Powdered colouring materials may be chosen from mineral pigments, organic pigments, mother-of-pearls and mixtures thereof.

[0181] 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.

[0182] According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

[0183] The term "mineral pigment" means any pigment that meets the definition in the Ullmann Encyclopedia under the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include zirconium or cerium oxides, as well as zinc, iron (black, yellow, or red), or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metallic powders such as aluminum powder and copper powder. The following mineral pigments may also be used: Ta2O5, Ti3O5, Ti 2O3, TiO, ZrO2 mixed with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

[0184] The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can go up to 100 µm, preferably from 200 nm to 5 µm, and more preferably from 300 nm to 1 pm.

[0185] According to a particular embodiment of the invention, the pigments have a size characterized by a D

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

[0186] Sizes are measured by static light scattering using a commercial Malvern Master Sizer 3000® particle size analyzer, allowing for the determination of the particle size distribution of all particles over a wide range from 0.01 pm to 1000 pm. The data are processed based on the classical Mie scattering theory. This theory is best suited for size distributions ranging from submicron to multimicron and allows for the determination of an "effective" particle diameter. This theory is notably described in Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

[0187] D

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

[0188] 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.

[0189] 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.

[0190] 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 include 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.

[0191] 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 titanium dioxide pigments and oxide pigments. black, red and yellow iron sold under the commercial reference NAI® by the company by MIYOSHI KASEI.

[0192] 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.

[0193] Among mineral pigments, nacres can also be mentioned. They can be chosen from white pearlescent pigments such as mica covered 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.

[0194] The pigments that can be used according to the invention can also be organic pigments.

[0195] 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.

[0196] 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 Cil 1725, 15510, 45370, 71105, the 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 the pigments obtained by oxidative polymerization of indole derivatives,phenolic compounds as described in patent FR2 679 771.

[0197] These pigments can also be in the form of composite pigments as described in patent EPI 184426. These composite pigments can be composed including 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 onto the core.

[0198] 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.

[0199] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0200] Among the organic dyes, we can mention cochineal carmine. We can also mention the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0201] Examples of lacquers include the product known as D&C Red 7 (CI 15 850 :1).

[0202] Preferably, the powdered 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. a. Fat-soluble coloring agents

[0203] A composition according to the invention may comprise at least one liposoluble coloring material and preferably at a rate of at least 0.01% by weight relative to the total weight of the composition.

[0204] For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the color effect sought and the colonic intensity provided by the coloring materials considered, and its adjustment clearly falls within the competence of the person skilled in the art.

[0205] For the purposes of this invention, "liposoluble colouring material" means any compound, generally organic, natural or synthetic, soluble in an oily phase or solvents miscible with a fat and capable of colouring.

[0206] Suitable liposoluble colorants for the invention include, in particular, synthetic or natural liposoluble 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, yellow quinoline, annatto, curcumin.

[0207] Preferably, the composition according to the invention comprises at least one powdered colouring material of the mineral pigment type, in particular chosen from metallic oxides, and more particularly chosen from titanium dioxides, black, red or yellow iron oxides, coated or uncoated, and mixtures thereof.

[0208] According to a particularly preferred mode, the composition according to the invention comprises at least one powdered colouring material selected from titanium dioxides coated according to the invention by isopropyl triisostearyl titanate, black, red or yellow iron oxides coated by isopropyl triisostearyl titanate, and mixtures thereof. Cosmetic applications

[0209] The composition 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.

[0210] According to a particularly preferred embodiment, the composition of the invention is anhydrous.

[0211] For the purposes of the invention, the expression "anhydrous composition" designates respectively a composition which contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water by weight of its total weight, and in particular a composition free of water.

[0212] More specifically, the composition according to the invention is a eyebrow care and / or makeup product such as a mascara.

[0213] Such compositions are in particular prepared according to the general knowledge of the person skilled in the art.

[0214] Packaging and application assembly or kit

[0215] The present invention also relates to an assembly, or kit, for the packaging and application of a cosmetic composition for coating keratinous materials, comprising: - a packaging device comprising said cosmetic composition of keratinous material coating as previously described, - an applicator of said composition.

[0216] According to another aspect, the invention also relates to a makeup set comprising: i) an applicator ii) a composition according to the invention arranged inside a container.

[0217] The container may delimit one or more compartment(s). The container may, for example, be in the form of a tube.

[0218] Such an applicator may be integral with a cap mounted reversibly on said container between a sealing position of said container and a ma- keel.

[0219] 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.

[0220] 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.

[0221] Throughout the application, the expression "contains a" or "includes a" shall be understood as meaning "containing at least one" or "comprising at least one", unless otherwise specified.

[0222] It is understood that the following examples are provided for illustrative purposes only and are in no way limiting the scope of protection conferred by this application. Preparation examples

[0223] Example 1: Preparation of a 60% decamethylcyclopenta-siloxane solution of silicone resin modified by 3-glyceroxypropyl groups

[0224] A reactor was loaded with 1300 g of a 50% decamethylcyclopenta-siloxane solution of a powdered organosilicon resin containing hydrosilyl groups, of average composition formula (E4) (weight average molecular weight, 4480; amount of hydrogen gas evolution, 8.0 mL / g), 30.7 g of glycerol mono-allyl ether of formula (E5), 1300 g of 2-propanol and 0.7 g of a 0.5% chloroplatinic acid solution in 2-propanol, and the reaction was carried out by heating for 6 hours at 100°C. The solvent was then removed by heating under reduced pressure. Next, 325 g of ethanol were added, after which 6.5 g of a 5% aqueous sodium hydroxide solution were added, hydrolyzing the unreacted hydrosilyl groups, after which neutralization was carried out by adding 0.8 g of concentrated hydrochloric acid.After neutralization, 195 g of 0.01 N aqueous hydrochloric acid were added, hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene, and neutralization was carried out with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was heated under reduced pressure to drive off the solvent and filtered, giving a decamethylcyclopentasiloxane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). The solution was clear and colorless.

[0225] The decamethylcyclopentasiloxane solution of this silicone resin modified with 3-glyceroxypropyl groups was heated to 120–130°C under reduced pressure to remove the decamethylcyclopentasiloxane. The product thus obtained was a solid powder with an HLB of 0.9. (Me3SiO 1 / 2)27.s(HMe2SiO 1 / 2) 1.0(8^4 / 2)35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiOi / 2)27j8(R2Me2SiOi / 2) 1^(8104^)353 (E6) R2=-CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H

[0226] Example 2: Preparation of a 60 wt% isododecane solution of a silicone resin modified by 3-glyceroxypropyl groups

[0227] 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 Ethanol was added, after which 6.5 g of a 5% aqueous sodium hydroxide solution were added, hydrolyzing the unreacted hydrosilyl groups. Neutralization was then carried out by adding 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of 0.01 N aqueous hydrochloric acid were added, hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene. Neutralization was then 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 filtration was performed, yielding an isododecane solution of the silicone resin modified by 3-glyceroxypropyl groups.

[0228]

[0229] formula (E6). (Me3SiO i / 2)27j8(HMe2SiO i / 2) 1 XSiCU / ^s^ (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (Me3SiO i / 2)27j8(R2Me2SiO i / 2) 1 XSiCU / ^s^ (E6) R2= -CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H. Examples of eyebrow makeup compositions The following compositions have been prepared. Ingredients Ex 3 (invention) Ex 3a (not invention) SILICONE RESIN (3-GLYCEROXYPROPYL) DIME-THYLSILOXY TRIMETHYLSILOXY-SILICATE OF FORMULA (21) IN 50% SOLUTION IN LTSODODECANE (X-25-9138A® BY SHIN ETSU) (glycerol-based silicone resin) 9.09 (4.54% by weight of active ingredient) 0 TRIMETHYLSILOXYSILICATE IN 75% SOLUTION IN LTSODODECANE (SILSOFT 74 FLUID® - MOMENTIVE PERFORMANCE MATERIALS) (non-glycerol-based silicone resin) 18 (13.5% by weight of active ingredient) 18 (13.5% by weight of active ingredient) DIMETHICONE IN 25% SOLUTION IN LTSODODECANE (SILSOFT B3820 BLEND® -MOMENTIVE PERFORMANCE MATERIALS) (silicone gum) 48 (12% by weight of active material) 48 (12% by weight of active material) DISTEARDIMONIUM HECTORITE (BENTONE 38 VCG® RHEOLOGICAL ADDITIVE -ELEMENTIS) 5 5 PROPYLENE CARBONATE 1.65 1.65 TITANIUM DIOXIDE (AND) ISOPROPYL TITANIUM TRIL SOSTEARATE (BTD-401® - KOBO) 2.47 2.47 RED IRON OXIDES (AND) ISOPROPYL TITANIUM TRIL SOSTEARATE (BWRO-I2® - KOBO) 0.59 0.59 YELLOW IRON OXIDES (AND) ISOPROPYL TITANIUM TRIL SOSTEARATE (BWY0-I2® - KOBO) 0.9 0.9 BLACK IRON OXIDES (AND) ISOPROPYL TITANIUM TRIL SOSTEARATE (BWB0-I2® - KOBO) 1.12 1.12 ISODODECANE qs 100 qs 100 Composition preparation protocol

[0231] 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 minutes, then cooled to room temperature (25°C).

[0232] In vitro tests for measuring durability: resistance to makeup remover oil. Test protocol.

[0233] A layer of each example formula was applied to Supplale in a 1x2 cm rectangle using a brush. The application was allowed to dry for 1 hour. Five colorimetric measurements were taken on each application before application of the makeup remover (To) using a Konica CM 700d spectrophotometer (Minolta). The average values ​​of Lo*, a0*, and b0* were measured under illuminant D65 (average daylight including UV rays).

[0234] Three drops of Shu Uemura - Ultime 8 Cleansing Oil® were applied to the sample obtained with each example formula. The sample to be evaluated was rubbed in a circular motion four times. It was rinsed with water and then blotted with a tissue to remove excess water. This operation was repeated five times on each sample. Five colorimetric (T5) data measurements were taken on each sample by measuring the average values ​​of L5*, a5*, and b5* under illuminant D65. This operation was repeated five times on each previously prepared sample. The resistance to cleansing oil of each example composition was evaluated by calculating the AE* according to the following equation:

[0235] [Math 1]:

[0236] The results obtained are shown in the table below Formula Example 3 invention Example 3 a outside invention without glycerol resin Resistance to makeup remover oil AE 12.0+1.93 25.49 + 0.99 The results of comparative tests showed that example 3 of the invention comprising the association of the non-glycerol silicone resin TRIMETHYLSILOXY-SILICATE, the glycerol silicone resin 3-GLYCEROXYPROPYL) DIME-THYLSILOXY TRIMETHYLSILOXYSILICATE and a silicone gum exhibited excellent resistance to makeup remover oil unlike example 3a outside the invention without glycerol silicone resin.

Claims

Claims

1. Composition, preferably for the care and / or makeup of keratin materials, in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours, comprising, in particular in a physiologically acceptable medium: (a) at least one non-glycerolated silicone resin; and (b) at least one glycerolated silicone resin; and (c) at least one silicone gum; and (d) at least one oily phase comprising at least one volatile hydrocarbon oil; and (e) a lipophilic thickener.

2. Composition according to claim 1, wherein the non-glycerolated silicone resin (a) is chosen from MQ type silicone resins, T type silicone resins, MQT type silicone resins, and mixtures thereof.

3. Composition according to claim 1 or 2, comprising at least one non-glycerolated silicone resin (a) chosen from silicone resins of MQ type, in particular of Trimethylsiloxysilicate type.

4. Composition according to claim 3, where the non-glycerolated resin (a) of the Trimethylsiloxysilicate type is in solution in isododecane, in particular in solution at 75% by weight of active material in isododecane.

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

6. Composition according to any one of the preceding claims, where the glycerolated silicone resin(s) (b) is (are) present in an active material content ranging from 0.1 to 40% by weight relative to the total weight of the composition, preferably ranging from 0.2 to 30% by weight and more preferably from 0.5 to 15% by weight relative to the total weight of the composition.

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

8. Composition according to claim 7, wherein the glycerolated silicone resin (b) contains at least one dimethylsiloxane unit R(CH3)2SiOi / 2 comprising a hydrocarbon radical R comprising a monoglycerol group.

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

10. Composition according to claim 9, where the glycerol silicone resin(s) (b) of formula (1) are chosen from those in which - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30; - the index i in the general formula (2) of the polyglycerol group R2 is an integer which satisfies the condition 0 < i < 3.

11. Composition according to claim 9 or 10, where the glycerolated silicone resin(s) (b) of formula (1) have a weight-average molecular mass which preferably varies from 1000 to 100,000 and more preferably from 3000 to 50,000.

12. Composition according to any one of claims 9 to 11, where the glycerolated silicone resin(s) (b) 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.

13. A composition according to any one of claims 9 to 12, wherein the glycerolated silicone resin(s) (b) has (have) a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, ranging from 0.1 to 15, and more preferably from 1.0 to 8.

0.

14. Composition according to any one of claims 9 to 13, comprising at least one glycerol silicone resin (b) of formula (1) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type 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.

15. Composition according to claim 14, where the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

16. Composition according to claim 15, where the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution at 49.5% by weight of active material in isododecane.

17. Composition according to any one of the preceding claims, comprising at least one glycerolated silicone resin (a) and at least one non-glycerolated silicone resin (b) in a weight ratio of the quantity of glycerolated silicone resin to the quantity of non-glycerolated silicone resin greater than or equal to 0.8, and more preferably greater than or equal to 1.

0.

18. Composition according to any one of the preceding claims, comprising at least one volatile hydrocarbon oil chosen from C8-C16 isoalkanes of petroleum origin, in particular isododecane.

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

20. Composition according to any one of the preceding claims, wherein the silicone gum (c) is chosen from silicones of formula in which: RI, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,

21. R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical, X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical, and n and p being whole numbers chosen such that the molecular mass of the silicone gum (c) is greater than or equal to 180,000 g / mol. Composition according to claim 20, where n and p vary from 0 to 3000, knowing that n and p are not affected simultaneously. ^Claim 22] Composition according to any one of the preceding claims, wherein the silicone gum (c) is in the form of a solution in an organic solvent, preferably chosen from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular C8-C16 such as isododecane, methylene chloride, pentane, dodecane, tridecane, tetradecane or mixtures thereof, more particularly the solvent is isododecane. ^Claim 23] Composition according to claim 22, wherein the proportion of silicone gum (c) in the organic solvent solution represents from 5 to 40% by weight, and more preferably from 10 to 30% by weight relative to the total weight of said solution.^Claim 24] Composition according to any one of the preceding claims, wherein the silicone gum(s) (c) is (are) present at active material contents ranging from 5 to 30% by weight, and more particularly from 8 to 15% by weight. ^Claim 25] Composition according to any one of the preceding claims, wherein the silicone gum (c) is a polydimethylsiloxane with the INCI name DI-METHICONE of the following formula: CK CK CK 1 r 1, 4 4 L 0: S i " Ô St,—CK CK. CH, CHs in which n is less than or equal to 3000, and particularly said gum is in the form of a solution in isododecane, and more particularly in the form of a 25% by weight solution in isododecane.^Claim 26] Composition according to any one of the preceding claims, wherein the lipophilic thickener (e) is a lipophilic clay, and more particularly a hectorite modified with distearyl dimethyl ammonium chloride with the INCI name: DISTEARDIMONIUM HECTORITE. ^Claim 27] Composition according to any one of the preceding claims, wherein the lipophilic thickener(s) (e) are present in concentrations ranging, preferably, from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition. ^Claim 28] Composition according to any one of the preceding claims, further comprising at least one coloring matter, preferably. chosen from powdery coloring matters, fat-soluble dyes, and their mixtures.

29. Composition according to claim 28, where the pulverulent coloring matter(s) is (are) present in a content of less than or equal to 50.0% by weight, preferably ranging from 25 to 40% by weight, more particularly from 3 to 15% by weight relative to the total weight of the composition.

30. Composition according to claim 28 or 29, where the pulverulent coloring material(s) is (are) chosen from metal oxides, and more particularly chosen from titanium dioxides, coated or uncoated black, red or yellow iron oxides, and mixtures thereof.

31. Composition according to claim 30, comprising at least one pulverulent coloring matter chosen from titanium dioxides coated with isopropyl triisostearyl titanate, black, red or yellow iron oxides coated with isopropyl triisostearyl titanate, and mixtures thereof.

32. Composition according to any one of the preceding claims, characterized in that it is anhydrous.

33. Assembly, or kit, for packaging and applying a cosmetic composition for coating keratin materials comprising: - a packaging device comprising the composition as defined in any one of claims 1 to 32; - an applicator for said composition.

34. A method of coating, in particular curling keratin materials, in particular eyebrows and the skin around the eye and eyebrows, comprising the application to said keratin fibres of a composition as defined according to any one of claims 1 to 32.