WO2021214053A1

WO2021214053A1 - Process for densifying keratin fibers, based on silicone, an alkoxysilane and a coloring agent

Info

Publication number: WO2021214053A1
Application number: PCT/EP2021/060235
Authority: WO
Inventors: Alexis LIARD
Original assignee: L'oreal
Priority date: 2020-04-21
Filing date: 2021-04-20
Publication date: 2021-10-28
Also published as: FR3109305B1; FR3109305A1

Abstract

The present patent application relates to a process for coloring an area of skin bearing keratin fibers, which consists in applying, to said area of skin, and optionally to said keratin fibers, a composition comprising at least one silicone of formula (I), at least one alkoxysilane of formula (II) and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

Description

PROCESS FOR DENSIFYING KERATIN FIBERS, BASED ON SILICONE, AN ALKOXYSILANE AND A COLORING AGENT

[0001] The present invention relates to a process for the visual densification of keratin fibers, more particularly the hair and very especially its roots, beard hair, moustache hair, eyelashes and eyebrows, by coloring at least one area of skin bearing said keratin fibers and optionally coloring said keratin fibers. More particularly, the process consists in coloring the skin which bears keratin fibers using a composition comprising at least one silicone of formula (I), at least one alkoxysilane of formula (II) and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

Technical field

[0002] It is known practice in the cosmetics industry to use compositions for visually densifying keratin fibers such as the hair or bodily hairs such as the eyelashes, the eyebrows, beard hair or moustache hair.

[0003] For example, for visual densification of the eyebrows, it is known practice to use felt-tip pens or tattooing for drawing lines imitating the presence of eyelashes and to visually fill out the eyebrows, notably when they are sparse. Furthermore, these products cannot always modify the initial color of the eyebrows and the color introduced is sparingly persistent over time and sparingly resistant to water or sweat.

[0004] Furthermore, it is possible to permanently color keratin fibers, such as the hairs of the eyebrows or of the moustache, using “oxidation” dyes, which consists in applying to the hair one or more dye precursors and an oxidizing agent.

[0005] However, these methods do not lead toward providing sufficient densification at the place where the density of the keratin fibers is lower and/or uneven.

[0006] Thus, the aim of the present invention is to provide a process for obtaining a natural effect of visual densification of keratin fibers which holds over time.

[0007] This aim is achieved with the present invention, one subject of which is a process which consists in coloring, using a particular composition, at least one area of skin which bears keratin fibers, and optionally in also coloring said keratin fibers.

Disclosure of the invention [0008] One subject of the present invention is a process for coloring an area of skin bearing keratin fibers, which consists in applying to said area of skin, and optionally to said keratin fibers, a composition comprising: a) at least one silicone of formula (I) as defined below, b) at least one alkoxysilane chosen from the compounds of formula (II) as described below, oligomers thereof and/or mixtures thereof, and c) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

[0009] The present invention also relates to a kit for coloring an area of skin bearing keratin fibers, comprising a dye composition as defined above, and a makeup-removing composition as defined below.

[0010] The term “at least one ” means one or more.

[0011] The term “ keratin fibers’ ’ means in particular the hair and non-head hairs, such as the eyelashes, the eyebrows, beard hair or moustache hair.

[0012] The area of skin which bears the keratin fibers may be the skin of the scalp, skin at the eyebrows or eyelashes, skin of the face which bears the beard hairs, moustache hairs, and the sideburns.

[0013] The process according to the invention makes it possible to obtain, by coloring the skin close to the keratin fibers, an effect of visual densification of the keratin fibers. The coloring obtained withstands shampooing or washing, and the external attacking factors to which the fibers may be subjected, such as blow-drying and perspiration. It makes it possible in particular to obtain a smooth, uniform deposit.

[0014] Moreover, this composition for obtaining colored skin and keratin fibers can be removed easily either immediately after application of the dye composition or after a certain amount of time, i.e. a few days to a few weeks after the application of the dye composition.

[0015] The invention is not limited to the examples illustrated. The features of the various examples may notably be combined within variants which are not illustrated.

[0016] The composition according to the invention is preferably a composition for coloring an area of skin bearing keratin fibers such as the hair.

[0017] For the purposes of the present invention and unless otherwise indicated: - an “ alkyF radical denotes a linear or branched saturated radical containing, for example, from 1 to 20 carbon atoms;

- an “ aminoalkyr radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

- a “ cycloalkyF radical denotes a saturated cyclic hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 40 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical possibly being substituted with one or more (Ci-C4)alkyl groups such as methyl;

- an “ aryF radical is a monocyclic or bicyclic, fused or non-fused, unsaturated cyclic aromatic radical comprising from 6 to 30 carbon atoms; preferably, the aryl group comprises 1 ring containing 6 carbon atoms, such as phenyl;

- an “ alkoxy ” radical denotes an “alkyl-oxy” radical with “ alkyF as defined previously.

[0018] Silicone of formula (I):

[0019] The process according to the invention comprises a composition comprising at least one silicone of formula (I) below:

[0020]

[0021] in which: - R1 independently represents a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms;

- R2 independently represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, or an alkoxy group containing from 1 to 2 carbon atoms or a hydroxyl group or a monovalent radical of formula -CqkkqL in which q is a number ranging from 2 to 8, and L is an optionally quaternized amino group chosen from the following groups:

-N(R”)₂; -N⁺(R”)3 A ; -NR”-Q-N(R”)₂ and -NR”-Q-N⁺(R”)₃ A, in which R”, which may be identical or different, represents a hydrogen atom, a phenyl group, a benzyl group or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl group; Q denotes a linear or branched group of formula C_rH2_r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A represents a cosmetically acceptable anion, notably a halide such as fluoride, chloride, bromide or iodide;

- R3 represents a hydroxyl group; an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms, said alkyl group being optionally substituted with at least one group chosen from a hydroxyl group (OH) or a thiol group (SH); a cycloalkyl group containing from 3 to 20 carbon atoms, notably from 5 to 6 carbon atoms, said cycloalkyl being optionally substituted with at least one group chosen from a hydroxyl group (OH) or a thiol group (SH); an alkoxy group containing from 1 to 2 carbon atoms, optionally substituted with at least one group chosen from a hydroxyl group (OH) or a thiol group (SH); an aryl group containing from 6 to 12 carbon atoms, optionally substituted with at least one group chosen from a hydroxyl group (OH) or a thiol group (SH); or a radical -(X)_p -Si(R )₃ or a monovalent radical of formula -C_qH2_qL in which q is a number ranging from 2 to 8, and L is an amino group as described previously;

- A represents a saturated divalent hydrocarbon-based radical containing 1 carbon atom;

- X represents a hydrogen atom or a saturated divalent hydrocarbon-based radical containing 1 carbon atom;

- p is an integer ranging from 0 to 6; p’ is an integer equal to 0 or 1 or 2 or 3;

- k is an integer ranging from 0 to 6;

- q denotes an integer equal to 0 or 1 ; - j denotes an integer equal to 0 or 1 or 2;

- 1 denotes an integer equal to 0 or 1 ;

- y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; it being understood that if X represents a hydrogen atom, then t = 0 and p = 1 and if p = 0, then t = 1 and q = 1 and that at least one of the radicals Ri or ¾ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a radical -(X)_p -Si(R.2)2 or a monovalent radical of formula -C_qH2_qL in which q is a number ranging from 2 to 8, and L is an amino group as described previously.

[0022] Preferably, the silicone(s) of formula (I) are such that:

- Rl independently represents a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms such as methoxy or ethoxy, or an alkyl group containing from 1 to 2 carbon atoms such as a methyl;

- R2 independently represents an alkyl group containing from 1 to 4 carbon atoms, more preferentially 1 to 2 carbon atoms such as a methyl or an alkoxy group containing from 1 to 2 carbon atoms or a hydroxyl group;

- R3 represents a hydroxyl group or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms, or an alkoxy group containing from 1 to 2 carbon atoms or a radical -(X)_p -Si(R.2)2 or a monovalent radical of formula -C_qH2_qL in which q is a number ranging from 2 to 8, and L is an amino group chosen from the following groups:

-N(R₄)₂;

-N(R₄)-CH2-CH2-N(R₄)2; in which R4 represents a hydrogen atom; a phenyl group; a benzyl group or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl group;

- X represents a hydrogen atom or a hydrocarbon-based radical containing 1 carbon atom;

- p denotes an integer ranging from 0 to 6, and p’ is an integer equal to 0 or 1 or 2 or 3;

- j is equal to 0;

- k is an integer equal to 0 or 1; - q denotes an integer equal to 0 or 1 ;

- 1 denotes an integer equal to 0 or 1 ; and

- y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; and it being understood that if X represents a hydrogen atom, then t = 0 and p = 1 and if p = 0, then t = 1 and q = 1 and that at least one of the radicals Ri or ¾ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a monovalent radical of formula

-CqH2qL as described previously.

[0023] More preferentially, the silicone(s) of formula (I) are such that:

- Rl independently represents a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms such as methoxy or ethoxy, or an alkyl group containing from 1 to 2 carbon atoms such as methyl;

- R2 independently represents an alkyl group containing from 1 to 2 carbon atoms such as a methyl or an alkoxy group containing from 1 to 2 carbon atoms or a hydroxyl group;

- R3 represents a monovalent radical of formula -CqhkqL in which q is a number ranging from 2 to 8 and L is an amino group chosen from the following groups:

-N(R₄)₂;

- X represents a hydrogen atom, and p denotes an integer equal to 1;

- j is equal to 0;

- k is equal to 1;

- q denotes an integer equal to 0;

- 1 denotes an integer equal to 0;

- j is equal to 0; - y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; it being understood that at least one of the radicals Ri or R₃ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a monovalent radical of formula

-CqhkqL as described previously.

[0024] The silicone(s) of formula (I) used in the context of the invention may be chosen from:

- the compounds of formula (la) below:

[0025]

[0026] in which:

- Ri, which may be identical or different, independently represents a hydroxyl group; an alkyl group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms such as a methyl, or an alkoxy group containing from 1 to 2 carbon atoms;

- R’₂ and R”₂, which may be identical or different, independently represent an alkyl group containing from 1 to 4 carbon atoms, notably from 1 to 2 carbon atoms such as a methyl, or a hydroxyl group;

- a denotes an integer ranging from 0 to 10, b denotes an integer ranging from 0 to 500 with a+b > 4.

[0027] - the compounds of formula (lb) below: [0029] in which:

- Ri independently represents an alkyl group containing from 1 to 4 carbon atoms, and most particularly a methyl, or an alkoxy group containing from 1 to 2 carbon atoms;

- R2, R’2 and R”2, which may be identical or different, independently represent an alkyl group containing from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, or a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms;

- R3 represents a group -Xp’-Si(OR4)3 with R4 representing an alkyl group containing from 1 to 2 carbon atoms, X representing a saturated divalent hydrocarbon-based radical containing 1 carbon atom, and p’ denoting an integer ranging from 1 to 3;

- m denotes an integer ranging from 0 to 3;

- i denotes an integer ranging from 0 to 10, j denotes an integer ranging from 0 to 500 and i+j ranging from 0 to 510 with i+j > 4;

[0030] - and the compounds of formula (Ic) below:

[0031]

[0032] in which:

- Ri, which may be identical or different, represents an alkyl group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, such as a methyl; or an alkoxy group containing from 1 to 2 carbon atoms;

- R2 independently represents an alkyl group containing from 1 to 2 carbon atoms such as a methyl or ethyl; - R’2 and R”2, which may be identical or different, independently represent an alkyl group containing from 1 to 4 carbon atoms, more preferentially from 1 to 2 carbon atoms, or an alkoxy group containing from 1 to 2 carbon atoms such as a methoxy or ethoxy;

- i denotes an integer ranging from 0 to 10, n denotes an integer ranging from 0 to 500 with n+i ranging from 0 to 510 with n+i > 4;

[0033] - the compounds of formula (Id):

[0035] in which:

- m and n are numbers such that the sum (m + n) ranges from 1 to 500, n denoting a number ranging from 0 to 500, and m denoting a number ranging from 1 to 500;

- Ri, which may be identical or different, independently represents an alkyl group containing from 1 to 4 carbon atoms, more preferentially from 1 to 2 carbon atoms, for example a methyl; or a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms;

-N(R₄)₂;

-N(R₄)-CH2-CH2-N(R₄)2; in which R4 represents a hydrogen atom; a phenyl group; a benzyl group or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl group; and

- R5 represents a hydroxyl group or an alkyl group containing from 1 to 2 carbon atoms, for example a methyl, or an alkoxy group containing from 1 to 2 carbon atoms;

[0036] - and mixtures thereof. [0037] Among the silicones of formula (la), mention may be made of poly dimethyl siloxanes (PDMS) bearing hydroxyl end functions, such as the compounds sold by the company Shin- Etsu under the name KF-9701 or X-21-5841, or those sold by the company Sigma-Aldrich under the reference 481939 (Mn -550, -25 cSt), 481955 (-65 cSt), or 481963 (-750 cSt).

[0038] Mention may also be made of the compounds sold by the company Gelest under the name DMS-S12 (16-32 cSt), DMS-S15 (45-85 cSt), DMS-S21 (90-120 cSt), DMS-S27 (700-

800 cSt) or DMS-S31 (-1000 cSt).

[0039] Among the silicones of formula (lb), mention may be made of polydimethylsiloxanes (PDMS) bearing trialkoxysilane side functions, such as those sold by the company Siltech under the name Silmer TMS C50.

[0040] Among the silicones of formula (Ic), mention may be made of polydimethylsiloxanes (PDMS) bearing trialkoxysilane end functions, such as those sold by the company Power Chemical under the name SiSiB® PF2110, or those sold by the company Siltech under the name Silmer TMS Di-10 or Silmer TMS Di-50.

[0041] Among the silicones of formula (Id) mention may be made of the compound having the trade name KF 857, sold by the company Shin-Etsu, or the compound having the trade name KF 862, sold by the company Shin-Etsu.

[0042] Preferably, the silicone(s) are chosen from the silicones of formulae (la) and (Id) and mixtures thereof.

[0043] More preferentially, the silicone(s) used in the context of the invention are chosen from the compounds of formula (la) in which:

- Ri independently represents an alkyl group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms such as a methyl;

- R’2 and R”2 independently represent an alkyl group containing from 1 to 4 carbon atoms, more particularly from 1 to 2 carbon atoms such as a methyl;

- b denotes an integer ranging from 0 to 20, a denotes an integer ranging from 0 to 10 with a+b > 4. [0044] The silicone(s) of formula (I) may be present in a total amount ranging from 0.1% to 30% by weight, preferably from 1% to 25% by weight and more preferentially from 1% to 20% by weight relative to the total weight of the composition.

[0045] Alkoxysilane:

[0046] The process according to the invention comprises a composition comprising at least one alkoxysilane chosen from the compounds of formula (II) below, oligomers thereof and/or mixtures thereof:

[0047] [Chem.6]

R'^iiOR²^_!)

(P)

[0048] in which:

- R¹ represents an alkoxy group containing from 1 to 10 carbon atoms, a linear or branched, saturated or unsaturated, cyclic or acyclic Ci to C22 and notably Ci to C20 hydrocarbon-based radical, which may be substituted with at least one group chosen from a hydroxyl group (OH); a thiol group; an amino group NH2; an alkylamino group NHR in which R denotes a linear or branched alkyl radical containing from 1 to 20 carbon atoms, notably from 1 to 10 carbon atoms, or an alkoxy group containing from 1 to 10 carbon atoms; a cycloalkyl containing from 3 to 40 carbon atoms; an aryl containing from 6 to 30 carbon atoms; R¹ possibly being interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO);

- R² represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms;

- x denotes an integer ranging from 1 to 3.

[0049] R¹ and R² may be identical or different.

[0050] The term “ oligomer ” means compound(s) including at least two silicon atoms, obtained by oligomerization or polymerization of the compounds of formula (II).

[0051] Preferably, R¹ represents an alkoxy group containing from 1 to 10 carbon atoms, such as an ethoxy, or R¹ represents a linear or branched, saturated Ci to C22 and notably Ci to C20 hydrocarbon-based radical, which is preferably linear, said hydrocarbon-based radical possibly being substituted with at least one amino group NH2 or alkylamino group NHR, in which R denotes a linear or branched alkyl radical containing from 1 to 20 carbon atoms, notably from 1 to 10 carbon atoms. [0052] More preferentially, R¹ represents a saturated linear Ci to G, hydrocarbon-based radical, which may be substituted with an amino group NH2.

[0053] Preferably, R² represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferentially an ethyl.

[0054] The alkoxy silane(s) of formula (II), the oligomers thereof and/or mixtures thereof may be chosen from:

- the compounds of formula (Ila) and/or (lib) below, oligomers thereof, alone or as a mixture:

[0055]

[0056]

[0057] in which:

- Ra and Rb, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms;

- Rc represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an alkylaryl group containing from 7 to 12 carbon atoms;

- Rd and Re, which may be identical or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as an ethyl;

- k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3; - Rf represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (III) below:

[0058]

[0059] in which Rn represents a hydroxyl group (OH); an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably a methyl.

[0060] Among the alkoxysilanes of formula (Ha), the oligomers thereof and/or mixtures thereof, mention may notably be made of 3 -aminopropyltriethoxy silane (APTES),

3-aminopropylmethyldiethoxysilane (APMDES) and N- cyclohexylaminomethyltriethoxysilane.

[0061] APTES may be purchased, for example, from the company Dow Corning under the name Xiameter OFS-6011 Silane or from the company Momentive Performance Materials under the name Silsoft A-l 100 or from the company Shin-Etsu under the name KBE-903.

[0062] The compounds of formula (Ila) may also denote Dynasylan SIVO 210 or Dynasylan 1505 sold by the company Evonik.

[0063] N-Cycloheylaminomethyltri ethoxy silane may be purchased, for example, from the company Wacker under the name Geniosil XL 926.

[0064] Among the alkoxysilanes of formula (lib), the oligomers thereof and/or mixtures thereof, mention may notably be made of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltri ethoxy silane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane and mixtures thereof.

[0065] TEOS may be purchased, for example, from the company Evonik under the name Dynasylan® A or Dynasylan® A SQ. MTES may be purchased, for example, from the company Evonik under the name Dynasylan® MTES. DMDES may be purchased, for example, from the company Gelest under the reference SID3404.0. [0066] Preferably, the alkoxysilane(s) chosen from the compounds of formula (II), the oligomers thereof and/or mixtures thereof are chosen from 3 -aminopropyltri ethoxy silane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES),

N-cyclohexylaminomethyltriethoxysilane, tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltri ethoxy silane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane and mixtures thereof, more preferentially 3 -aminopropyltri ethoxy silane (APTES), tetraethoxysilane (TEOS) and mixtures thereof.

[0067] Preferably, the alkoxysilane(s) of formula (II), the oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (Ila) below:

[0068]

[0069] in which:

- Ra and Rb, which are identical, represent a hydrogen atom or Ra denotes a hydrogen atom and Rb denotes a C5-C6 cycloalkyl radical such as cyclohexyl;

- Rc represents an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;

- Rd and Re, which may be identical or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl;

- k denotes an integer ranging from 1 to 3 and more particularly 1 or 3.

[0070] Preferentially, the compounds of formula (Ila) are such that Ra and Rb represent a hydrogen atom, Rc represents an ethoxy group, Rd and Re are identical and represent an ethyl and k is equal to 3. [0071] Preferably, the alkoxysilane of formula (II), the oligomers thereof and/or mixtures thereof, is 3 -aminopropyltri ethoxy silane (APTES).

[0072] According to another preferred embodiment, the alkoxysilane(s) of formula (II), the oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (lib) below:

[0073]

[0074] in which

- Rc represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as an ethoxy;

- Rd represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as an ethyl;

- k denotes an integer ranging from 0 to 3, preferably equal to 0;

- Rf represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as an ethyl.

[0075] According to another more preferred embodiment, the alkoxysilane of formula (II), the oligomers thereof and/or mixtures thereof, is tetraethoxy silane (TEOS).

[0076] The alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof may be present in a total amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight and better still from 1% to 20% by weight, relative to the total weight of the composition.

[0077] Coloring agent:

[0078] The process according to the invention comprises a composition comprising at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

[0079] Preferably, the composition according to the invention comprises one or more pigments. [0080] The term “pigment” refers to any pigment that gives color to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0081] The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’ s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.

[0082] They may be natural, of natural origin, or non-natural.

[0083] These pigments may be in pigment powder or paste form. They may be coated or uncoated.

[0084] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

[0085] The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

[0086] The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on organic pigments.

[0087] The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoleine, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0088] In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2679 771.

[0089] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:

- Cosmenyl Yellow IOG: Yellow 3 pigment (Cl 11710);

- Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);

- Cosmenyl Orange GR: Orange 43 pigment (Cl 71105);

- Cosmenyl Red R: Red 4 pigment (Cl 12085);

- Cosmenyl Carmine FB: Red 5 pigment (Cl 12490);

- Cosmenyl Violet RL: Violet 23 pigment (Cl 51319);

- Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74160);

- Cosmenyl Green GG: Green 7 pigment (Cl 74260);

- Cosmenyl Black R: Black 7 pigment (Cl 77266).

[0090] The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184426. These composite pigments may be composed notably of particles including a mineral core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

[0091] The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

[0092] The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0093] Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45 380), D&C Orange 5 (Cl 45 370), D&C Red 27 (Cl 45 410), D&C Orange 10 (Cl 45 425), D&C Red 3 (Cl 45 430), D&C Red 4 (Cl 15 510), D&C Red 33 (Cl 17200), D&C Yellow 5 (Cl 19 140), D&C Yellow 6 (Cl 15 985), D&C Green (Cl 61 570), D&C Yellow 10 (Cl 77002), D&C Green 3 (Cl 42 053), D&C Blue 1 (Cl 42 090). [0094] An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (Cl 15 850:1).

[0095] The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from colored pigments, which afford a standard uniform opaque, semitransparent or transparent shade.

[0096] Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

[0097] Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the Cellini nacres sold by BASF (mica-Ti02-lake), Prestige sold by Eckart (mica-Ti02), Prestige Bronze sold by Eckart (mica-Fe203), and Colorona sold by Merck (mica-Ti02- Fe203).

[0098] Mention may also be made of the gold-colored nacres sold notably by the company BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone GO 12 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink- orange nacres sold notably by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

[0099] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.

[00100] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

[00101] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum.

[00102] The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.

[00103] The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined, and more particularly so as to optimize this effect in terms of color rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or tint.

[00104] These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form. [00105] The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.

[00106] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.

[00107] When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials.

[00108] More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

[00109] The reflective material may include a layer of metal or of a metallic material.

[00110] Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[00111] Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver-coated borosilicate substrate.

[00112] Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

[00113] Use may also be made of particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[00114] Examples that may be mentioned include aluminum powder, bronze powder or copper powder coated with Si02 sold under the name Visionaire by the company Eckart. [00115] Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

[00116] The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colors, and also particular optical effects such as metallic effects or interference effects.

[00117] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.

[00118] The pigments may be dispersed in the composition by means of a dispersant.

[00119] The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxy stearic acid in particular and of Cx to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel PI 00 by the company Uniqema, and mixtures thereof.

[00120] As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C. [00121] The pigments used in the composition may be surface-treated with an organic agent.

[00122] Thus, the pigments that have been surface-treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

[00123] The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.

[00124] The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

[00125] Preferably, the surface-treated pigments are coated with an organic layer.

[00126] The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

[00127] The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.

[00128] An organic agent covalently bonded to the pigments will preferably be used. [00129] The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.

[00130] Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;

- a methicone treatment, for instance the SI surface treatment sold by LCW;

- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;

- a dimethicone/trimethyl siloxy silicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

- an aluminum dimyristate treatment, such as the MI surface treatment sold by Miyoshi;

- a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;

- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;

- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;

- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;

- an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;

- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito. [00131] According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition.

[00132] The term “submicron” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

[00133] According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersantpigment) of between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.

[00134] The dispersant(s) may thus have a silicone backbone, such as silicone poly ether and dispersants of amino silicone type other than the alkoxysilanes described previously. Among the suitable dispersants, mention may be made of:

- amino silicones, i.e. silicones comprising one or more amino groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers,

- silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego®

RC 1043, sold by Evonik,

- polydimethylsiloxane (PDMS) silicones with carboxyl groups such as X- 22162 and X- 22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP- 607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403,

Tego® RC 1412 by Evonik.

[00135] According to a particular embodiment, the dispersant(s) are of aminosilicone type other than the alkoxysilanes described previously and are cationic.

[00136] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.

[00137] In one variant of the invention, the pigment(s) according to the invention are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) according to the invention are mineral pigments.

[00138] The composition may comprise one or more direct dyes. [00139] The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fiber.

[00140] They may be ionic or nonionic, preferably cationic or nonionic.

[00141] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

[00142] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (III) and (IV) and the azo cationic dyes (V) and (VI) below:

Het⁺-C(Ra)=N-NCRb)-Ar, Q

(III)

[00143]

Het⁺-N(Ra)-N=C(Rb)-Ar₌ Q-

(IV)

[00144]

Het⁺-N=N-Ar, Q- ^

[00145]

Ar⁺-N=N-Ar” Q-

[00146] (VI)

[00147] in which formulae (III) to (VI):

- Het⁺ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cs) alkyl group such as methyl;

- Ar⁺ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C₈)alkylammonium, such as trimethylammonium;

- Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cx)alkyl, ii) optionally substituted (Ci-Cx)alkoxy, iii) (di)(Ci-C₈)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C₈)alkylamino, v) optionally substituted

N-(Ci-C₈)alkyl-N-aryl(Ci-C₈)alkylamino or alternatively Ar represents a julolidine group;

- Ar” represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci-Cs)alkyl, hydroxyl, (di)(Ci-C₈)(alkyl)amino, (Ci-C₈)alkoxy or phenyl groups;

- Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-Cs)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;

- Q- represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

[00148] In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (III) to (VI) as defined previously, more particularly, the cationic direct dyes bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP 714954, preferentially the following direct dyes:

[00149]

[00150]

[00151] in which formulae (VII) and (VIII):

- R¹ represents a (Ci-C4)alkyl group such as methyl; - R² and R³, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl; and

- R⁴ represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cx)alkyl, optionally substituted (Ci-Cx)alkoxy, or (di)(Ci-C₈)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferentially CH,

- Q is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesylate.

[00152] In particular, the dyes of formulae (VII) and (VIII) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q being an anionic counterion as defined previously, particularly halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesylate.

[00153] The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including in its structure at least one CO₂R or SO₃R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.

[00154] As acid dyes according to the invention, mention may be made of the dyes of formulae (IX), (IX’), (X), (X’), (XI), (XI’), (CP), (CIG), (XIII), (XIV), (XV) and (XVI) below:

[00155] a) the diaryl anionic azo dyes of formula (IX) or (IX¹):

[00156]

[00157]

[00158] in which formulae (IX) and (IX’):

- R7, Re, R9, Rio, R’7, R’S, R’9 and R’IO, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

- (O)CO -, M⁺ with M⁺ as defined previously;

- R”-S(0)₂-, with R” representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;

- R’”-S(0)₂-X’- with R”’ representing an optionally substituted alkyl or aryl group, X’ as defined previously;

- (di)(alkyl)amino;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)₂S(0 )-, M⁺ and iv) alkoxy with M⁺ as defined previously;

- optionally substituted heteroaryl; preferentially a benzothiazolyl group;

- cycloalkyl; notably cyclohexyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl, (0)₂S(0 )-, M⁺ or phenylamino groups; - or alternatively two contiguous groups R₇ with Rx or Rx with R₉ or R₉ with Rio together form a fused benzo group A’; and R’₇ with R’x or R’x with R’₉ or R’₉ with R’_IO together form a fused benzo group B’; with A’ and B’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)₂S(0-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-X”-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X’, X” and Ar as defined previously;

[00159] - W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (IX) and (IX’) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A’, B, B’ or C; preferentially sodium sulfonate.

[00160] As examples of dyes of formula (IX), mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;

[00161] and, as examples of dyes of formula (IX’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38.

[00162] b) the pyrazolone anionic azo dyes of formulae (X) and (X’): [00163]

[00164]

[00165] in which formulae (X) and (X’):

- Rii, Ri₂ and R₁₃, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0)₂S(0-), M+ with M+ as defined previously;

- Ri4 represents a hydrogen atom, an alkyl group or a group -C(0)0-, M+ with M+ as defined previously;

- Ri5 represents a hydrogen atom;

- R₁₆ represents an oxo group, in which case R’i₆ is absent, or alternatively R₁₅ with Ri₆ together form a double bond;

- Ri₇ and Ris, which may be identical or different, represent a hydrogen atom, or a group chosen from:

- (0)₂S(0 )-, M⁺ with M⁺ as defined previously;

- Ar-0-S(0)₂- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups; - Ri₉ and R₂₀ together form either a double bond, or a benzo group D’, which is optionally substituted;

- R’i6, R’i₉ and R’₂o, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;

- R21 represents a hydrogen atom or an alkyl or alkoxy group;

- R and R_b, which may be identical or different, are as defined previously; preferentially, R_a represents a hydrogen atom and R_b represents an aryl group;

- Y represents either a hydroxyl group or an oxo group;

- - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (X) and (X’) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+ on one of the rings D or E; preferentially sodium sulfonate.

[00166] As examples of dyes of formula (X), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (X’), mention may be made of: Acid Yellow 17;

[00167] c) the anthraquinone dyes of formulae (XI) and (CG):

[00168]

[00169]

[00170] in which formulae (XI) and (CG):

- R22, R-23, R-24, R-25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (0)₂S(0 )-, M⁺ with M⁺ as defined previously;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)₂S(0 )-, M⁺ with M⁺ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- (0)₂S(0 )-, M⁺ with M⁺ as defined previously;

[00171] Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxy alkyl such as hydroxy ethyl;

- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0)₂S(0-)-, M+ with M+ as defined previously; iii) R°-C(X)-X’-, R°- X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously, preferentially R° represents an alkyl group;

- cycloalkyl; notably cyclohexyl;

[00172] Z, represents a group chosen from hydroxyl and NR’28R’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XI) and (CG) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical C(0)0-, M+; preferentially sodium sulfonate.

[00173] As examples of dyes of formula (XI), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; and, as an example of a dye of formula (XT), mention may be made of: Acid Black 48;

[00174] d) the nitro dyes of formulae (XII) and (CIG):

[00175]

[00176]

[00177] in which formulae (XII) and (CIG):

- Kao, R-31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: - alkyl;

- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;

- hydroxyl, mercapto;

- nitro, nitroso;

- polyhaloalkyl;

- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- withR°, X, X’ and X” as defined previously;

- (0)₂S(0-)-, M+ with M+ as defined previously;

- (O)CO -, M⁺ with M⁺ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R₃₀, R₃₁ and R₃₂ represent a hydrogen atom;

[00178] - Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;

- W is as defined previously; W particularly represents an -NH- group;

- ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;

- n is 1 or 2;

- p represents an integer inclusively between 1 and 5;

- q represents an integer inclusively between 1 and 4;

- u is 0 or 1 ;

- when n is 1, J represents a nitro or nitroso group; particularly nitro;

- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)_m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;

- M’ represents a hydrogen atom or a cationic counterion;

, which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously; it being understood that formulae (XII) and (CIG) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+; preferentially sodium sulfonate.

[00179] As examples of dyes of formula (XII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (CIG), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4^,-N,N-(2”-hydroxyethyl)amino-2^,-nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7;

[00180] d) the triarylmethane dyes of formula (XIII):

[00181]

[00182] in which formula (XIII):

- R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted with a group (0)_mS(0 )-, M⁺ with M⁺ and m as defined previously;

- R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino; - hydroxyl, mercapto;

- nitro, nitroso;

- (O)CO -, M⁺ with M⁺ as defined previously;

- or alternatively two contiguous groups Ru with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: G; with G optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)₂S(0-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-C(X)-X”-; with M+, R°, X, X’ and X” as defined previously; in particular, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (0)₂S(0-)-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with an (0)₂S(0-)- group; it being understood that at least one of the rings G, H, I or G comprises at least one sulfonate radical (0)₂S(0-)- or one carboxylate radical -C(0)0-; preferentially sulfonate.

[00183] As examples of dyes of formula (XIII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50;

[00184] e) the xanthene-based dyes of formula (XIV):

[00186] in which formula (XIV): - R45, R-46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;

- R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

[00187]

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- (0)₂S(0 ) , M⁺ with M⁺ representing a hydrogen atom or a cationic counterion;

- (O)CO , M⁺ with M⁺ as defined previously; particularly R53, R54, R55 and R48 represent a hydrogen or halogen atom;

[00188] - G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom;

- L represents an alkoxide 0-, M+; a thioalkoxide S-, M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium;

- L’ represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0)_mS(0-)-, M+ groups with m and M+ as defined previously;

- Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;

- M+ is as defined previously.

[00189] As examples of dyes of formula (XIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[00190] f) the indole-based dyes of formula (XV): [00191]

[00192] R53, R54, R55, R56, R57, R58, R59 and R50, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- (O)CO -, M⁺ with M⁺ as defined previously;

- G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly, G represents an oxygen atom;

- Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XV) comprises at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+; preferentially sodium sulfonate.

[00193] As examples of dyes of formula (XV), mention may be made of: Acid Blue 74.

[00194] g) the quinoline-based dyes of formula (XVI):

[00195]

[00196] - R_6I represents a hydrogen or halogen atom or an alkyl group;

- R62, R63 and Rr_>4, which may be identical or different, represent a hydrogen atom or a group (0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion; or alternatively lUi with R452, or lUi with R454, together form a benzo group optionally substituted with one or more groups (0)₂S(0 ) , M⁺ with M⁺ representing a hydrogen atom or a cationic counterion; it being understood that formula (XVI) comprises at least one sulfonate radical (0)₂S(0 ) , M⁺, preferentially sodium sulfonate.

[00197] As examples of dyes of formula (XVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[00198] Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.

[00199] Preferably, the direct dyes are chosen from anionic direct dyes.

[00200] The coloring agent(s) may be present in a total content ranging from 0.001% to

20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of the composition.

[00201] The pigment(s) may be present in a total content ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 0.5% to 10% by weight, relative to the total weight of the composition. [00202] The direct dye(s) may be present in a total content ranging from 0.001% to 10% by weight relative to the total weight of the composition, preferably from 0.005% to 5% by weight relative to the total weight of the composition.

[00203] The composition according to the invention may comprise water. Preferably, water is present in a content ranging from 0.1% to 50% by weight, more preferentially from 0.5% to 40% by weight relative to the total weight of the composition.

[00204] The composition according to the invention may comprise less than 2% by weight of water relative to the total weight of the dye composition.

[00205] Organic solvents:

[00206] The process according to the invention comprises a composition which may comprise one or more organic solvents.

[00207] Examples of organic solvents that may be mentioned include lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance

2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxy ethanol, and mixtures thereof.

[00208] Preferably, the composition comprises one or more organic solvents chosen from C1-C4 lower alkanols, more preferentially ethanol.

[00209] The organic solvents may be present in a total amount inclusively between 0.1% and 60% by weight approximately relative to the total weight of the dye composition, preferably between 1% and 50% by weight and more preferentially inclusively between 5% and 45% by weight relative to the total weight of the composition.

[00210] Additives:

[00211] The process according to the invention comprises a composition which may contain any adjuvant or additive usually used.

[00212] Among the additives that may be contained in the composition, mention may be made of reducing agents, thickeners, softeners, antifoams, moisturizers, UV-screening agents, peptizers, solubilizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers, preserving agents, oils, waxes and mixtures thereof.

[00213] Preferably, the composition comprises a pH agent such as hydrochloric acid. [00214] The composition according to the invention may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two- phase or multi-phase lotion.

[00215] A person skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, notably their solubility in the support, and secondly the intended application of the composition.

[00216] According to a preferred embodiment, the process according to the invention comprises a composition comprising a silicone of formula (la), 3 -aminopropyltri ethoxy silane (APTES) and pigments.

Process for coloring and/or removing makeup from and/or cleansing an area of skin bearing keratin fibers

[00217] The present invention relates to a process for coloring an area of skin bearing keratin fibers, which consists in applying to said area of skin, and optionally to said keratin fibers, a dye composition as described previously.

[00218] The composition described above may be used on an area of skin bearing wet or dry keratin fibers and also on any type of skin and of fibers.

[00219] The application to the skin may be performed using a fine brush, a felt tip or a coarse brush.

[00220] The application to the keratin fibers of the area of skin may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush such as a mascara brush, or with the fingers.

[00221] The application to the skin and the keratin fibers, where appropriate, may be performed using the same application means or using a different means.

[00222] After the application of the composition, the fibers may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C. According to a particular embodiment, this temperature is greater than 45°C and less than 220°C. [00223] A drying step may be performed on the area of skin bearing keratin fibers immediately after the application of the composition or after a leave-on-time which may range from 1 minute to 30 minutes.

[00224] During drying, a mechanical action on the area of skin bearing keratin fibers may be exerted, such as combing, brushing or running the fingers through. This operation may similarly be performed once the fibers have dried, naturally or otherwise.

[00225] The drying step may be performed, for example, with a hood dryer or a hair dryer.

[00226] Preferably, the process according to the invention comprises a step of applying to said area of skin a makeup-removing composition comprising at least one hydrocarbon-based oil.

[00227] Thus, the process according to the invention may comprise a step of applying a makeup-removing composition to an area of skin bearing keratin fibers. This step may take place after the coloring of the area of skin bearing keratin fibers with the dye composition as described previously, optionally after a given time, i.e. days or weeks after the application of the dye composition to said area of skin.

[00228] The makeup-removing composition may correspond to a makeup-removing composition conventionally used in cosmetics. Preferably, the makeup-removing composition comprises at least one hydrocarbon-based oil.

[00229] Preferably, the hydrocarbon-based oil(s) are chosen from synthetic esters of formula R1COOR2 in which Ri represents a fatty acid residue including from 8 to 29 carbon atoms, and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, and mixtures thereof, more preferentially from isopropyl myristate, isononyl isononanoate and/or mixtures thereof.

[00230] Preferably, the application of the dye composition to said area of skin is performed before applying a makeup-removing composition.

[00231] The application of the makeup-removing composition may be performed on an area of skin bearing wet or dry keratin fibers and also on all types of skin.

[00232] The makeup-removing process is generally performed at room temperature (between 15°C and 25°C).

[00233] The application of the makeup-removing composition may be performed immediately after the application of the dye composition (i.e. a few minutes to a few hours after the application of the dye composition), or in the days or weeks following the application of the dye composition.

[00234] The makeup-removing composition may be applied with the aid of any suitable support, which is notably capable of absorbing it, for example a fibrous makeup-removing disk, for example a woven or nonwoven, cotton wool, a flocked film, a sponge, a wipe, or a twisted or injection- molded mascara application brush.

[00235] The makeup-removing composition may be contained in a container and taken up gradually each time makeup is removed. As a variant, the makeup-removing composition impregnates the support used for makeup removal, the support possibly being packaged, in this case, for example in leaktight packaging.

[00236] After the makeup-removing composition has been used, it is possible for the area of skin to be not rinsed. As a variant, it may be rinsed. The rinsing may be performed, for example, with running water, without addition of a soap.

[00237] The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.

Example

Example 1:

The compositions below are prepared:

Composition 1 below (in g/100 g) (i.e. solution of 3 -aminopropyltri ethoxy silane (APTES)) is prepared according to the process below:

- APTES (APTES Silsoft A-l 100 sold by the company Momentive Performance Materials) is mixed with an aqueous solution brought to pH 1 by adding HC1, a solution of ethanol is then added and said mixture is placed on a VWR brand magnetic stirrer (rotation speed 500 rpm) for 24 hours at room temperature.

Table 1

Composition 2 below (in g/100 g) (i.e. alcoholic solution of silicone) is prepared according to the process below:

- the polydimethylsiloxane (PDMS) compound bearing hydroxyl end functions (PDMS reference 481939 sold by the company Sigma-Aldrich) is diluted in an ethanol solution in which the pigment (iron oxide sold by the company Sun Chemical under the name SunPuro Red Iron Oxide®) is dispersed.

Table 2

Protocol:

Composition 1 is mixed with composition 2 in a 50/50 ratio and said mixture is applied by finger to areas of skin bearing keratin fibers (namely to a forearm with hairs) at a rate of 2 mg per cm² of skin. The areas of skin covered with the mixture of compositions 1 and 2 are then dried rapidly with a hairdryer.

After a few seconds, the hairs on the area of skin are dry, colored and appear visually denser.

Moreover, 24 hours after the application of the mixture to said area of skin, a step of washing with a standard shampoo (Gamier Ultra Doux) is performed. Said area of skin is then rinsed and dried with a hairdryer.

It is observed that the color on the keratin fibers and the skin is resistant to water and to washing a few times with a standard shampoo.

Example 2:

Compositions A and B were prepared using the ingredients of which the contents, expressed as mass percentages of active material (am) relative to the total weight of the composition, are indicated in the table below.

Protocol:

The compositions A e B are each applied by finger to an area of skin supporting keratin fibers (forearm with hairs) at a rate of 2 mg per cm² of skin. The areas are then dried with a hairdryer, before being evaluated with a spectrocolorimeter.

In order to evaluate the resistance of the color to shampoo, the areas are washed with 0.5g of a standard shampoo (20 circular passages of the hand) then rinsed with water (10 circular passages) and then dried. This protocol is repeated once in order to evaluate the resistance of the color after 2 shampoos.

The dyeing obtained by each composition was evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included). In this L* a* b* system, the three parameters respectively denote the intensity of the color (L*), the green/red color axis (a*) and the blue/yellow color axis (b*).

The resistance of the color to shampoo is represented by the difference in color DE of the colored areas before and after the shampoos:

The higher the value of DE, the greater the color difference, the more the color is degraded. The lower the value of DE, the smaller the color difference, so the less the color is degraded.

Results:

It is observed that the color obtained with the process B according to the invention is more resistant to shampoo than the color obtained with the comparative process A.

Claims

[Claim 1] A process for coloring an area of skin bearing keratin fibers, which consists in applying to said area of skin, and optionally to said keratin fibers, a composition comprising: a) at least one silicone of formula (I) below:

in which:

- R1 independently represents a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms;

- R2 independently represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, or an alkoxy group containing from 1 to 2 carbon atoms or a hydroxyl group or a monovalent radical of formula -CqhkqL in which q is a number ranging from 2 to 8, and L is an optionally quaternized amino group chosen from the following groups:

-N(R”)₂; -N⁺(R”)3 A ; -NR”-Q-N(R”)2 and -NR”-Q-N⁺(R”)₃ A, in which R”, which may be identical or different, represents a hydrogen atom, a phenyl group, a benzyl group or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl group; Q denotes a linear or branched group of formula C_rH2_r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A represents a cosmetically acceptable anion, notably a halide such as fluoride, chloride, bromide or iodide;

- R3 represents a hydroxyl group; an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms, said alkyl group being optionally substituted with at least one group chosen from a hydroxyl group or a thiol group; a cycloalkyl group containing from 3 to 20 carbon atoms, notably from 5 to 6 carbon atoms, said cycloalkyl being optionally substituted with at least one group chosen from a hydroxyl group or a thiol group; an alkoxy group containing from 1 to 2 carbon atoms, optionally substituted with at least one group chosen from a hydroxyl group or a thiol group; an aryl group containing from 6 to 12 carbon atoms, optionally substituted with at least one group chosen from a hydroxyl group or a thiol group; or a radical -(X)_p -Si(R2)2 or a monovalent radical of formula -C_qH2_qL in which q is a number ranging from 2 to 8, and L is an amino group as described previously;

- k is an integer ranging from 0 to 6;

- q denotes an integer equal to 0 or 1 ;

- j denotes an integer equal to 0 or 1 or 2;

- 1 denotes an integer equal to 0 or 1 ;

- y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; it being understood that if X represents a hydrogen atom, then t = 0 and p = 1 and if p = 0, then t = 1 and q = 1 and that at least one of the radicals Ri or ¾ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a radical -(X)_p -Si(R2k or a monovalent radical of formula -C_qH2_qL in which q is a number ranging from 2 to 8, and L is an amino group as described previously; b) at least one alkoxysilane chosen from the compounds of formula (II) below, oligomers thereof and/or mixtures thereof:

R'^iiOR²^) in which:

- R¹ represents an alkoxy group containing from 1 to 10 carbon atoms, a linear or branched, saturated or unsaturated, cyclic or acyclic Ci to C22 and notably Ci to C20 hydrocarbon-based radical, which may be substituted with at least one group chosen from a hydroxyl group; a thiol group; an amino group; an alkylamino group NHR in which R denotes a linear or branched alkyl radical containing from 1 to 20 carbon atoms, notably from 1 to 10 carbon atoms, or an alkoxy group containing from 1 to 10 carbon atoms; a cycloalkyl containing from 3 to 40 carbon atoms; an aryl containing from 6 to 30 carbon atoms; R¹ possibly being interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group;

- x denotes an integer ranging from 1 to 3; and c) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

[Claim 2] The process as claimed in claim 1, characterized in that the silicone(s) of formula (I) are such that:

- R1 independently represents a hydroxyl group or an alkoxy group containing from 1 to 2 carbon atoms such as methoxy or ethoxy, or an alkyl group containing from 1 to 2 carbon atoms such as a methyl;

- R3 represents a hydroxyl group or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms, or an alkoxy group containing from 1 to 2 carbon atoms or a radical -(X)p -Si(R.2k or a monovalent radical of formula -CqTkqL in which q is a number ranging from 2 to 8, and L is an amino group chosen from the following groups:

-N(R₄)₂;

- j is equal to 0;

- k is an integer equal to 0 or 1;

- q denotes an integer equal to 0 or 1 ;

- 1 denotes an integer equal to 0 or 1 ; and

- y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; and it being understood that if X represents a hydrogen atom, then t = 0 and p = 1 and if p = 0, then t = 1 and q = 1 and that at least one of the radicals Ri or ¾ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a monovalent radical of formula -CqH_2qL as described previously.

[Claim 3] The process as claimed in either of the preceding claims, characterized in that the silicone(s) of formula (I) are such that:

- R3 represents a monovalent radical of formula -C_qTk_qL in which q is a number ranging from 2 to 8 and L is an amino group chosen from the following groups:

-N(R₄)₂;

-N(R₄)-CH2-CH2-N(R₄)2; in which R₄ represents a hydrogen atom; a phenyl group; a benzyl group or a saturated monovalent hydrocarbon-based radical, for example a C₁-C₂₀ alkyl group;

- X represents a hydrogen atom, and p denotes an integer equal to 1;

- j is equal to 0;

- k is equal to 1;

- q denotes an integer equal to 0;

- 1 denotes an integer equal to 0;

- j is equal to 0;

- y denotes an integer ranging from 0 to 10, z denotes an integer ranging from 0 to 500 with x+z ranging from 0 to 500 and x+y+z > 4; it being understood that at least one of the radicals Ri or R₃ denotes a hydroxyl radical or an alkoxy radical containing from 1 to 2 carbon atoms or a monovalent radical of formula -CqTkqL as described previously.

[Claim 4] The process as claimed in any one of the preceding claims, characterized in that the silicone(s) of formula (I) are chosen from the compounds of formula (la) below:

in which:

- R’2 and R”2, which may be identical or different, independently represent an alkyl group containing from 1 to 4 carbon atoms, notably from 1 to 2 carbon atoms such as a methyl, or a hydroxyl group;

[Claim 5] The process as claimed in claim 4, characterized in that the silicone(s) of formula (I) are chosen from the compounds of formula (la) in which:

- R’2 and R”2 independently represent an alkyl group containing from 1 to 4 carbon atoms, more particularly from 1 to 2 carbon atoms such as methyl;

- b denotes an integer ranging from 0 to 20, a denotes an integer ranging from 0 to 10 with a+b > 4.

[Claim 6] The process as claimed in any one of claims 1 to 3, characterized in that the silicone(s) of formula (I) are chosen from the compounds of formula (Id) below:

in which:

- R3 represents a monovalent radical of formula -CqTbqL in which q is a number ranging from 2 to 8 and L is an amino group chosen from the following groups:

-N(R₄)₂;

- R5 represents a hydroxyl group or an alkyl group containing from 1 to 2 carbon atoms, for example a methyl, or an alkoxy group containing from 1 to 2 carbon atoms.

[Claim 7] The process as claimed in any one of the preceding claims, characterized in that the silicone(s) of formula (I) are present in a total amount ranging from 0.1% to 30% by weight, preferably from 1% to 25% by weight, more preferentially from 1% to 20% by weight relative to the total weight of the composition.

[Claim 8] The process as claimed in any one of the preceding claims, characterized in that the alkoxysilane(s) of formula (II), the oligomers thereof and/or mixtures thereof are chosen from the compounds of formulae (Ila) and/or (lib) below, and the oligomers thereof, alone or as a mixture:

in which:

- k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;

- Rf represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (III) below:

in which Rn represents a hydroxyl group (OH); an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, preferably a methyl.

[Claim 9] The process as claimed in any one of the preceding claims, characterized in that the alkoxysilane(s) chosen from the compounds of formula (II), the oligomers thereof and/or mixtures thereof are chosen from 3 -aminopropyltri ethoxy silane (APTES),

3 -aminopropylmethyldi ethoxy silane (APMDES), N-cyclohexylaminomethyltri ethoxy silane, tetraethoxysilane (TEOS), methyltri ethoxy silane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane and mixtures thereof, more preferentially 3 -aminopropyltri ethoxy silane (APTES) or tetraethoxysilane (TEOS), and mixtures thereof.

[Claim 10] The process as claimed in any one of the preceding claims, characterized in that the alkoxysilane(s) of formula (II), the oligomers thereof and/or mixtures thereof are present in a total amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight and better still from 1% to 20% by weight relative to the total weight of the composition.

[Claim 11] The process as claimed in any one of the preceding claims, characterized in that the composition comprises water, and the water is preferably present in a content ranging from 0.1% to 50% by weight and more preferentially from 0.5% to 40% by weight relative to the total weight of the composition.

[Claim 12] The process as claimed in any one of the preceding claims, characterized in that the composition comprises one or more organic solvent(s) preferably chosen from C1-C4 lower alkanols, more preferentially ethanol.

[Claim 13] The process as claimed in any one of the preceding claims, characterized in that it involves a step of applying a makeup-removing composition comprising at least one hydrocarbon-based oil to said area of skin.

[Claim 14] The process as claimed in claim 13, characterized in that the hydrocarbon- based oil(s) are chosen from synthetic esters of formula R1COOR2 in which Ri represents a fatty acid residue including from 8 to 29 carbon atoms, and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, and mixtures thereof, more preferentially from isopropyl myristate, isononyl isononanoate and/or mixtures thereof.

[Claim 15] The process as claimed in either of claims 13 and 14, characterized in that the application of the dye composition as defined in any one of claims 1 to 12 to said area of skin is performed before applying the makeup-removing composition. [Claim 16] A kit for coloring an area of skin bearing keratin fibers, comprising:

- a dye composition as defined in any one of claims 1 to 12, and

- a makeup-removing composition as defined in either of claims 13 and 14.