Eyebrow forming composition comprising a non-glycerolated silicone resin, a glycerolated silicone resin, a volatile hydrocarbon oil and a thickener

Abstract

The present invention relates to an anhydrous composition for caring for and / or structuring keratin materials, in particular the eyebrows and the skin around the eyes and eyebrows, which comprises, in a physiologically acceptable medium: a) at least one non-glycerolated silicone resin; and b) at least one glycerolized silicone resin; and c) at least one oily phase containing at least one volatile hydrocarbon; and d) a lipophilic thickener. The present invention also relates to a method for coating keratinous materials, in particular the eyebrows and the skin around the eyes and eyebrows, and more particularly to a method for structuring said keratinous materials, comprising the application of a composition as defined above.

Description

[Technical Field]

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

[0002] In the field of eyebrow makeup, consumers have access to several types of solutions: - Eyebrow pencils are easy to use but only last a day. They are often based on a pigmented core that transfers color by transferring substances onto the skin. - Pens that are similarly easy to use but last only a day. They are often made from a water-based formula that contains dyes. - Salon tattoo services that are very painful but last for months. Anhydrous gels such as the commercially available Inked Waterproof Brow Gel® from Urban Decay (Mintel ID 7578707) and the Up to 3 Day Styling Gel® from Maybelline (Mintel ID 10361806), which contain a combination of isododecane and MQ resin: trimethylsiloxysilicate and silicone polyamide: nylon-611 / dimethicone copolymer.

[0003] Users of makeup formulations for keratinous materials such as the eyebrows and the skin around the eyes and eyebrows are looking for products with longer wear properties over time, which is reflected in particular by better resistance of the deposited film to sebum, a complex mixture of lipids synthesized under hormonal stimulation by the sebaceous glands present in the dermis. The presence of sebum around the eyes and eyebrows tends to reduce the wear properties of the eyebrow products.

[0004] There is still a need to find new compositions for caring for and / or making up keratin materials, in particular the eyebrows and the skin around the eyes and eyebrows, which make it possible to obtain cosmetic products with better wear properties of the deposits over time, and in particular better resistance to sebum.

[0005] Unexpectedly, the inventors have discovered a composition for caring for and / or making up keratinous materials, in particular eyebrows, including eyebrow hairs, the skin and its contours for the implantation of said hairs, which comprises, in particular in a physiologically acceptable medium: a) at least one non-glycerolated silicone resin of the MQ type; and b) at least one glycerolized silicone resin; and c) at least one oily phase containing at least one volatile hydrocarbon oil; and d) It has been discovered that it is possible to achieve these objectives by using compositions containing lipophilic thickeners.

[0006] This discovery forms the basis of the present invention. Summary of the Invention [Means for solving the problem]

[0007] A first subject of the present invention is therefore a composition for caring for and / or making up keratinous materials, in particular eyebrows, including eyebrow hairs, the skin intended for implanting said hairs and their contours, comprising, in particular in a physiologically acceptable medium: a) at least one non-glycerolated silicone resin of the MQ type; and b) at least one glycerolized silicone resin; and c) at least one oily phase containing at least one volatile hydrocarbon oil; and d) A composition comprising a lipophilic thickener.

[0008] A second subject of the invention is a method for coating keratinous materials, in particular the eyebrows and the skin around the eyes and eyebrows, and more particularly a method for making up said keratinous materials, comprising applying a composition as defined above. DETAILED DESCRIPTION OF THE INVENTION

[0009] definition In the context of the present invention, the term "keratinous material" is intended to mean in particular eyebrows, including the eyebrow hairs, the skin for implanting the eyebrow hairs and their contours. For the purposes of the present invention, the term "keratinous material" also extends to synthetic false eyebrows.

[0010] The term "physiologically acceptable" means that it has a pleasant color, odor and feel, does not cause any unacceptable discomfort (stinging or tightness) that would tend to deter the consumer from using the composition, and is compatible with the keratin material.

[0011] The term "glycerolated silicone resin" is understood to mean any silicone resin that contains at least one organosiloxane unit in its chemical structure that contains one or more monoglycerol or polyglycerol groups.

[0012] In particular, glycerolized silicone resins are 1 / 2 The glycerolated silicone resin contains at least one organosiloxane unit of the type R(CH3)2SiO, where R, R' and R'' are identical or different and represent hydrocarbon radicals, at least one of which contains a monoglycerol group or a polyglycerol group, and more particularly, the glycerolated silicone resin contains at least one dimethylsiloxane R(CH3)2SiO, containing a hydrocarbon radical R containing a monoglycerol group. 1 / 2 Contains units.

[0013] The term "hydrocarbon group" is understood to mean a group containing mainly hydrogen and carbon atoms and, optionally, one or more functional groups selected from hydroxyl groups, ester groups, ether groups and carboxyl groups.

[0014] The term "monoglycerol group" is understood to mean any group that contains in its chemical structure a -O-CH2-CHOH-CH2OH group.

[0015] The term "polyglycerol group" refers to a group whose chemical structure includes at least two -(O-CH2-CHOH-CH2) m It is understood to mean any group comprising a chain containing repeating glycerol units.

[0016] Non-glycerolated silicone resin The composition according to the invention comprises at least one non-glycerolated silicone resin of the MQ type.

[0017] More generally, the term "resin" refers to a compound whose structure is three-dimensional. "Silicone resin" is also known as "siloxane resin." Therefore, for purposes of this invention, polydimethylsiloxane is not a silicone resin.

[0018] The nomenclature for silicone resins (also known as siloxane resins) is known as "MDTQ" designation, where the resin is described as a function of the various siloxane monomer units it contains, with each letter in "MDTQ" characterizing a type of unit.

[0019] The letter M represents the compound of the formula R1R2R3SiO 1 / 2 where the silicon atom is linked to only one oxygen atom of the polymer containing this unit.

[0020] The letter "D" represents the difunctional unit R1R2SiO 2 / 2 where the silicon atom is linked to two oxygen atoms.

[0021] The letter "T" stands for RSiO 3 / 2 represents a trifunctional unit of

[0022] Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley and Sons, New York, (1989), pp. 265-270, and in U.S. Pat. Nos. 2,676,182, 3,627,851, 3,772,247, 5,248,739 or 5,082,706, 5,319,040, 5,302,685, and 4,935,484.

[0023] In the units M, D and T defined above, R, i.e. R1, R2 and R3, represents a hydrocarbon-based group (in particular an alkyl group) containing 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

[0024] Finally, the letter Q represents the tetrafunctional unit SiO 4 / 2 where the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.

[0025] MQ resin: Examples of MQ-type silicone resins include those of the formula [(R1)3SiO 1 / 2 ] x (SiO 4 / 2 ) y (MQ units), in which x and y are integers ranging from 50 to 80, and the group R1 represents a group as defined above, preferably an alkyl group containing 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

[0026] Examples of solid silicone resins of the MQ type, of the trimethylsiloxysilicate type, include those sold by General Electric under the reference SR1000®, by Wacker under the reference TMS 803®, by Shin-Etsu under the name KF-7312J®, or by Dow Corning under the names DC749® or DC593®.

[0027] Preferably, the composition according to the invention comprises, as silicone resin, at least one resin of MQ type, more particularly a resin of trimethylsiloxysilicate type, such as those sold under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker, or under the name KF-7312J® by Shin-Etsu, or under the names DC749® or DC593® by Dow Corning, or under the reference SILSOFT 74 FLUID by the company MOMENTIVE PERFORMANCE MATERIALS.

[0028] In particular, a trimethylsiloxysilicate resin in solution in isododecane, in particular a solution containing 75% by weight of active material in isododecane, such as the commercial product sold under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS, is used.

[0029] According to a particular embodiment of the present invention, the non-glycerolated silicone resin is present in the composition in an active substance content ranging from 4% to 35% by weight relative to the total weight of the composition, preferably ranging from 6% to 30% by weight relative to the total weight of the composition, and more preferably ranging from 8% to 25% by weight.

[0030] Glycerolated Silicone Resin The composition according to the present invention comprises at least one glycerolated silicone resin.

[0031] Glycerolated silicone resins contain one or more mono- or polyglycerol groups in their chemical structure.

[0032] According to a particular embodiment of the present invention, the glycerolated silicone resin is present in an active substance 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 relative to the total weight of the composition, and more preferably ranging from 0.5% to 15% by weight.

[0033] The glycerolated silicone resin according to the invention is preferably selected from those of the following formula (1): [Chemical formula 1] (R 1 3SiO 1 / 2 ) a (R 2 (CH3)2SiO 1 / 2 ) b (R 3 3SiO 1 / 2 ) c (R 1 2SiO 2 / 2 ) d (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) f (1) (In the formula, -Each R 1 are the same or different alkyl, aryl or aralkyl groups having 1 to 30 carbon atoms, or halogen-substituted, amino-substituted or carboxyl-substituted groups of the latter; -Each R 2 is a monoglycerol or polyglycerol group of the following general formula (2): [Chemical formula 2] -(CH2)2-C l H 2l -O-(CH2CH(OH)CHO) i R 4 (2) (In the formula, -R 4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, - The subscripts l and i are integers satisfying the conditions 0 ≦ l ≦ 15 and 0 < i ≦ 5, and - Each R 3 is the same or different group of the following general formula (3), general formula (4), general formula (5) or general formula (6), [Chemical formula 3] -(CH2)2-C m H 2m -(SiOR 1 2)j-SiR 1 3(3) [Chemical formula 4] -(CH2)2-C m H 2m -SiR 1 k1 -(OSiR 1 3) 3-k1) (4) [Chemical formula 5] -(CH2)2-C m H 2m -SiR 1 k1 -(OSiR 1 k2 (OSiR 1 3) 3-k2 ) 3-k1 (5) [Chemical formula 6] -(CH2)2-C m H 2m -SiR 1 k1 -(OSiR 1 k2 (OSiR 1 k3 (OSiR 1 3) 3-k3 ) 3-k2 ) 3-k1 (6) In the formula, - Each R 1 is the same or different alkyl group, aryl group or aralkyl group having 1 to 30 carbon atoms, or a group substituted with halogen, a group substituted with amino or a group substituted with carboxyl of the latter; - The subscripts m, j and k1 to k3 are integers satisfying the conditions 0 ≦ m ≦ 5, 0 ≦ j ≦ 500, 0 ≦ k1 ≦ 2, 0 ≦ k2 ≦ 2 and 0 ≦ k3 ≦ 2; - The subscripts a, b, c, d, e, and f are numbers 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.

[0034] The glycerolated silicone resin according to the present invention is described in the specification of US Patent Application Publication No. 20200332065A1 by SHIN ETSU.

[0035] According to a specific embodiment, the glycerolated silicone resin of formula (1) defined above is - The subscripts b and c satisfy the conditions 0 < b ≦ 30 and 0 ≦ c ≦ 30; - The monoglycerol group or polyglycerol group R 2 is selected from those in which the subscript i in the general formula (2) satisfies the condition 0 < i ≦ 3 and is an integer.

[0036] According to a specific embodiment, the glycerolated silicone resin of formula (1) has a subscript c that satisfies the condition 0 < c ≦ 400, R 3 is a group of the general formula (3), and when the subscript j satisfies the condition 0 ≦ j ≦ 10, it is in a solid form at 25°C.

[0037] According to a specific embodiment, the glycerolated silicone resin has a weight average molecular weight in the range of 1000 to 100000.

[0038] The glycerolated silicone resin according to the present invention is amphiphilic, that is, it has two parts with different polarities. Generally, one part is lipophilic (soluble or dispersible in the oil phase), and the other part is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (hydrophilic-lipophilic balance), which is the ratio of the hydrophilic part to the lipophilic part in the molecule. "HLB" is the ratio between the hydrophilic part and the lipophilic part of the molecule and is described, for example, in "The HLB system. A Time-Saving Guide to Emulsifier Selection" (published by ICI Americas Inc; 1984). The value of the HLB of the glycerolated silicone resin according to the present invention preferably varies from 0.1 to 15 according to the Griffin method.

[0039] The glycerolated silicone resin according to the present invention is A) The following formula (7): [Chemical formula 7] (R13SiO 1 / 2 ) a H n R1 3-n SiO 1 / 2 ) b+c (R12SiO 2 / 2 )d(R1SiO 3 / 2 ) e (SiO 4 / 2 ) f (7) (In the formula, - Each R1 is the same or different and is an alkyl group, aryl group or aralkyl group having 1 to 30 carbon atoms, or a group substituted with halogen, a group substituted with amino or a group substituted with carboxyl of the latter; - The subscripts a, b, c, d, e and f are integers satisfying the conditions of 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 satisfying the condition of 1 ≦ n ≦ 3) of a silicone resin containing a hydrosilyl group, B) The following general formulas (8), (9), (10), (11) and (12): [Chemical Formula 8] CH2=CH-C l H 2l -O-(CH2CH(OH)CH2O) i R4 (8) [Chemical Formula 9] CH2=CH-C m H 2m -(SiOR12) j -SiR13(9) [Chemical Formula 10] CH2=CH-C m H 2m -SiR1 k1 -(OSiR13) 3-k1 (10) [Chemical Formula 11] CH2=CH-C m H 2m -SiR1 k1 -(OSiR1 k2 (OSiR13) 3-k2 ) 3-k1 (11) [Chemical Formula 12] CH2=CH-C m H 2m -SiR1 k1 -(OSiR1 k2 (OSiR1 k3 (OSiR13) 3-k3 ) 3-k2 ) 3-k1 (12) (In the formula, -R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, -Subscripts l and i are integers satisfying the conditions of 0 ≦ l ≦ 15 and 0 < i ≦ 5, -Subscripts m, j, and k1 to k3 are integers satisfying the conditions of 0 ≦ m ≦ 5, 0 ≦ j ≦ 500, 0 ≦ k1 ≦ 2, 0 ≦ k2 ≦ 2, and 0 ≦ k3 ≦ 2. The silicone resin can be obtained by a preparation method including a hydrosilylation step with one or more compounds selected from compounds terminated with an alkenyl group containing a hydrosilyl group of formula (7) that reacts with at least one compound of formula (8).

[0040] The hydrosilylation reaction is carried out, for example, in the presence of a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R4, l, m, i, j, and k1 to k3 are as defined above.

[0041] A silicone resin containing hydrosilyl groups was used as the starting material. The silicone resin containing the hydrosilyl group of formula (7) may be solid or liquid at 25°C, but is preferably solid from the viewpoint of film-forming properties. From the viewpoint of usability, the resin is preferably diluted with an organic solvent. It is preferable to use a solvent having a boiling point higher than the reflux temperature during hydrolysis.

[0042] Examples of organic solvents used for dilution include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-based 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 viewpoints of storage stability and non-volatility, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

[0043] The hydrosilyl group-containing silicone resin of formula (7) is (i) hydrolyzing a mixture of one or more compounds selected from organosilicon compounds represented by the following general formulas (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group represented by the following general formulas (15) and (16), and one or more compounds selected from hydrolyzable silanes represented by the following general formula (17), partial hydrolyzed condensates of these hydrolyzable silanes, and metal salts of these hydrolyzable silanes, in the presence of an acid catalyst; [Chemical formula 13] R 1 3SiOSiR 1 3(13) [Chemical formula 14] R 1 3SiX 1 (14) [Chemical formula 15] H n R 1 (3-n) SiOSiR 1 (3-n) H n (15) [Chemical formula 16] H n R 1 (3-n) Six 2 (16) (In the formula, -Each R 1 are the same or different alkyl, aryl or aralkyl groups having 1 to 30 carbon atoms, or halogen-substituted, amino-substituted or carboxyl-substituted groups of the latter; -X 1 and X 2 is a hydrolyzable functional group; and -n satisfies the condition 1≦n≦3) [Chemical formula 17] Six 3 4(17) (In the formula, X 3 is a hydrolyzable functional group) ii) neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acid catalyst; and iii) followed by condensation.

[0044] In the general formulae (13), (14), (15) and (16), R 1 The examples and preferred ranges for are the same as those described above.

[0045] In general formula (14), X 1 is a hydrolyzable functional group directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Among these, methoxy, ethoxy, and chlorine atoms are preferred from the viewpoints of availability and hydrolysis rate.

[0046] In general formula (16), X 2 is a hydrolyzable functional group directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Among these, methoxy, ethoxy, and chlorine atoms are preferred from the viewpoints of availability and hydrolysis rate.

[0047] In the general formula (17), X 3 is a hydrolyzable functional group directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Among these, alkoxy groups are preferred, and from the viewpoints of availability and hydrolysis rate, methoxy or ethoxy groups are preferred. The hydrolyzable group X on the molecule 3 can be similar or different groups.

[0048] 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-octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldisiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane, and 1,3-dimethyl-1,1,3-tetravinyldisiloxane. Of these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

[0049] Examples of the organosilicon compound of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane. Among these, trimethylchlorosilane and trimethylethoxysilane are preferred.

[0050] Examples of organosilicon compounds containing a hydrosilyl group of general formula (15) include 1,1,3,3-tetramethyldisiloxane and 1,1,1,3,3-pentamethyldisiloxane, with 1,1,3,3-tetramethyldisiloxane being particularly preferred.

[0051] In the general formulas (15) and (16), n satisfies the condition 1≦n≦3. In the general formula (15), H and R bonded to one of the silicone atoms 1 and H and R bonded to the other silicon atom. 1 The "n"s attached to may be the same or different.

[0052] Examples of organosilicon compounds containing a hydrosilyl group of the general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, etc. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0053] Examples of hydrolyzable silanes of general formula (17) include tetrachlorosilane, tetramethoxysilane, and tetraethoxysilane. Examples of partial hydrolysis condensates of hydrolyzable silanes include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silanes include water glass, sodium silicate, potassium silicate, etc. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0054] In the present invention, a partial hydrolyzed condensate 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) can be added to the mixture 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) can be added after such hydrolysis and before the rehydrolysis described below. [Chemical formula 18] R 1 Six 4 3(18) [Chemical formula 19] R 1 2SiX 5 2(19) (In the formula, -Each R 1 are the same or different alkyl, aryl or aralkyl groups having 1 to 30 carbon atoms, or halogen-substituted, amino-substituted or carboxyl-substituted groups of the latter; -X 4 and X 5 is a hydrolyzable functional group).

[0055] In general formulas (18) and (19), R 1 The examples and preferred ranges for are the same as those described above.

[0056] In general formula (18), X 4 is a hydrolyzable functional group directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Among these, a methoxy group, an ethoxy group, or a chlorine atom is preferred from the viewpoint of availability and hydrolysis rate. A hydrolyzable group X on the same molecule is 4 may be similar or different.

[0057] In the general formula (19), X 5 is a hydrolyzable functional group directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, alkenoxy groups, acyloxy groups, amide groups, and oxime groups. Among these, a methoxy group, an ethoxy group, or a chlorine atom is preferred from the viewpoint of availability and hydrolysis rate. A hydrolyzable group X on the same molecule is 5 may be similar or different.

[0058] Examples of the silicon compound of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, tripropyltrimethoxysilane, and methyltrichlorosilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, and methyltrichlorosilane are preferred.

[0059] Examples of the silicon compound of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane, and dimethyldichlorosilane. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldichlorosilane are preferred.

[0060] A specific example of a method for producing the hydrosilyl group-containing silicone resin used as a raw material in this invention is described below. A reactor is charged with a solvent (particularly an organic solvent) and hydrolysis raw materials (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 hydrosilyl groups of general formulas (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolyzable condensates of these hydrolyzable silanes, and metal salts of these hydrolyzable silanes), an acid is added as a catalyst, and water is added dropwise with stirring. In this case, it is also possible to add the organic solvent after the dropwise addition of water is completed. Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0061] The temperature during the dropwise addition of water is set to 0°C to 80°C, more preferably 0°C to 50°C. By maintaining the temperature within this range, the heat of reaction of the hydrolysis reaction of the hydrolysis starting material in the system can be kept low. The amount of water to be added dropwise is expressed as a molar ratio per mole of hydrolyzable functional group (alkoxy group, etc.), and is 0.6 to 2, preferably 1.0 to 1.8. By setting the amount of water added within this range, deactivation of the hydrosilyl group can be further suppressed.

[0062] To prevent a decrease in the reaction rate due to a uniform reaction system retention or an increase in viscosity 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 having a boiling point higher than the reflux temperature during the hydrolysis.

[0063] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane.

[0064] In some cases, alcoholic solvents having 1 to 10 carbon atoms can be used simultaneously. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Since alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of long-chain alcoholic solvents limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol, and 2-propanol are particularly preferred.

[0065] The solvent used is contained in an amount of 1% to 80% (in this specification and the following, "%" refers to mass percent), particularly 5% to 50%, based on the total reaction system. Within this range, the reaction system remains homogeneous and the reaction occurs efficiently.

[0066] Examples of the acid catalyst 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, citric acid, etc. The acid catalyst can be used in a small amount, preferably about 0.001% to 10% of the total reaction system.

[0067] After the dropwise addition of water as described above, the hydrolysis reaction is carried out by heating the system to a temperature of 50° C. to 150° C., preferably 80° C. to 120° C., for about 2 to 8 hours. During this time, the deactivation of the hydrosilyl group can be further suppressed by carrying out the reaction at a temperature below the boiling point of the hydrosilyl group-containing organic compound used.

[0068] After carrying out the hydrolysis in this manner on the starting product of the hydrolysis in the presence of an acid catalyst, the system is cooled to a temperature of 10°C to 100°C, preferably 10°C to 60°C, more preferably 10°C to 30°C, and even more preferably 25°C.

[0069] After the hydrolysis, the mixture is neutralized at 10°C to 40°C using a basic catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide. The combined use of a strong basic catalyst and a weak basic catalyst inhibits deactivation of the hydrosilyl groups and further accelerates the condensation reaction of the organosilicon resin. Examples of such strong basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weak basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate. Regarding the combination of a strong basic catalyst and a weak basic catalyst, a combination of sodium hydroxide and calcium carbonate is preferred, as this facilitates the production of a high molecular weight. This results in a sufficiently large molecular weight, more reliably producing a high molecular weight organosilicon resin containing hydrosilyl groups.

[0070] The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. Neutralization with a basic catalyst in an amount 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 the production of a high-molecular-weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents relative to the acid catalyst. By adding an amount within this range, the condensation reaction of the organosilicon resin containing hydrosilyl groups is promoted, allowing the production of a resin with the desired molecular weight.

[0071] After neutralization, the formed alcohol, solvent, and excess water can be removed by heating at 95°C to 120°C under normal or reduced pressure. After confirming that the formed alcohol, solvent, and excess water have been removed, the mixture is heated at 120°C to 150°C for approximately 2 to 5 hours to carry out a condensation reaction. This produces an organosilicon resin containing hydrosilyl groups.

[0072] In the above process for preparing a silicone resin containing hydrosilyl groups, the total molar amount of the compounds of general formulas (13), (14), (15) and (16) is SiO 2 in the compound of general formula (17). 4 / 2 The ratio of the molar amounts of units is expressed as the molar ratio ((13)+(14)+(15)+(16)), (19) which is preferably 0.3:1 to 2:1, more preferably 0.6:1 to 1.3:1.

[0073] Furthermore, the molar ratio of the total molar amount of the compounds of general formulas (13) and (14) to the total molar amount of the compounds of general formulas (15) and (16), expressed as ((13) + (14)):((15) + (16)), is preferably 0.3:1.0 to 2.0:1.0, and more preferably 0.6:1.0 to 1.3:1.0. By adjusting the ratio within these ranges, the amount of hydrosilyl groups contained in the hydrosilyl group-containing organosilicon resin can be more accurately and quantitatively varied. In the present invention, by changing the amount of the compounds of general formulas (15) and (16) supported in this manner, the amount of hydrosilyl groups contained in the organosilicon resin can be quantitatively changed.

[0074] In the above process for preparing a silicone resin containing hydrosilyl groups, after hydrolysis, it is also possible to gradually add dropwise, in the presence of an acid catalyst, one or more compounds selected from organosilicon compounds containing hydrosilyl groups of general formulas (15) and (16) to a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14) and one or more compounds selected from hydrolyzable silane of general formula (17), partial hydrolyzed condensates of these hydrolyzable silanes, and metal salts of these hydrolyzable silanes.

[0075] Next, rehydrolysis is carried out. At this time, the rehydrolysis reaction is preferably carried out by heating for about 2 to 8 hours at a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example, preferably at a temperature of 40 to 150°C, more preferably at a temperature of 40 to 120°C. By carrying out the reaction within this temperature range, deactivation of the hydrosilyl groups can be further suppressed.

[0076] In the process for preparing a silicone resin containing hydrosilyl groups, the reaction of formula (20) below can occur, in which some of the hydrosilyl groups are deactivated. [Chemical formula 20] [ka] (In the formula, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n' is an integer of 1 to 3.)

[0077] However, by appropriately setting the order of addition of raw materials, i.e., by hydrolyzing a mixture of one or more compounds selected from organosilicon compounds of general formulas (13) and (14) with one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes, and metal salts of these hydrolyzable silanes, and then adding one or more compounds selected from organosilicon compounds containing hydrosilyl groups of general formulas (15) and (16) and performing rehydrolysis, the above reaction (20) can be minimized. This reaction can be further suppressed by strategically changing the amount of raw materials added and the type of catalyst.

[0078] The amount of hydrosilyl groups contained in the hydrosilyl group-containing organosilicon resin obtained in this way can be easily adjusted, and by changing the amount of hydrosilyl group-containing organosilicon compound supported, it is even possible to introduce a large amount of hydrosilyl groups.In addition, the amount of hydrolysis starting material used, the type and amount of acid catalyst added, reaction temperature and time, the amount and method of solvent added, the molecular weight range, shape, and other properties of the organosilicon resin can be adjusted, and thus hydrosilyl group-containing organosilicon resins for desired uses can be prepared.

[0079] The hydrosilyl group-containing silicone resin obtained as described above has the average formula (7) and contains Q units (SiO 4 / 2 ) and M units ((R 1 3SiO 1 / 2 ) and (H n R 1 3-n SiO 1 / 2 )) is an essential component, and D unit (R 1 2SiO 2 / 2 ) and T units (R 1 SiO 3 / 2Take [[ID=]] as an arbitrary constituent. It may be solid or liquid at 25°C, but is preferably solid from the viewpoint of film formability. Among the examples, MQ resin, MTQ resin, MDQ resin and MDTQ resin can be mentioned. The weight average molecular weight is preferably 2000 to 30000, but from the viewpoints of performance and ease of operations such as filtration, the range of 3000 to 15000 is more preferable. The weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene in gel permeation chromatography (GPC).

[0080] Preparation method of glycerolated silicone resin Specific examples of the process for preparing the glycerolated silicone resin according to the present invention are described below.

[0081] As described above, the glycerolated silicone resin according to the present invention A) The following average formula (7): (R 1 3SiO 1 / 2 ) a (H n R 1 3-n SiO 1 / 2 ) b+c (R 1 2SiO 2 / 2 ) d (R1SiO 3 / 2 )e(SiO 4 / 2 ) f (7) (In the formula, - Each R 1 is the same or different, an alkyl group, aryl group or aralkyl group having 1 to 30 carbon atoms, or a group substituted with halogen, a group substituted with amino or a group substituted with carboxyl of the latter; - The subscripts a, b, c, d, e and f are integers satisfying the conditions of 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 satisfying the condition of 1≦n≦3) of a silicone resin containing a hydrosilyl group (B) The following general formulas (8), (9), (10), (11) and (12) CH2=CH-C l H 2l -O-(CH2CH(OH)CH2O)iR 4 (8) CH2=CH-C m H 2m -(SiOR 1 2) j- SiR 1 3(9) CH2=CH-C m H 2m -SiR 1 k1 -(OSiR 1 3) 3-k1 (10) CH2=CH-C m H 2m -SiR 1 k1 -(OSiR 1 k2 (OSiR 1 3) 3-k2)3-k1 (11) CH2=CH-C m H 2m -SiR 1 k1 -(OSiR 1 k2 (OSiR 1 k3 (OSiR 1 3) 3-k3)3-k2)3-k1 (12) (In the formula, -R 4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, -subscripts l and i are integers satisfying the conditions of 0≦l≦15 and 0<i≦5, -subscripts m, j and k1 to k3 are integers satisfying the conditions of |0≦m≦5, 0≦j≦500, 0≦k1≦2, 0≦k2≦2 and 0≦k3≦2)). It can be obtained by a hydrosilylation step using one or more compounds selected from compounds terminated with an alkenyl group: The silicone resin contains a compound of general formula (8).

[0082] The hydrosilyl group-containing organosilicon resin of the average composition formula (7) is mixed with a compound having a terminal alkenyl group of the general formula (8), (9), (10), (11) or (12) in a molar ratio expressed as hydrosilyl group / terminal unsaturated group, which is preferably from 0.5 to 2.0, more preferentially from 0.8 to 1.2.

[0083] 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-vinylsiloxane complex. Since an excessive amount of catalyst causes discoloration of the sample, the platinum or rhodium content is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0084] If necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, aromatic hydrocarbons such as toluene and xylene, ketone 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 viewpoint of reactivity, ethanol, 1-propanol, and 2-propanol are preferred.

[0085] The amount of solvent used is preferably 1% to 80%, more preferably 5% to 50%, of the entire reaction system. Within this range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0086] The conditions for the addition reaction are not particularly limited, but it is preferable to reflux the mixture by heating at a temperature of 50°C to 150°C, particularly 80°C to 120°C, for about 1 hour to 10 hours.

[0087] After the addition reaction, a step of removing the rhodium or platinum catalyst used in the activated carbon may be included. The amount of activated carbon used is preferably 0.001% to 5.0%, particularly 0.01% to 1.0%, of the total system. By keeping the amount of activated carbon within this range, discoloration of the sample can be further suppressed.

[0088] After the addition reaction, if necessary, a step of removing the remaining hydrosilyl groups can be included. In particular, when intended for use in applications such as cosmetics, these hydrosilyl groups may be deactivated over time by dehydrogenation, which poses a safety problem. Therefore, it is preferable to include a step of maintaining the hydrosilyl groups.

[0089] Examples of the process for removing hydrosilyl groups include adding a basic catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide to hydrolyze unreacted hydrosilyl groups, followed by neutralization by adding an acid catalyst in an amount equivalent to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include strongly basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate. From the viewpoint of promoting the dehydrogenation reaction, the use of a strongly basic catalyst is particularly preferred, with sodium hydroxide being particularly preferred. Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, oleum, 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 an acid or base alone, it is best to use them together with water and heat to a temperature below the boiling point of water.

[0090] After the addition reaction, a deodorizing step to reduce odor can be included, if necessary. In particular, when used in applications such as cosmetics, odors tend to develop over time, so a deodorizing step is preferable. The deodorizing mechanism of a typical polyether-modified silicone can be explained as follows. When an addition reaction between an allyl-etherified polyether and a hydropolyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as a side reaction, forming a propenyl-etherified polyether. This propenyl-etherified polyether is unreactive with the hydropolyorganosiloxane and remains in the system as an impurity. When water acts on this propenyl-etherified polyether, the propenyl ether hydrolyzes, producing propionaldehyde, which is thought to produce an unpleasant odor. It is known that the hydrolysis reaction is further accelerated in the presence of an acid catalyst. Therefore, when polyether-modified silicone is used in water-based cosmetics, the polyether becomes acidic over time due to oxidative degradation, accelerating the hydrolysis reaction described above and resulting in the generation of a foul odor.

[0091] There are two typical examples of deodorizing processes: The first is to add an acid catalyst to the solution after the addition reaction to hydrolyze all of the propenyl ether remaining in the system, and then remove the resulting propionaldehyde by stripping purification (Japanese Patent No. 2137062).

[0092] Specific examples of acid catalysts used in the first method include hydrochloric acid, sulfuric acid, sulfurous acid, oleum, 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. When it is necessary to remove the used acid, it is preferable to use an acid with a low boiling point such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Similarly, from the viewpoint of treatment effectiveness, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

[0093] The treatment temperature is preferably 80°C or less to avoid oxidation of the hydrophilic groups. The amount of acidic aqueous solution added is preferably 0.1% to 100% based on the organic group-modified organosilicon resin, and more preferably 5% to 30%.

[0094] From the viewpoint of productivity, a preferred step is to add an aqueous solution to the post-reaction liquid to adjust the pH to 7 or less, heat and stir the mixture, and then perform strip purification. The strip purification can be carried out at room temperature or under reduced pressure. The temperature condition is preferably fixed at 120°C or less. In order to efficiently purify the strip under these temperature conditions, this operation is preferably carried out under reduced pressure. When carried out at normal pressure, it is preferably carried out under a stream of an inert gas such as nitrogen or argon.

[0095] The second approach is to add hydrogen to the solution after the addition reaction, thereby alkylating the unsaturated double bond (subjecting it to a hydrogenation reaction), and controlling the formation of propionaldehyde over time in a stable manner (U.S. Pat. No. 5,225,509, JP-A-07-330907).

[0096] The hydrogenation reaction includes the method using hydrogen and the method using metal hydrides, and there are also homogeneous reactions and heterogeneous reactions. These methods can be used alone or in combination. However, heterogeneous catalytic hydrogenation using solid catalysts is preferred because it has the advantage that there is no trace of the catalyst used in the product.

[0097] The solid catalyst may be, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron, or the like, in an unbound form or in a compound form. In this case, a catalyst carrier is not required. However, if a catalyst carrier is used, the carrier may be, for example, activated carbon, silica, silica-alumina, alumina, or zeolite. These catalysts may be used alone or in combination. A preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with alkali, the pH of the reaction system must be carefully measured. Furthermore, the reaction system becomes weakly alkaline, making it particularly effective for deodorization when the hydrolysis reaction is carried out in an acidic aqueous solution.

[0098] The hydrogenation reaction is generally carried out at a pressure of 1 MPa to 100 MPa and a temperature of 50°C to 200°C, and can be carried out batchwise or continuously. In the case of a batch process, the reaction time depends on, for example, the amount of catalyst and the temperature, but is generally 3 to 12 hours. The hydrogen pressure can be adjusted to an appropriate constant pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure stops changing, and can therefore be determined by carefully monitoring the pressure gauge.

[0099] The amount of aldehyde contained in the glycerolized silicone resin purified by this acid treatment and this hydrogenation reaction can be reduced to 70 ppm or less, preferably 20 ppm or less, and more preferably 10 ppm or less.

[0100] In addition, the above two types of deodorization processes may be combined. In an approach involving acid treatment, decomposition and removal of aldehyde compounds are possible, but there is a limit to the complete removal of unsaturated double bonds, so the formation of odor aldehydes cannot be completely suppressed. In an approach involving a hydrogenation reaction, by removing unsaturated double bonds, it is possible to reduce the amount of aldehyde compounds formed as a result. However, aldehyde condensates formed by the condensation of a part of aldehydes remain in the system even after such treatment and are difficult to remove by stripping purification. As a result, by alkylating the remaining unsaturated double bonds when the solution after the addition reaction is subjected to hydrogenation and then adding an acid catalyst to decompose the aldehyde condensates in the system, complete deodorization is possible (WO 2002 / 05588 pamphlet).

[0101] The weight-average molecular weight of the glycerolated silicone resin of the average formula (1) is preferably from 1,000 to 100,000. From the viewpoints of operability such as filtration and performance, the weight-average molecular weight is preferably from 3,000 to 50,000. In the following, the weight-average molecular weight can be determined as the weight-average molecular weight in terms of polystyrene in gel permeation chromatography (GPC).

[0102] The glycerolated silicone resin according to the present invention can be in a form that can be solid or liquid at 25°C. From the viewpoint of film formability, it is preferably solid.

[0103] In particular, when the subscripts b and c satisfy the conditions of 0 < b ≤ 30 and 0 ≤ c ≤ 30, the subscript i of the general formula (2) satisfies the condition of 0 < i ≤ 3, and the subscript j of the general formula (3) satisfies the condition of 0 ≤ j ≤ 10, the glycerolated silicone resin according to the present invention of the formula (1) is in a solid form at 25°C and preferably has a weight-average molecular weight in the range from 1,000 to 100,000, more preferably in the range from 3,000 to 50,000.

[0104] The glycerolated silicone resin according to the present invention has a hydrophilic-lipophilic balance (HLB) determined by the Griffin's formula, preferably in the range of 0.1 to 15, more preferably in the range of 1.0 to 8.0.

[0105] According to a preferred form, the composition of the present invention comprises at least one glycerolated silicone resin of formula (1) of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type corresponding to the following formula (21): [Chemical formula 21] [(CH3)3SiO 1 / 2 a [R(CH3)2SiO 1 / 2 b (SiO 4 / 2 ) f (21) (wherein -R represents -a 3-glyceroxypropyl group having a C3H6OCH2-CH(OH)CH2OH structure, -the subscripts a, b and f are integers satisfying the conditions of 0≦a≦400, 0<b≦30, 0<f≦1000 and 0.5≦(a+b) / f≦1.5).

[0106] According to a particularly preferred form, the glycerolated silicone resin of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

[0107] For the purposes of the present invention, the term "volatile oil" refers to any oil that can evaporate upon contact with the skin in less than 1 hour at room temperature and atmospheric pressure. Volatile oils have, at room temperature and atmospheric pressure, inter alia, a non-zero vapor pressure and are, inter alia, volatile cosmetic compounds that are liquid at room temperature and have a vapor pressure in the range of 2.66 Pa to 40000 Pa, particularly in the range of 2.66 Pa to 13000 Pa, more particularly in the range of 2.66 Pa to 1300 Pa.

[0108] ​​The volatile oil according to the present invention may be selected from the group consisting of hydrocarbon oils, silicone oils, and mixtures thereof.

[0109] The term "hydrocarbon oil" is understood to mean an oil containing mainly hydrogen and carbon atoms and, optionally, one or more functional groups selected from hydroxyl, ester, ether and carboxyl groups.

[0110] Within the meaning of the present invention, "silicone oil" refers to an oil containing at least one Si-O group, more particularly an organopolysiloxane.

[0111] The volatile hydrocarbon-based oils that may be used in the compositions according to the invention may be chosen from branched C8 to C16 alkanes.

[0112] Mention may be made, inter alia, of isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and C8 to C16 isoalkanes (also known as isoparaffins) of petroleum origin, such as, for example, oils sold under the trade names Isopar® or Permethyl®. More preference is given to using isododecane.

[0113] Examples of volatile silicone oils that can be used in the present invention include volatile silicone oils such as volatile linear or cyclic silicone oils, particularly those having a viscosity of 2 to 8 centistokes (2×10 -6 ~8×10 -6 m 2 / s), particularly those containing 2 to 7 silicon atoms, optionally containing an alkyl or alkoxy group containing 1 to 10 carbon atoms. Volatile silicone oils that can be used in particular in the present invention include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; and mixtures thereof. More preferably, decamethylcyclopentasiloxane (D5) is used.

[0114] According to a particularly preferred embodiment, the glycerolated silicone resin of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type of formula (21) is in the form of a solution containing 49.5% by weight of active material in isododecane, for example the product manufactured by SHIN ETSU under the trade name X-25-9138A®, having a weight-average molecular weight of 11,000.

[0115] According to a preferred embodiment, in order to improve the grease resistance of the composition of the invention, the composition of the invention comprises at least one glycerolated silicone resin and at least one non-glycerolated silicone resin in a mass ratio of the amount of glycerolated silicone resin to the amount of non-glycerolated silicone resin of greater than or equal to 0.8, more preferentially greater than or equal to 1.0.

[0116] Volatile hydrocarbon oils The composition according to the invention comprises an oily phase comprising at least one volatile hydrocarbon oil.

[0117] The term "oil" refers to oil at room temperature (25°C) and atmospheric pressure (760 mmHg or 10 5 is understood to mean any fatty substance that is liquid at temperatures below 100°C (Pa).

[0118] The term "oily phase" is understood to mean an organic phase that is liquid at room temperature (25°C) and atmospheric pressure and is immiscible in water. It comprises at least one oil and any component that is soluble or miscible in said phase.

[0119] The volatile hydrocarbon oils that may be used in the compositions according to the invention may be chosen from branched C8 to C16 alkanes.

[0120] Mention may be made, inter alia, of isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and C8 to C16 isoalkanes (also known as isoparaffins) of petroleum origin, such as, for example, oils sold under the trade names Isopar® or Permethyl®.

[0121] Mention may also be made of branched C8-C16 esters such as isohexyl neopentanoate. Other volatile hydrocarbon oils may also be used, such as petroleum distillates, in particular those sold by Shell under the name Shell Solt®.

[0122] The volatile hydrocarbon oils that may be used in the compositions according to the invention may be chosen from volatile linear alkanes containing from 6 to 14 carbon atoms.

[0123] As examples of linear alkanes suitable for use in the present invention, mention may be made of the alkanes (mixtures of various alkanes differing by at least one carbon) described in WO 2007 / 068371 or WO 2008 / 155059 by Cognis, which are obtained from fatty alcohols which are themselves obtained from coconut kernel oil or palm oil.

[0124] As examples of linear C6 to C14 alkanes suitable for use in the present invention, mention may be made of n-hexane (C6), n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13) and n-tetradecane (C14), and mixtures thereof.

[0125] Mention may be made, inter alia, of n-dodecane (C12) and n-tetradecane (C14), sold by Sasol under the references Parafol 12-97® and Parafol 14-97®, respectively, and also mixtures thereof.

[0126] According to another embodiment, a mixture of n-dodecane and n-tetradecane is used, in particular the dodecane / tetradecane mixture in a mass ratio of 85 / 15 sold by Biosynthis under the trade designation Vegelight 1214®.

[0127] According to yet another embodiment, mixtures of volatile linear C9-C12 alkanes with the INCI name C9-12 Alkane may also be used, such as the product sold by Biosynthis under the trade designation Vegelight Silk®.

[0128] According to yet another embodiment, a mixture of n-undecane (C11) and n-tridecane (C13) is used, such as that obtained in Examples 1 and 2 of Cognis' application WO 2008 / 155059 and that sold by BASF under the trade name Cetiol Ultimate®.

[0129] According to a particularly preferred embodiment, the volatile hydrocarbon oil is selected from branched C8 to C16 alkanes, more particularly isododecane, mixtures of volatile linear C9 to C12 alkanes and mixtures of n-undecane (C11) and n-tridecane (C13).

[0130] According to a particularly preferred embodiment, the composition of the invention comprises at least one volatile oil chosen from C8 to C16 isoalkanes (also called isoparaffins) of petroleum origin, in particular isododecane.

[0131] The volatile hydrocarbon oil is preferably present in the composition of the invention in a content of up to 80% by weight, preferably between 40% and 70% by weight, relative to the total weight of said composition.

[0132] Lipophilic thickener The composition according to the invention comprises at least one lipophilic thickener.

[0133] The term "lipophilic thickener" is understood to mean any molecule that is lipophilic or lipodispersible in the oily phase of the composition and is capable of increasing the viscosity of the composition.

[0134] As lipophilic thickener at least one lipophilic clay is preferably used.

[0135] Clay refers to materials based on hydrated silicates and / or aluminosilicates with a layered structure.

[0136] The clays may be natural or synthetic and they have been made lipophilic by treatment with alkyl ammonium salts such as C10-C22 ammonium chlorides, especially stearalkonium chloride or distearyldimethylammonium chloride.

[0137] They may be chosen from bentonites, in particular bentonite, hectorite and montmorillonite, beidellite, saponite, nontronite, sepiolite, biotite, attapulgite, vermiculite and zeolites.

[0138] These are preferably selected from hectorite and bentonite.

[0139] According to a particularly preferred embodiment, in particular C10 to C22 quaternary ammonium chloride modified, hydrophobically modified bentonite and hydrophobically modified hectorite, for example: stearalkonium chloride-modified bentonites, such as those sold under the names Claytone AF®, Garamite VT®, Tixogel® LG-M, Tixogel® MP 250, Tixogel® VZ and Tixogel® VZ-V XR by BYK Additives Inc. or those sold under the names Viscogel® B3, Viscogel® B4, Viscogel® B7, Viscogel® B8, Viscogel® ED, Viscogel® GM, Viscogel® S4 and Viscogel® SD by Bentec SPA; stearalkonium chloride-modified bentonite in the presence of at least propylene carbonate and at least one oil, such as the commercial products Dub Velvet Gum® from Stearinerie Dubois Fils, Miglyol GEL T® from Cremer Oleo, Tixogel® CGT 6030, Tixogel® DBA 6060, Tixogel® FTN, Tixogel® FTN 1564, Tixogel® IPM, Tixogel® LAN, Tixogel® LAN 1563 from BYK Additives Inc; distearyldimethylammonium chloride modified hectorite (INCI name: Disteardimonium Hectorite), such as the product sold under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialities; - hectorites modified with distearyldimethylammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil, such as those sold under the names 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 or Bentone® VS-5 by Elementis Specialities; those sold under the names Creagel Bentone CPS / Hectone CPS or Creagel Bentone ID® / Hectone ID by Creations Couleurs; NS Gel DM1®, NS Gel PTIS® or NS MGel® by Next Step Laboratories Stop. An organophilic clay selected from the commercially available product sold under the trademark 1152 will be used.

[0140] More particularly, use is made of hectorite modified with distearyldimethylammonium chloride (INCI name: Disteardimonium Hectorite), such as the product sold under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialties.

[0141] The lipophilic thickener may be present in the composition at a concentration preferably ranging from 0.5% to 10% by weight, and more preferentially from 1% to 6% by weight, relative to the total weight of the composition.

[0142] Silicone Polyamide According to one particular embodiment, the composition according to the invention also comprises at least one silicone polyamide.

[0143] The silicone polyamide is preferably a solid at room temperature (25° C.) and atmospheric pressure (760 mmHg).

[0144] For purposes of this invention, the term "polymer" means a compound containing at least 2 repeat units, preferably at least 3 repeat units, and better still, 10 repeat units.

[0145] The silicone polyamides of the compositions of the present invention may be polyorganosiloxane type polymers, such as those described in US Patent Nos. 5,874,069, 5,919,441, 6,051,216 and 5,981,680. According to the present invention, the silicone polymers may belong to two groups: (1) a polyorganosiloxane containing at least two amide groups, the two groups being located in the polymer chain; and / or (2) Polyorganosiloxanes containing at least two amide groups, these two groups being located on the grafts or branches.

[0146] According to a first variant, the silicone polymer is a polyorganosiloxane as defined above, in which the units capable of establishing hydrogen interactions are located in the polymer chain.

[0147] The silicone polymer more particularly has the general formula I(I): [Chemical formula 22] [ka] (In the formula, when G represents -C(O)-NH-Y-NH-, G' represents C(O), and when G represents -NH-C(O)-YC(O)-, G' represents -NH-; R may be the same or different 4 , R 5 , R 6 and R 7 teeth, saturated or unsaturated, linear, branched or cyclic C1-C40 hydrocarbon groups, which may contain one or more oxygen, sulfur and / or nitrogen atoms in their chain and which may be partially or completely substituted with fluorine atoms, - a C6-C10 aryl group optionally substituted with one or more C1-C4 alkyl groups; represents a group selected from polyorganosiloxane chains which may contain one or more oxygen, sulfur and / or nitrogen atoms, X groups, which may be the same or different, represent straight-chain or branched C1-C30 alkylenediyl groups which may contain one or more oxygen and / or nitrogen atoms in the chain; Y is a saturated or unsaturated C1 to C50 straight or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene divalent radical, which may contain one or more oxygen, sulfur and / or nitrogen atoms and / or may bear as a substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with one to three C1 to C3 alkyl, C1 to C3 hydroxyalkyl and C1 to C6 aminoalkyl groups, or Y represents a group corresponding to formula (23): [Chemical formula 23] [ka] (In the formula, T represents a linear or branched, saturated or unsaturated, trivalent or tetravalent C3 to C24 hydrocarbon group, which may optionally be substituted with a polyorganosiloxane chain and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al; R 8 represents a linear or branched C1-C50 alkyl group or polyorganosiloxane chain which may contain one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups which may be attached to another chain of the polymer; n is an integer ranging from 2 to 500, preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700, and even better from 6 to 200. Preferably, m is an integer ranging from 50 to 150.

[0148] According to one embodiment of the present invention, the group R of the polymer 4 , R 5 , R 6 and R 7 Preferably, 80% of the groups R of the polymer are selected from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. 4 , R 5 , R 6 and R 7 80% of the carbon atoms are methyl groups.

[0149] According to the present invention, Y may represent a variety of divalent groups, optionally containing one or two free valencies to establish bonds with other units of the polymer or copolymer. - a linear C1-C20, preferably C1-C10 alkylene group, -C30 to C56 branched alkylene groups which may contain rings and non-conjugated unsaturation; -C5-C6 cycloalkylene group, - a phenylene group optionally substituted with one or more C1-C40 alkyl groups; - a C1-C20 alkylene group containing 1 to 5 amide groups; - a C1-C20 alkylene group containing one or more substituents selected from hydroxyl, C3-C8 cycloalkane, C1-C3 hydroxyalkyl and C1-C6 alkylamine groups; polyorganosiloxane chains of formula (24) or (25): [Chemical formula 24] [ka] [Chemical formula 25] [ka] (In the formula, R 4 , R 5 , R 6 , R 7 , T and m are as defined above) represents a group selected from

[0150] According to a second variant, the polyorganosiloxane has formula (II): [Chemical formula 26] [ka] (In the formula, R 4 and R 6 are the same or different and are as defined above for formula (I), R 10 is R 4 and R 6 represents a group as defined above for 12 wherein X and G are as defined above for formula (I), and R 12 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated C1 to C50 hydrocarbon group which optionally contains in its chain one or more atoms selected from O, S and N and is optionally substituted with one or more fluorine atoms and / or one or more hydroxyl groups or phenyl groups optionally substituted with one or more C1 to C4 alkyl groups; R11 is the formula -XGR 12 wherein X, G and R 12 is as defined above, m1 is an integer ranging from 1 to 998; m2 is an integer ranging from 2 to 500.

[0151] According to a particular embodiment of the invention, the silicone polyamide may be a homopolymer, ie a polymer comprising several identical units, in particular units of formula (I) or formula (II).

[0152] According to another particular embodiment of the present invention, silicone polyamides are formed from copolymers comprising several different units of formula (I), i.e., R 4 , R 5 , R 6 , R 7 It is also possible to use polymers in which at least one of the following is different in one of the units: X, G, Y, m, and n. Copolymers can also be used. 4 , R6, R 10 , R 11 , m1 and m2 may be formed from several units of formula (II) which differ in at least one of the units.

[0153] It is also possible to use polymers comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) being optionally identical to one another or different.

[0154] According to one variant of the invention, it is also possible to use polymers which further comprise at least one hydrocarbon-based unit containing two groups capable of establishing hydrogen interactions, chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamide, guanidino and biguanidino groups, and combinations thereof.

[0155] These copolymers can be block or grafted polymers.

[0156] According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula -C(O)NH and -HNC(O).

[0157] In this case, the film-forming agent has the formula (III) or (IV): [Chemical formula 27] [ka] or [Chemical formula 28] [ka] (In the formula, R 4 , R 5 , R 6 , R 7 , X, Y, m and n are as defined above).

[0158] In these polyamides of formula (III) or (IV), m is in the range from 1 to 700, in particular from 15 to 500, in particular from 50 to 200, and n is in the range from 1 to 500, preferably from 1 to 100 and better still from 4 to 25, X is preferably a linear or branched alkylene chain having 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, in particular 5 to 15 carbon atoms, more in particular 10 carbon atoms, and Y is preferably an alkylene chain which may be linear or branched or may contain rings and / or unsaturation, containing 1 to 40 carbon atoms, in particular 1 to 20 carbon atoms, more preferably 2 to 6 carbon atoms, in particular 6 carbon atoms.

[0159] In formulas (III) and (IV), the alkylene group representing X or Y may contain the following components in the alkylene moiety: - 1 to 5 amide, urea, urethane or carbamate groups, -C5 or C6 cycloalkyl group, and - a phenylene group optionally substituted with 1 to 3 identical or different C1-C3 alkyl groups It may optionally contain at least one of the following.

[0160] In formulae (III) and (IV), the alkylene group may also be -hydroxyl group, -C3 to C8 cycloalkyl group, - 1 to 3 C1 to C40 alkyl groups, - a phenyl group optionally substituted by 1 to 3 C1-C3 alkyl groups, -C1 to C3 hydroxyalkyl groups, and It may be substituted with at least one component selected from the group consisting of -C1 to C6 aminoalkyl groups.

[0161] In these formulas (III) and (IV), Y may also be a group represented by the formula (29): [Chemical formula 29] [ka] (In the formula, R 8 represents a polyorganosiloxane chain), and T represents a group of formula (30): [Chemical formula 30] [ka] (wherein a, b, and c are independently integers ranging from 1 to 10; R 13 is a hydrogen atom or R4, R5, R 6 and R 7 (which is a group such as those defined with respect to

[0162] In formulas (III) and (IV), R 4 , R 5 , R 6 and R 7 preferably independently represent a linear or branched C1 to C40 alkyl group, preferably CH3, C2H5, n-C3H7 or an isopropyl group, a polyorganosiloxane chain, or a phenyl group optionally substituted with 1 to 3 methyl or ethyl groups.

[0163] According to a preferred embodiment, the silicone polyamide comprises at least one unit of formula (III) or (IV).

[0164] As already indicated, the polymer may contain identical or different units of formula (III) or (IV).

[0165] The polymer may therefore be a polyamide containing several units of formula (III) or (IV) of different lengths, i.e., a polymer of formula (V): [Chemical formula 31] [ka] (Wherein X, Y, n and R 4 ~R 7 has the meaning given above, and different m 3 and m 4 is selected in the range of 1 to 1000, and p is an integer in the range of 2 to 300. In this formula, the units can be structured to form either block copolymers, or random or alternating copolymers.

[0166] In this copolymer, the units may not only differ in length but also in chemical structure, for example containing different groups Y. In this case, the polymer has the formula (VI): [Chemical formula 32] [ka] (In the formula, R 4 ~R 7 , X, Y, m3, m4, n and p have the above meanings, and Y1 may correspond to Y but is selected from the groups defined for Y).

[0167] As noted above, the various units may be structured to form either block copolymers, or random or alternating copolymers.

[0168] In a first embodiment of the present invention, the film-forming agent may be composed of a graft copolymer. Thus, a polyamide containing silicone units may be grafted and optionally crosslinked with silicone chains containing amide groups. Such a polymer may be synthesized with a trifunctional amine. In this case, the polymer may have the formula (VII): [Chemical formula 33] [ka] (Wherein, the same or different X 1 and X 2has the meaning indicated for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), R 14 ~R 21 But R 4 ~R 7 wherein m5 and m6 are numbers in the range of 1 to 1000, and p is an integer in the range of 2 to 500).

[0169] In formula (VII), p is in the range of 1 to 25, more preferably 1 to 7; R 14 ~R 21 is a methyl group, T is a compound having the formula: [Chemical formula 34] [ka] wherein R 22 is a hydrogen atom or R 4 ~R 7 is a group selected from the groups defined for 23 , R 24 and R 25 are independently a linear or branched alkylene group, more preferably of the formula: [Chemical formula 35] [ka] In particular, R 23 , R 24 and R 25 is -CH2-CH2-, m1 and m2 are in the range of 15 to 500, and more preferably 15 to 45; X 1 and X 2 Ga-(CH2) 10 - and Preferably, Y represents -CH2-.

[0170] These polyamides containing grafted silicone units of formula (VII) can be copolymerized with silicone polyamides of formula (II) to form block, alternating or random copolymers. The weight percentage of grafted silicone units (VII) in the copolymer can range from 0.5% to 30% by weight.

[0171] According to the present invention, as already indicated, the siloxane units can be in the main chain or backbone of the polymer, but they can also be present in grafted or pendant chains. In the main chain, the siloxane units can be in the form of segments as described above. In the pendant or grafted chains, the siloxane units can appear individually or in segments.

[0172] According to a variant of one embodiment of the present invention, copolymers of silicone polyamides and hydrocarbon-based polyamides or copolymers comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units can be used, where the silicone polyamide units can be located at the ends of the hydrocarbon-based polyamide.

[0173] According to a preferred embodiment, the silicone polyamide comprises units of formula (III). [ka] (In the formula, R 4 , R 5 , R 6 and R 7 each independently represents a linear or branched C1 to C40 alkyl group, preferably CH3, C2H5, n-C3H7 or an isopropyl group, a polyorganosiloxane chain, or a phenyl group optionally substituted with 1 to 3 methyl or ethyl groups; m is in the range of 1 to 700, particularly 15 to 500, and in particular 50 to 200; and n is in the range of 1 to 500, preferably 1 to 100, and more preferably 4 to 25.

[0174] Preferably, according to this embodiment, the silicone polyamide comprises a group R 4, R 5 , R 6 and R 7 represents a methyl group, one of X and Y represents an alkylene group of 6 carbon atoms, and the other represents an alkylene group of 11 carbon atoms, and n represents the degree of polymerization (DP) of the polymer.

[0175] As examples of such silicone polyamides, mention may be made of the compounds sold by Dow Corning under the names Dowsil 2-8179 Gellant® (DP100) and Dowsil 2-8178 Gellant® (DP15), whose INCI name is Nylon-611 / Dimethicone Copolymer.

[0176] Advantageously, the composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) with the index m having a value of about 100.

[0177] The subscript m corresponds to the degree of polymerization of the silicone portion of the polymer.

[0178] More preferably, the composition according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m is in the range from 50 to 200, in particular from 75 to 150, and preferably about 100.

[0179] An example of a silicone polymer that can be used is one of the silicone polyamides obtained according to Examples 1 to 3 of US Pat. No. 5,981,680.

[0180] According to a preferred embodiment, polyamide silicone having the INCI name: Nylon-611 / Dimethicone Copolymer, sold by Dow Corning under the INCI name: Dowsil 2-8179 Gellant® (DP100), is used.

[0181] The polymers and / or copolymers used in the compositions of the invention advantageously have a solid to liquid state transition temperature in the range from 45° C. to 190° C. Preferably, they have a solid to liquid state transition temperature in the range from 70° C. to 130° C., and even more preferably in the range from 80° C. to 105° C.

[0182] The content of silicone polyamide, expressed as active substance, is preferably in the range of 5% to 30% by weight, more preferably 10% to 25% by weight, and more particularly 8% to 15% by weight, relative to the weight of composition (B).

[0183] cosmetic additives The compositions may contain conventional cosmetic additives such as colorants, preservatives, fragrances, antioxidants, moisturizers, lipophilic active agents such as vitamins, lipophilic UV screening agents, fillers, and the like.

[0184] Of course, one skilled in the art will take care to select any additional additives and / or amounts thereof such that the advantageous properties of the compositions according to the present invention are not adversely affected or substantially unaffected by the envisaged addition.

[0185] coloring agent The composition according to the present invention may further comprise at least one colorant.

[0186] According to a particular embodiment of the invention, the colorant may be chosen from powder colorants, liposoluble dyes, and mixtures thereof.

[0187] a) Powdered colorant The powdered colorant may be selected from mineral pigments, organic pigments, pearlescent agents and mixtures thereof.

[0188] The term "pigments" means white or colored, inorganic or organic particles that are insoluble in aqueous media and are intended to color and / or opacify the resulting composition and / or deposit. These pigments can be white or colored, inorganic and / or organic.

[0189] According to a particular embodiment, the pigments used according to the invention are chosen from inorganic pigments.

[0190] The term "inorganic pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's Encyclopaedia. Among the inorganic pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow, or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metal powders such as aluminum and copper powder. The following inorganic pigments may also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 in a mixture with TiO2, ZrO2, Nb2O5, CeO2, or ZnS.

[0191] The size of the pigments used in connection with the present invention may generally range from more than 100 nm to 10 μm, preferably from 200 nm to 5 μm, and more preferentially from 300 nm to 1 μm.

[0192] According to a particular embodiment of the invention, the pigment diameter is characterized by a D

[50] greater than 100 nm and may range up to 10 μm, preferably between 200 nm and 5 μm, more preferably between 300 nm and 1 μm.

[0193] The size is measured by static light scattering using a commercially available MasterSizer 3000® particle size analyzer from Malvern, which allows the determination of the full particle size distribution over a wide range that can extend from 0.01 μm to 1000 μm. The data are processed based on the standard Mie scattering theory. This theory is most suitable for size distributions in the submicron to multimicron range; it allows the determination of the "effective" particle size. This theory is described, inter alia, in the publication by Van de Hulst, HC, Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

[0194] D

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

[0195] According to a particular form of the invention, the inorganic pigment comprises an oleophilic or hydrophobic coating, said coating preferably being present in the oily phase of the composition according to the invention.

[0196] According to a particular embodiment of the present invention, the pigment may be coated in accordance with the present invention with at least one compound selected from metal soaps; N-acylamino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

[0197] According to a particular embodiment, pigments may be coated in accordance with the present invention with N-acylamino acids or salts thereof, which may comprise an acyl group containing 8 to 22 carbon atoms, such as a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, or cocoyl group.

[0198] 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 pigment may be coated with an N-acylamino acid derivative, which may be, in particular, a glutamic acid derivative and / or its salt, more particularly stearoyl glutamate, such as aluminum stearoyl glutamate. Examples of pigments treated with aluminum stearoyl glutamate include titanium dioxide pigments and black, red, and yellow iron oxide pigments sold by Miyoshi Kasei Co., Ltd. under the trade name NAI®.

[0199] According to a preferred embodiment, the pigment according to the invention can be coated with isopropyl triisostearyl titanate. Examples of isopropyl titanium triisostearate (ITT) treated pigments include titanium dioxide pigments sold by Kobo under the trade names BWBO-I2® (iron oxide CI 77499 and isopropyl titanium triisostearate), BWYO-I2® (iron oxide CI 77492 and isopropyl titanium triisostearate) and BWRO-I2® (iron oxide CI 77491 and isopropyl titanium triisostearate), as well as black, red and yellow iron oxides.

[0200] Among the mineral pigments, mention may also be made of pearlescent agents, which may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, titanium mica with iron oxide, especially titanium mica with ferric blue or chromium oxide, titanium mica with organic pigments of the aforementioned type, and also nacreous pigments based on bismuth oxychloride.

[0201] The pigments that can be used according to the invention can also be organic pigments.

[0202] "Organic pigment" means any pigment that meets the definition in the chapter on organic pigments of Ullmann's encyclopedia. The organic pigment may be selected from, inter alia, nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

[0203] Organic pigments are, for example, carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments which are codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, yellow pigments which are codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, green pigments which are codified in the Color Index under the references CI 61565, 61570 and 74260, orange pigments which are codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, red pigments which are codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, The red pigments may be selected from those designated as 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, as well as pigments obtained by oxidative polymerization of indole or phenol derivatives, as described in French Patent No. 2 679 771.

[0204] These pigments may be in the form of composite pigments, such as those described in EP 1 184 426. These composite pigments may consist, inter alia, of particles comprising an inorganic core at least partially covered with an organic pigment and at least one binder for fixing the organic pigment to the core.

[0205] The pigment may also be a lake, the term "lake" meaning an insolubilized dye adsorbed onto an insoluble particle, the resulting mass remaining insoluble during use.

[0206] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0207] Among the organic dyes, mention may be made of cochineal carmine. Mention may also be made of products known under the following names: D&C Red 21 (CI 45380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 4 (CI 15510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green (CI 61570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42053) or D&C Blue 1 (CI 42090).

[0208] As an example of a lake, mention may be made of the product known under the name D&C Red 7 (CI 15 850:1).

[0209] Preferably, the powdered colorant is present in the composition in a content of not more than 50% by weight, preferably from 25% to 40% by weight, more particularly from 3% to 15% by weight, relative to the total weight of the composition.

[0210] b) liposoluble colorants The composition according to the invention may comprise at least one liposoluble colorant, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition.

[0211] For obvious reasons, this amount is subject to great variation depending on the strength of the desired color effect and the color intensity imparted by the colorant under consideration, adjustment of which is clearly within the capabilities of one skilled in the art.

[0212] For the purposes of the present invention, the term "oil-soluble colorant" is intended to mean any compound, natural or synthetic, usually organic, that is soluble in an oily phase or in a solvent that is miscible with fatty substances and that is capable of imparting color.

[0213] Lipid-soluble dyes that are suitable for use in the present invention may include, inter alia, synthetic or natural liposoluble dyes such as DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan Brown, quinoline yellow, annatto and curcumin.

[0214] Preferably, the composition according to the invention comprises at least one powdered colorant of inorganic pigment type, in particular chosen from metal oxides, more in particular coated or uncoated titanium dioxide or iron oxides and mixtures thereof.

[0215] According to a particularly preferred embodiment, the composition according to the invention comprises at least one powder colorant selected from titanium dioxide according to the invention coated with one of black, red or yellow iron oxides coated with isopropyl triisostearyl titanate, black, red or yellow iron oxides coated with isopropyl triisostearyl titanate, and mixtures thereof.

[0216] Cosmetic applications The composition used according to the invention may be a composition for caring for and / or structuring keratinous materials, in particular eyebrows, including eyebrow hairs, the skin for implanting said hairs and their contours.

[0217] According to a particularly preferred form, the compositions of the invention are anhydrous.

[0218] For the purposes of the present invention, the expression "anhydrous composition" denotes a composition containing less than 5% by weight of water, preferably less than 2% by weight of water, indeed even less than 0.5% by weight of water, respectively, relative to its total weight, and in particular a composition that is free of water.

[0219] More particularly, the composition according to the invention is a makeup product such as eyebrow care and / or mascara.

[0220] Such compositions are in particular prepared according to the general knowledge of the person skilled in the art.

[0221] Packaging and Application Assembly or Kit The present invention also provides an assembly or kit for packaging and applying a cosmetic composition for coating keratinous materials, comprising: a packaging device containing said cosmetic composition for coating keratinous materials as described above, - an assembly or kit comprising an applicator for said composition.

[0222] According to another aspect, the present invention also provides a method for producing a method of manufacturing a pharmaceutical composition comprising: i) Applicator ii) A makeup assembly comprising a composition according to the invention disposed in a container.

[0223] The container may define one or more compartments. The container may, for example, be in the form of a tube.

[0224] Such an applicator may be integral with a cap that is reversibly attached to the container between a closed position and a cosmetic position of the container.

[0225] In the alternative, such an applicator may be irreversibly attached to said container.Examples of applicators include those of the felt or brush type, which may be made of synthetic fibers.

[0226] It is understood that in the context of the present invention, the weight percentages given for compounds or compound families are always expressed as weight relative to the total weight of the composition.

[0227] Throughout this patent application, the term "including one" should be understood to mean "including at least one," unless otherwise specified.

[0228] It will be understood that the following examples are presented by way of illustration and in no way limit the scope of protection conferred by this patent application. [Example]

[0229] Formulation example Example 1: Preparation of a decamethylcyclopentasiloxane solution containing 60% 3-glyceroxypropyl group-modified silicone resin A reactor was charged with 1300 g of a decamethylcyclopentasiloxane solution containing 50% hydrosilyl group-containing powdered organosilicon resin (weight average molecular weight: 4480; hydrogen gas generation rate: 8.0 ml / g) having the average composition (E4), 30.7 g of glycerol monoallyl ether of formula (E5), 1300 g of 2-propanol, and 0.7 g of a 0.5% solution of chloroplatinic acid in 2-propanol. The reaction was heated at 100 °C for 6 hours, followed by heating under reduced pressure to remove the solvent. Next, 325 g of ethanol was added, followed by 6.5 g of 5% aqueous sodium hydroxide to hydrolyze unreacted hydrosilyl groups, followed by neutralization with 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of 0.01 N aqueous hydrochloric acid was added to hydrolyze unreacted allyl ether groups on the polyoxyalkylene, and the mixture was neutralized with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was heated under reduced pressure to remove the solvent, and then filtered to obtain a decamethylcyclopentasiloxane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6). The solution was clear and colorless.

[0230] The decamethylcyclopentasiloxane solution of this 3-glyceroxypropyl group-modified silicone resin was heated to 120°C to 130°C under reduced pressure to remove the decamethylcyclopentasiloxane. The resulting product was a solid powder with an HLB of 0.9. (MeSiO 1 / 2 ) 27.8 (HMe2SiO 1 / 2 ) 1.6 (SiO 4 / 2 ) 35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (MeSiO 1 / 2 ) 27.8 (R 2 Me2SiO 1 / 2 ) 1.6 (SiO 4 / 2 ) 35.3 (E6) R 2 =-CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H

[0231] Example 2: Preparation of an isododecane solution containing 60% by mass of 3-glyceroxypropyl group-modified silicone resin A reactor was charged with 1300 g of an isododecane solution containing 50% hydrosilyl group-containing organosilicon resin powder having the average composition formula (E4) (weight average molecular weight: 4480; hydrogen gas generation rate: 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 2-propanol solution. The reaction was heated at 100 °C for 6 hours, followed by heating under reduced pressure to remove the solvent. Next, 325 g of ethanol was added, followed by 6.5 g of 5% aqueous sodium hydroxide to hydrolyze unreacted hydrosilyl groups, followed by neutralization with 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of 0.01 N aqueous hydrochloric acid was added to hydrolyze unreacted allyl ether groups on the polyoxyalkylene, and the mixture was neutralized with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was then heated under reduced pressure to remove the solvent, and filtered to obtain an isododecane solution of the silicone resin of formula (E6) modified with 3-glyceroxypropyl groups. (MeSiO 1 / 2 ) 27.8 (HMe2SiO 1 / 2 ) 1.6 (SiO 4 / 2 ) 35.3 (E4) CH2=CH-CH2-O-(CH2CH(OH)CH2O)-H (E5) (MeSiO 1 / 2 ) 27.8 (R 2 Me2SiO 1 / 2 ) 1.6 (SiO 4 / 2 ) 35.3 (E6) R 2 =-CH2-CH2-CH2-O-(CH2CH(OH)CH2O)-H.

[0232] Examples of eyebrow makeup compositions The following compositions were prepared:

[0233] [Table 1]

[0234] Protocol for preparation of the composition Disteardimonium hectorite was pre-dispersed in isododecane. All ingredients were added to an Orsa tank, then heated to 70°C, homogenized for 30 minutes, and then cooled to room temperature (25°C).

[0235] Test for measuring wear properties: Sebum resistance Test Protocol Each of Formulas 1, 2 and 3 was spread with a manual spreader (100 microns).

[0236] The film is allowed to dry for 24 hours.

[0237] Two drops of each solution of artificial sebum were deposited onto the film.

[0238] The droplets are left on the film for 24 hours.

[0239] Excess solution is removed by wiping with cotton wool.

[0240] The resistance of the film is evaluated (e.g., traces of droplets, melted film on edges, holes, etc.).

[0241] A finger cot was used to rub the film at the location where the drop was deposited.

[0242] The resistance of the film before and after abrasion is evaluated according to three resistance criteria: A: Good film resistance B: Significant alteration of the film C: Film disappearance

[0243] The results obtained are shown in the table below.

[0244] [Table 2]

[0245] The results of the comparative test showed that Examples 1 and 2 of the present invention, which contain a combination of the non-glycerolated silicone resin trimethylsiloxysilicate and the glycerolated silicone resin (3-glyceroxypropyl) dimethylsiloxytrimethylsiloxysilicate, showed excellent sebum resistance both before and after rubbing, unlike Example 3, which does not contain a glycerolated silicone resin and combines the non-glycerolated silicone resin trimethylsiloxysilicate with the silicone polyamide NYLON-611 / dimethicone copolymer.

Claims

1. A composition for caring for and / or structuring keratinous materials, in particular eyebrows, including eyebrow hairs, the skin for implanting said hairs and their contours, comprising, in particular in a physiologically acceptable medium: a) at least one non-glycerolated silicone resin of the MQ type, and b) at least one glycerolated silicone resin; and c) at least one oily phase containing at least one volatile hydrocarbon; and d) A composition comprising a lipophilic thickener.

2. 10. The composition of claim 1, comprising at least one silicone resin of the trimethylsiloxysilicate type.

3. 3. The composition of claim 2, wherein the trimethylsiloxysilicate resin is in solution in isododecane, in particular in a solution containing 75% by weight of active material in isododecane.

4. 4. Composition according to any one of claims 1 to 3, wherein the non-glycerolated silicone resin is present in an active matter 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 preferentially ranging from 8% to 25% by weight relative to the total weight of the composition.

5. 5. Composition according to any one of claims 1 to 4, wherein the glycerolized silicone resin is present in an active substance 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 preferentially ranging from 0.5% to 15% by weight relative to the total weight of the composition.

6. 6. The composition according to claim 1, wherein the glycerolated silicone resin comprises at least one organosiloxane unit of the RR'R''SiO1 / 2 type, where R, R' and R''', which may be identical or different, represent hydrocarbon groups, at least one of said groups comprising a monoglycerol group or a polyglycerol group.

7. The glycerolated silicone resin comprises at least one dimethylsiloxane R(CH) containing a hydrocarbon group R containing a monoglycerol group. ３ ) ２ SiO １／２ The composition of claim 6 comprising a unit.

8. The glycerolized silicone resin is represented by the following formula (1): (R １ ３ Yes １／２ ) ａ (R ２ (CH) ３ ) ２ Yes １／２ ) ｂ (R ３ ３ Yes １／２ ) ｃ (R １ ２ Yes ２／２ ) ｄ (R １ Yes ３／２ ) ｅ (Yes) ４／２ ) ｆ (1) (In the formula, -Each R １ are the same or different alkyl, aryl or aralkyl groups having 1 to 30 carbon atoms, or halogen-substituted, amino-substituted or carboxyl-substituted groups of the latter; -Each R ２ is a monoglycerol or polyglycerol group of the following general formula (2): -(CH ２ ) ２ -C ｌ H ２ｌ -O-(CH ２ CH(OH)CH ２ O) ｉ R ４ (2) (In the formula, -R ４ is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, - The subscripts l and i are integers that satisfy the conditions 0≦l≦15, 0<i≦5. -Each R ３ represents the following general formula (3), general formula (4), general formula (5) or general formula (6): -(H) ２ ) ２ -C ｍ H ２ｍ -(SiPR １ ２ )j-SiR １ ３ (3) -(CH ２ ) ２ -C ｍ H ２ｍ -SiR １ ｋ１ -(OSiR １ ３ ) ３－ｋ１） (4) -(CH ２ ) ２ -C ｍ H ２ｍ -SiR １ ｋ１ -(OSiR １ ｋ２ (OSiR １ ３ ) ３－ｋ２ ) ３－ｋ１ (5) -(CH ２ ) ２ -C ｍ H ２ｍ -SiR １ ｋ１ -(OSiR １ ｋ２ (OSiR １ ｋ３ (OSiR １ ３ ) ３－ｋ３ ) ３－ｋ２ ) ３－ｋ１ (6) (In the formula, -Each R １ are the same or different alkyl, aryl or aralkyl groups having 1 to 30 carbon atoms, or halogen-substituted, amino-substituted or carboxyl-substituted groups of the latter; - the subscripts m, j and k １ ~k ３ are integers satisfying the conditions 0≦m≦5, 0≦j≦500, 0≦k1≦2, 0≦k2≦2, and 0≦k3≦2; The composition according to any one of claims 1 to 7, wherein the subscripts a, b, c, d, e and f are selected from the following: identical or different radicals, where 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.

9. The glycerolated silicone resin of formula (1) is The subscripts b and c satisfy the conditions 0<b≦30 and 0≦c≦30, -polyglycerol group R ２ The composition according to claim 8, wherein the subscript i in the general formula (2) is selected from integers satisfying the condition 0<i≦3.

10. 10. Composition according to claim 8 or 9, wherein said glycerolated silicone resin of formula (1) has a weight average molecular weight preferably ranging from 1000 to 100,000, more preferentially from 3000 to 50,000.

11. The glycerolated silicone resin of the average formula (1) satisfies the condition 0<c≦400, and R ３ is a group of general formula (3) and the subscript j satisfies the condition 0≦j≦10, the composition being in solid form at 25° C.

12. 12. The composition of any one of claims 8 to 11, wherein the glycerolated silicone resin has a hydrophilic-lipophilic balance (HLB), as determined by Griffin's formula, in the range of 0.1 to 15, more preferably 1.0 to 8.

0.

13. at least one glycerolated silicone resin of formula (1) of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type, corresponding to formula (21) below: [(CH ３ ) ３ Yes １／２ ] ａ [R(CH) ３ ) ２ Yes １／２ ] ｂ (Yes) ４／２ ) ｆ (21) (In the formula, -R is the structure -C ３ H ６ OCH ２ -CH(OH)CH ２ OH represents a 3-glyceroxypropyl group; The composition according to any one of claims 8 to 12, wherein the subscripts 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.

14. 14. The composition according to claim 13, wherein the glycerolated silicone resin of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

15. 15. The composition of claim 14, wherein the glycerolated silicone resin of the (3-glyceroxypropyl)dimethylsiloxytrimethylsiloxysilicate type of formula (21) is in the form of a solution containing 49.5% by weight of active material in isododecane.

16. 16. The composition according to any one of claims 1 to 15, comprising at least one glycerolated silicone resin and at least one non-glycerolated silicone resin, in a mass ratio of the amount of glycerolated silicone resin to the amount of glycerolated silicone resin greater than or equal to 0.8, more preferentially greater than or equal to 1.

0.

17. 17. The composition according to any one of claims 1 to 16, comprising at least one volatile oil selected from C8-C16 isoalkanes of petroleum origin, in particular isododecane.

18. 18. The composition according to any one of claims 1 to 17, wherein the volatile hydrocarbon oil is present in a content of preferably up to 80% by weight, preferably between 40% and 70% by weight, relative to the total weight of the composition.

19. 19. A composition according to any one of the preceding claims, wherein the lipophilic thickener is a lipophilic clay, more particularly a hectorite modified with distearyldimethylammonium salt, having the INCI name: Disteardimonium Hectorite.

20. 20. The composition according to any one of the preceding claims, wherein said lipophilic thickener is present in a concentration ranging preferably from 0.5% to 10% by weight, more preferentially from 1% to 6% by weight, relative to the total weight of the composition.

21. 21. The composition according to any one of claims 1 to 20, further comprising at least one silicone polyamide polymer having an anhydrous gel such as commercially available Inked Waterproof Brow Gel® from Urban Decay (Mintel ID 7578707) and Styling Gel® up to 3 Days from Maybelline (Mintel ID 10361806), preferably comprising a combination of nylon 611,5 / dimethicone copolymer with the following INCI names.

22. 22. Composition according to claim 21, in which the content of silicone polyamide, expressed as active substance, ranges from 5% to 30% by weight, more preferentially from 10% to 25% by weight and more particularly from 8% to 15% by weight relative to the weight of the composition.

23. A composition according to any one of the preceding claims, further comprising at least one colorant, preferably selected from powder colorants, liposoluble dyes and mixtures thereof.

24. 24. The composition according to claim 23, wherein the powder colorant is present in a content of up to 50.0% by weight, preferably ranging from 25% to 40% by weight, and more particularly ranging from 3% to 15% by weight, relative to the total weight of the composition.

25. 25. A composition according to claim 23 or 24, wherein the powdered colorant is selected from metal oxides, more particularly from coated or uncoated titanium dioxide or black, red or yellow iron oxide, and mixtures thereof.

26. 26. The composition of claim 25, comprising at least one powder colorant selected from titanium dioxide coated with isopropyl triisostearyl titanate, black, red, or yellow iron oxide coated with isopropyl triisostearyl titanate, and mixtures thereof.

27. Composition according to any one of claims 1 to 26, characterized in that it is anhydrous.

28. 1. An assembly or kit for packaging and applying a cosmetic composition for coating keratinous materials, comprising: - a packaging device containing a composition according to any one of claims 1 to 27; - an applicator for said composition Assembly or kit comprising:

29. A method for coating, in particular curling, keratinous material, in particular eyebrows and the skin around the eyes and eyebrows, comprising applying a composition according to any one of claims 1 to 27 to said keratinous fibres.

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