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Title:
HAIR DYEING PROCESS USING A TITANIUM SALT, A FATTY ETHER AND A NATURAL DYE
Document Type and Number:
WIPO Patent Application WO/2020/127441
Kind Code:
A1
Abstract:
The present invention relates to a process for dyeing keratin fibers, comprising a step of treating the fibers by applying a composition containing at least one titanium salt and a step of treating the fibers by applying a composition containing at least one natural dye; it being understood that the process comprises the application of at least one fatty ether that is solid at room temperature and at atmospheric pressure, of formula R-O-R' in which R and R', which may be identical or different, denote a linear or branched alkyl or alkenyl radical, R and R' comprising at least 12 carbon atoms.

Inventors:
LALLEMAN BORIS (FR)
LAFUMA AURÉLIE (FR)
Application Number:
EP2019/085877
Publication Date:
June 25, 2020
Filing Date:
December 18, 2019
Export Citation:
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Assignee:
OREAL (FR)
International Classes:
A61K8/29; A61K8/97; A61Q5/06
Domestic Patent References:
WO2011086284A12011-07-21
WO2011086282A12011-07-21
Foreign References:
FR3029407A12016-06-10
FR3037238A12016-12-16
FR3029405A12016-06-10
FR2976793A12012-12-28
FR3014682A12015-06-19
FR3014681A12015-06-19
FR2814943A12002-04-12
FR2814945A12002-04-12
FR2814946A12002-04-12
FR2814947A12002-04-12
FR297673A
FR2951374A12011-04-22
DE4127230A11993-02-18
US4131576A1978-12-26
FR2633940A11990-01-12
Attorney, Agent or Firm:
FEVRIER, Murielle (FR)
Download PDF:
Claims:
Claims

[Claim 1 ] A process for dyeing keratin fibers, comprising:

i) a step of treating the fibers by applying a composition (A) containing at least one titanium salt; and

ii) a step of treating the fibers by applying a composition (B) containing at least one natural dye;

it being understood that the process comprises the application of at least one fatty ether that is solid at room temperature and at atmospheric pressure, of formula R-O-R' in which R and R', which may be identical or different, denote a linear or branched alkyl or alkenyl radical, R and R' comprising at least 12 carbon atoms, the solid fatty ether being applied separately or present in composition (A) and/or (B).

[Claim 2] The process as claimed in claim 1 , in which at least one titanium salt is chosen from organic salts, in particular of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV).

[Claim 3] The process as claimed in either of the preceding claims in which at least one titanium salt is chosen from dihydroxybis(lactato)titanium(IV) salts, preferably having the following formula:

[Claim 4] The dyeing process as claimed in any one of the preceding claims 1 or 2, in which the titanium salt is chosen from inorganic salts of Ti(ll), Ti(lll) or Ti(IV), more particularly of Ti(lll) or Ti(IV), even more particularly of Ti(IV); preferentially, the titanium salt(s) are chosen from titanium halides, titanium sulfates and titanium phosphates.

[Claim 5] The process as claimed in any one of the preceding claims, in which the total content of titanium salts in composition (A) ranges from 0.001 % to 20% by weight, preferably from 0.01 % to 15% by weight, more preferentially from 0.1 to 10% by weight and better still from 1 % to 8% by weight relative to the total weight of composition (A).

[Claim 6] The process as claimed in any one of the preceding claims, in which the natural dye(s) of composition (B) are chosen from hematoxylin, hematein, brazilin and brazilein, preferentially brazilin, the following plant extracts (genus and species): Haematoxylon campechianum, extract of oxidized logwood ( Haematoxylon campechianum), brasiletto ( Hematoxylum braziletto, rich in brazilin and protosappanin), sappan wood, anthocyanidols, preferably anthocyanidols from blueberry and 3-deoxyanthocyanidins from sorghum, polyene natural dyes such as curcumin, demethoxycurcumin and

bisdemethoxycurcumin, preferably curcumin.

[Claim 7] The process as claimed in any one of the preceding claims, in which the total content of natural dyes in composition (B) ranges from 0.001 % to 30% by weight, preferably from 0.5% to 25% by weight, preferably from 1 % to 20% by weight relative to the total weight of composition (B).

[Claim 8] The process as claimed in any one of the preceding claims, in which the solid fatty ether(s) of formula R-O-R' are such that R and R', which may be identical or different, denote a linear or branched C12-C40, preferably C12-C30, more preferentially C14-C24 alkyl or alkenyl radical; preferably, R and R', which may be identical or different, represent a linear C14-C24 alkyl radical;

preferentially, R and R' are identical and represent a linear C14-C24 and better still C16-C22 alkyl radical and better still R and R' denote a saturated radical, better still derived from stearyl alcohol (C18).

[Claim 9] The process as claimed in any one of the preceding claims, in which the total content of solid fatty ether(s) ranges from 0.1 % to 30% by weight relative to the weight of the composition containing them, preferably between 1 % and 25% by weight, preferentially between 5% and 15% by weight relative to the total weight of the composition containing them. [Claim 10] The process as claimed in any one of the preceding claims, in which composition (A) and/or (B) comprises at least one polysaccharide.

[Claim 11 ] The process as claimed in claim 10, in which the

polysaccharide(s) are chosen from microbial gums, preferably from

scleroglucan gums.

[Claim 12] The process as claimed in any one of the preceding claims, in which composition (A) and/or (B) comprises one or more organic solvents, chosen from protic aromatic solvents, C2-C6 alkanols, (C2-C6)alkanediols and (C2-C6)alkanetriols, more preferentially C2-C4 alkanols such as ethanol.

[Claim 13] The process as claimed in any one of the preceding claims, in which the leave-on time of composition (A) or (B) on the keratin fibers is between 1 minute and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 10 and 45 minutes and/or the leave-on period of said composition (A) or (B) as defined previously on the keratin fibers takes place at a temperature of between 20°C and 50°C, more preferentially between room temperature (25°C) and 45°C.

[Claim 14] The process as claimed in any one of the preceding claims, which comprises, in the following order, the application of composition (A) followed by a step of rinsing said fibers, and then the application of composition (B).

[Claim 15] A composition comprising at least one titanium salt as defined in any one of claims 1 to 5 and at least one fatty ether that is solid at room temperature and at atmospheric pressure as defined in any one of claims 1 , 8 and 9.

[Claim 16] The use of the composition as claimed in claim 15, for treating keratin fibers. [Claim 17] A multi-compartment device or kit comprising, in at least one of the compartments, composition (A), and in a separate compartment, composition (B), and optionally an additional compartment comprising a composition containing the at least one solid fatty ether as defined in any one of the preceding claims, compositions (A) and (B) being as defined in any one of the preceding claims.

Description:
Description

Title: Hair dyeing process using a titanium salt, a fatty ether and a natural dye

[0001 ] The present invention relates to a process for dyeing keratin fibers,

comprising a step of treating the fibers by applying a composition (A) containing at least one titanium salt; and a step of treating the fibers by applying a composition (B) containing at least one natural dye; it being understood that the process comprises the application of at least one solid fatty ether.

[0002] The present invention relates to a composition for treating keratin fibers,

preferably human keratin fibers such as the hair.

[0003] Several methods are known for dyeing human keratin fibers, and in particular the hair.

[0004] The first, known as oxidation dyeing or permanent dyeing, consists in using one or more oxidation dye precursors, more particularly one or more oxidation bases optionally combined with one or more couplers, in the presence of an alkaline agent and an oxidizing agent, which makes it possible, by oxidative condensation, to form a dye on the hair.

[0005] The second dyeing method, known as direct dyeing or semipermanent

dyeing, comprises the application of direct dyes, which are colored and coloring molecules that have affinity for fibers. The standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural direct dyes. Given the nature of the molecules used, they tend rather to remain on the surface of the fiber and penetrate relatively little into the fiber, when compared with the small molecules of oxidation dye precursors. The main advantage of this type of dyeing is that it does not require an oxidizing agent, which limits the degradation of the fibers. However, the resulting coloring is temporary.

[0006] In the field of dyeing using natural extracts such as ortho-diphenols (ODPs), it is also known practice to dye keratin materials such as the hair or the skin using ODPs in the presence of a metal salt, notably of manganese (Mn) and/or zinc (Zn). In particular, patent applications FR 2 814 943, FR 2 814 945, FR 2 814 946 and FR 2 814 947 propose compositions for dyeing the skin or keratin fibers, comprising a dye precursor that contains at least one ortho-diphenol, Mn and/or Zn oxides and salts, alkaline agents of hydrogen carbonate type in a particular Mn, Zn/hydrogen carbonate ratio and optionally an enzyme. According to these documents, it is possible to obtain colorings on keratin materials with atmospheric oxygen or any oxygen-generating system.

[0007] Other documents describe the use of ODPs in combination with Mn and Zn salts and other metal salts, including titanium salts, and a chemical oxidizing agent (FR 297 673, WO2011/086284, WO2011/086282 and FR 2 951 374).

[0008] Flowever, the colorings obtained using ODPs are not strong enough or

intense enough, and/or are not very persistent, notably in the case of hair fibers.

[0009] It is known practice to use metals at acidic pH for dyeing keratin fibers using a mordanting process, which consists in preparing the fibers before performing the dyeing operation in order to obtain persistent shades (Ullmann's Encyclopedia "Metal and Dyes", 2005 § 5.1 , page 8). Flowever, this process generally has the drawback of not always respecting the cosmeticity of the keratin fiber.

[0010] There is thus a real need to develop dyeing processes that can produce

sufficiently powerful and/or persistent colorings using natural direct dyes. More particularly, there is a need to obtain colorings that satisfactorily withstand external agents (light, bad weather, shampooing or sweat), which are persistent and homogeneous, i.e. showing little dyeing selectivity between the root and the end, while at the same time remaining strong and/or chromatic. In addition, it is necessary for the product to be stable and to have suitable working qualities.

[0011 ] This (these) aim(s) are achieved by the present invention, one subject of which is a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising:

i) a step of treating the fibers by applying a composition (A) containing at least one titanium salt; and

ii) a step of treating the fibers by applying a composition (B) containing at least one natural dye;

it being understood that the dyeing process comprises the application of at least one fatty ether that is solid at room temperature and at atmospheric pressure, of formula R-O-R' in which R and R', which may be identical or different, denote a linear or branched alkyl or alkenyl radical, R and R' comprising at least 12 carbon atoms.

[0012] A subject of the invention is also a composition comprising at least one

titanium salt, at least one fatty ether that is solid at room temperature and at atmospheric pressure as defined previously, and also the use of this composition for treating keratin fibers, notably the hair.

[0013] Another subject of the invention relates to a multi-compartment device

comprising, in at least one of the compartments, composition (A), and in a separate compartment, composition (B), and optionally an additional

compartment comprising a composition containing the at least one solid fatty ether as defined previously; compositions (A) and (B) being as defined

previously.

[0014] The process according to the invention has the advantage of dyeing human keratin fibers, notably the hair, intensely and with persistent dyeing results. In particular, the color homogeneity between the root and the end of the fibers is improved (low selectivity).

[0015] Other features and advantages of the invention will emerge more clearly on reading the description and the examples that follow.

[0016] For the purposes of the present invention and unless otherwise indicated:

- for the purposes of the present invention, the term“direct dye’’means colored species - natural and/or synthetic dyes - which are soluble in the cosmetic medium, these are dyes which diffuse on the surface of the keratin fibers; and

- the term“stable’’refers to a composition which does not show any significant change in appearance, odor, pH and/or rheology after storage, in particular after storage for 1 month at 4°C and/or 2 months at 45°C and/or at room temperature. Among the changes in appearance, mention may be made notably of phase separation, precipitation and creaming; and

- the term "a//cy/" radicals means saturated, linear or branched, generally C1-C20, particularly C1-C10, hydrocarbon-based radicals, preferably C1-C6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl; and

- the term "alkenyt' radicals means unsaturated and linear or branched C2-C20 hydrocarbon-based radicals; preferably comprising at least one double bond, such as ethylene, propylene, butylene, pentylene, 2-methylpropylene and decylene; and

- the expression "at least one" is equivalent to "one or more and

- the limits of a range of values are included in that range, notably in the expressions“between... and ..." and“ranging from ... to

[0017] The titanium salt(s):

[0018] Composition (A) used in step i) of the process according to the invention

comprises one or more titanium salts.

[0019] The titanium salt(s) of the invention may be one or more organic or mineral titanium salts.

[0020] For the purposes of the present invention, the term " organic titanium salt' means the salts per se resulting from the action of at least one organic acid on Ti which may be of oxidation state 1 , 2, 3 or 4, preferably of oxidation state 4, denoted Ti(IV).

[0021 ] The term " organic acid” means an acid, i.e. a compound that is capable of releasing a cation or proton H + or H 3 0 + , in aqueous medium, which includes at least one optionally unsaturated, linear or branched C 1 -C 20 hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl group and at least one acid chemical function chosen in particular from carboxyl COOH, sulfuric SO 3 H, SO 2 H, and phosphoric PO3H 2 , PO 4 H 2. In particular, the organic acid(s) are for forming the organic titanium salt(s) of the invention are chosen from the carboxylic acids of formula (I) below: in which formula (I):

- A represents a monovalent group when n has the value 0 or a polyvalent group when n is greater than or equal to 1 , a saturated or unsaturated, cyclic or noncyclic and aromatic or nonaromatic hydrocarbon-based group comprising from 1 to 50 carbon atoms which is optionally interrupted with one or more heteroatoms and/or optionally substituted, notably with one or more hydroxyl and/or amino groups; preferably, A represents a monovalent (Ci-Ce)alkyl group or a polyvalent (Ci-Ce)alkylene group optionally substituted with one or more hydroxyl and/or amino groups;

- n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2.

[0022] The organic acid(s) are preferably chosen from a-hydroxy acids such as lactic acid, glycolic acid, tartaric acid or citric acid.

[0023] Preferentially, the organic titanium salt derived from the action of one or more organic acids as defined previously, preferably carboxylic acid(s) of formula (I) as defined previously, is an optionally charged (in particular negatively charged) complex, which is complexed with one or more carboxylate groups of carboxylic acid(s).

[0024] Preferentially, the organic titanium salt(s) are chosen from those of formula (I- A) below:

in which formula (l-A):

- A is identical to that of formula (I)

- n, n' and n”, which may be identical or different, are equal to 1 , 2, 3 or 4 and n' + n" = 6;

- Mi and M2, which may be identical or different, represent a cationic counterion chosen in particular from cations of an alkali metal such as Na or K or of an alkaline-earth metal such as Ca or an organic cation such as ammonium, preferably ammonium or a hydrogen atom;

- TiYn’’denoting Ti(OH)n”, or Ti(0)n”/2, or Ti(0H)mi(0)m 2 with mi+m 2 = n”.

[0025] Preferentially, the radical A of compound (l-A) as defined previously

represents a monovalent (Ci-Ce)alkyl or polyvalent (Ci-Ce)alkylene group optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably with one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 2, inclusive; in particular, the carboxylic acid(s) used to form the organic titanium salt(s) of the invention are chosen from a-hydroxy acids and a-amino acids; preferably, the acid is chosen from citric acid, lactic acid, tartaric acid, glycolic acid and serine, more

preferentially chosen from lactic acid and glycolic acid.

[0026] Preferentially, the organic titanium salt(s) of the invention are chosen from those of formula (l-B) below:

in which formula (l-B):

- L’and L”, which may be identical or different, represent a divalent

(hetero)arylene, (Ci-Ce)alkylene or (C 2 -C 6 )alkenylene group, said alkylene and arylene groups being optionally substituted with one or more atoms or groups chosen from halo, (Ci-C 4 )alkyl, hydroxyl, thiol and (di)(Ci-C 4 )(alkyl)amino, carboxyl, and/or optionally interrupted with one or more heteroatoms such as oxygen;

preferably, L’and L’’are identical and represent a methylene or ethylene group optionally substituted with a (Ci-C 4 )alkyl group;

- X’and X”, which may be identical or different, represent a heteroatom such as oxygen, sulfur or amino Rc-N with Rc representing a hydrogen atom or a (C-i- C 4 )alkyl group; preferably, X and X" are identical and represent an oxygen atom;

- Y and Y’, which may be identical or different, are as defined for X 1 and X";

preferably, Y and Y are identical and represent an oxygen atom;

- R a and R b , which may be identical or different, represent a hydrogen atom or a (Ci-C6)alkyl, (C 2 -C 6 )alkenyl or (hetero)aryl group; particularly, R a and R b , which are identical, represent a hydrogen atom or a (Ci-C 4 )alkyl group, preferably hydrogen;

- M + , which may be identical or different, represents a cationic counterion such as a cation of an alkali metal (Na or K) or of an alkaline-earth metal (Ca) or an organic cation such as ammonium, preferably ammonium.

[0027] Preferably, the organic titanium salt(s) of the dyeing process are chosen from dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:

[0028] For the purposes of the present invention, the term " inorganic titanium salt' means the salts per se derived from the action of an inorganic acid on Ti.

[0029] The term " inorganic acid" means an acid which does not include any carbon atoms, apart from carbonic acid.

[0030] According to a particular embodiment of the invention, the titanium salt(s) are inorganic and are chosen from titanium halides, titanium sulfates and titanium phosphates. Preferably, the inorganic titanium salts are Ti(ll), Ti(lll) or Ti(IV) salts, more particularly Ti(lll) or Ti(IV) salts, even more preferentially Ti(IV) salts.

[0031 ] According to a preferred embodiment of the invention, the titanium salt(s) are organic titanium salts, and better still organic Ti(IV) salts. According to an advantageous embodiment of the invention, the organic Ti salt consists of a Ti(IV) atom and of 2 to 3 molar equivalents of at least one carboxylic acid of formula (I).

[0032] The titanium salt(s) are present in composition (A) of the dyeing process

according to the invention preferably in a content ranging from 0.001 % to 20%, more particularly from 0.01 % to 15%, preferentially from 0.1 % to 10% by weight and better still from 1 % to 8% by weight relative to the total weight of composition (A).

[0033] According to one embodiment, the organic titanium salt(s) and the inorganic titanium salts according to the invention are soluble in water in a proportion of at least 0.0001 g/l and better still at least 1 g/l.

[0034] According to a particular embodiment, the composition containing the titanium salt(s) is an aqueous composition. [0035] The natural dye(s)

[0036] In accordance with the present invention, composition (B) used in step ii) of the process according to the invention comprises one or more natural dyes.

[0037] The natural dyes may notably be chosen from lawsone, juglone, indigo,

indirubin, isatin, hennotannic acid, or gallic acid, alizarin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogallin, protocatechaldehyde, indigo, curcumin, spinulosin, apigenidin, orceins, carotenoids, polyphenols or ortho diphenols (also referred to as ODPs in the rest of the description), betanine, chlorophyllin, Monascus and any extract rich in ODPs. Use may also be made of extracts or decoctions comprising these natural dyes and notably henna-based and/or indigo-based extracts or poultices.

[0038] Use may also be made according to the invention of the ground material of plant parts, for instance the root, wood, bark or leaf containing natural dyes.

[0039] According to a particularly preferred embodiment of the invention, the natural dye(s) are chosen from ortho-diphenol(s).

[0040] In the context of the invention, the ODP(s) comprise one or more aromatic rings, at least one of which is a benzene ring substituted with at least two hydroxyl (OH) groups borne by two adjacent carbon atoms of said benzene group.

[0041 ] The aromatic ring is more particularly a fused aryl or fused heteroaromatic ring, i.e. optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, indole, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring including at least two hydroxyl groups borne by two adjacent carbon atoms of the aromatic ring. Preferentially, the aromatic ring of the ortho-diphenol derivatives is a benzene ring.

[0042] The term " fused ring " means that at least two saturated or unsaturated and heterocyclic or non-heterocyclic rings have a shared bond, i.e. at least one ring is placed alongside another ring. More particularly, the ODP(s) represent a compound of formula (II), or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as hydrates:

in which formula (II):

- R 1 to R 4 , which may be identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (Ci-C 2 o)alkyl carboxylate or (Ci-C 2 o)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (Ci-C 2 o)alkyl, viii) optionally substituted linear or branched (C 2 -C 2 o)alkenyl, ix) optionally substituted cycloalkyl, x) (C-i- C 2 o)alkoxy, xi) (Ci-C 2 o)alkoxy(C-i-C 2 o)alkyl, xii) (Ci-C 2 o)alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic which is saturated or unsaturated, optionally bearing a cationic or anionic charge and which is optionally substituted and/or optionally fused with an aromatic ring, preferably a benzene ring, said aromatic ring optionally being substituted, in particular with one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;

or two of the substituents borne by two adjacent carbon atoms R 1 - R 2 , R 2 - R 3 or R 3 - R 4 form, together with the carbon atoms bearing them, a saturated or unsaturated and aromatic or nonaromatic ring optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. In particular, the compound of formula (II) comprises from one to four rings.

[0043] A particular embodiment of the invention relates to one or more ODPs of formula (II), two adjacent substituents R 1 - R 2 , R 2 - R 3 or R 3 - R 4 of which cannot form, with the carbon atoms that bear them, a pyrrolyl radical. According to a variant, R 2 and R 3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls.

[0044] For the purposes of the present invention, and unless otherwise indicated:

- the saturated or unsaturated and optionally fused rings may also be optionally substituted;

- the "ary radicals are monocyclic or fused or non-fused polycyclic carbon-based radicals preferentially comprising from 6 to 30 carbon atoms, at least one ring of which is aromatic; preferentially, the aryl radical is chosen from phenyl, biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl;

- the " alkoxy" radicals are alkyl-oxy radicals with alkyl as defined previously, preferably C1-C10 alkyl, such as methoxy, ethoxy, propoxy and butoxy;

- the "alkoxyalkyr radicals are (Ci-C2o)alkoxy(C-i-C2o)alkyl radicals, such as methoxym ethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc. ;

- the“cycloalkyl’’radicals are C4-C8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular substituted with alkyl, alkoxy, carboxylic acid, hydroxyl, amine and ketone groups;

- the " alky or " alkenyt' radicals, when they are " optionally substituted", may be substituted with at least one atom or group borne by at least one carbon atom chosen from: i) halogen; ii) hydroxyl; iii) (Ci-C2)alkoxy; iv) (Ci-Cio)alkoxycarbonyl; v) (poly)hydroxy(C2-C4)alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted with a (Ci-C4)alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different C1-C6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted (Ci-C3)alkyl radicals, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom, c) a quaternary ammonium group -N+R’R”R”’, M- for which R’, R” and R’”, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; and M- represents the counterion of the corresponding organic acid, mineral acid or halide, d) or one optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (Ci-C 4 )alkyl radical, preferably methyl; x) acylamino (-N(R)-C(0)-R’) in which the R radical is a hydrogen atom or a (Ci-C 4 )alkyl radical optionally bearing at least one hydroxyl group and the R’ radical is a C 1 -C 2 alkyl radical; a carbamoyl ((R) 2 N-C(0)-) radical in which the R radicals, which may be identical or different, represent a hydrogen atom or a (Ci-C 4 )alkyl radical optionally bearing at least one hydroxyl group; xi) alkylsulfonylamino (R’-S(0) 2 -N(R)-) in which the R radical represents a hydrogen atom or a (Ci-C 4 )alkyl radical optionally bearing at least one hydroxyl group and the R’ radical represents a (Ci-C 4 )alkyl radical, a phenyl radical; xii) aminosulfonyl ((R) 2 N-S(0) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a (Ci-C 4 )alkyl radical optionally bearing at least one group chosen from a) hydroxyl, b) carboxyl -C(0)-OH in the acid or salified form (preferably salified with an alkali metal or a substituted or

unsubstituted ammonium); xiii) cyano; xiv) nitro; xv) carboxyl or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted with one or more hydroxyl groups; xvii) glycosyloxy; and a phenyl group optionally substituted with one or more hydroxyl groups;

- the "ary or " heterocyclic " radicals or the aryl or heterocyclic part of the radicals, when they are " optionally substituted", may be substituted with at least one atom or group borne by at least one carbon atom chosen from:

i) (Ci-C-io)alkyl, preferably C-i-Cs alkyl, optionally substituted with one or more radicals chosen from the following radicals: hydroxyl, (Ci-C 2 )alkoxy,

(poly)hydroxy(C 2 -C 4 )alkoxy, acylamino, amino substituted with two identical or different C 1 -C 4 alkyl radicals optionally bearing at least one hydroxyl group or it being possible for the two radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7- membered, preferably 5- or 6-membered, heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; ii) halogen; iii) hydroxyl; iv) C 1 -C 2 alkoxy; v) C 1 -C 10 alkoxycarbonyl; vi) (poly)hydroxy(C 2 -C 4 )alkoxy; vii) amino; viii)

5- or 6-membered heterocycloalkyl; ix) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted with a (Ci-C 4 )alkyl radical preferably methyl; x) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted Ci- C 3 alkyl radicals, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom, c) one quaternary ammonium group - N + R’R”R”’, M- for which R’, R” and R”\ which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl group; and M- represents the counterion of the corresponding organic acid, mineral acid or halide, d) one optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, optionally substituted with a (Ci-C 4 )alkyl radical, preferentially methyl; xi) acylamino (-N(R)-C(0)-R’) in which the radical R is a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R’ is a C 1 -C 2 alkyl radical; xii) carbamoyl ((R) 2 N-C(0)-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xiii) alkylsulfonylamino (R’S(0) 2 - N(R)-) in which the radical R represents a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R’ represents a C-i- C 4 alkyl radical or a phenyl radical; xiv) aminosulfonyl ((R) 2 N-S(0) 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xv) carboxyl in the acid or salified form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium); xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferentially trifluoromethyl; xix) a glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; xxi) a glycosyloxy group; and xxii) a phenyl group optionally substituted with one or more hydroxyl groups;

- for the purposes of the present invention, the term "glycosyl" radical means a radical derived from a mono- or polysaccharide;

- the radicals " containing one or more silicon atoms " are preferably

polydimethylsiloxane, polydiphenylsiloxane, polydimethylphenylsiloxane or stearoxy dimethicone radicals;

- the " heterocyclic " radicals are radicals comprising, in at least one ring, one or more heteroatoms chosen in particular from O, N and S, preferably O or N, optionally substituted notably with one or more alkyl, alkoxy, carboxyl, hydroxyl, amine or ketone groups. These rings may comprise one or more oxo groups on the carbon atoms of the heterocycle; mention may notably be made, among the heterocyclic radicals that may be used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl or thienyl groups; even more preferably, the heterocyclic groups are fused groups, such as benzofuryl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl, coumarinyl or isocoumarinyl groups, it being possible for these groups to be substituted, in particular with one or more OH groups.

[0045] According to a preferred embodiment of the invention, the dye composition used in the process for dyeing keratin fibers comprises, as natural dye, one or more natural ODPs.

[0046] Examples that may be mentioned include:

- flavanols, for instance catechin and epicatechin gallate,

- flavonols, for instance quercetin,

- anthocyanidins, for instance cyanidin, delphinidin or petunidin,

- anthocyanins or anthocyans, for instance myrtillin,

- ortho-hydroxybenzoates, for example gallic acid salts,

- flavones, for instance luteolin,

- hydroxystilbenes, for example tetrahydroxy-3,3',4,5'-stilbene, optionally oxylated (for example glucosylated),

- 3,4-dihydroxyphenylalanine and derivatives thereof,

- 2,3-dihydroxyphenylalanine and derivatives thereof,

- 4,5-dihydroxyphenylalanine and derivatives thereof,

- dihydroxycinnamates, such as caffeic acid and chlorogenic acid,

- ortho-polyhydroxycoumarins,

- ortho-polyhydroxyisocoumarins,

- ortho-polyhydroxycoumarones,

- ortho-polyhydroxyisocoumarones,

- ortho-polyhydroxychalcones,

- ortho-polyhydroxychromones,

- quinones,

- hydroxyxanthones,

- 1 ,2-dihydroxybenzene and derivatives thereof,

- 1 ,2,4-trihydroxybenzene and derivatives thereof,

- 1 ,2,3-trihydroxybenzene and derivatives thereof, - 2,4,5-trihydroxytoluene and derivatives thereof,

- proanthocyanidins,

- chroman and chromene compounds,

- proathocyanins,

- tannic acid,

- gallic acid,

- ellagic acid,

- and mixtures of the preceding compounds.

As ODP, mention may also be made of hematoxylin, hematein, brazilin and brazilein.

Hematoxylin (Natural Black 1 - Brazilin (Natural Red 24 - CAS 517-28-2) CAS 474-07-7)

Brazilein is a conjugated form of a chroman compound with the tautomeric structures illustrated below.

Brazilein [0047] Among the ODPs of hematoxylin/hematein and brazilin/brazilein type, examples that may be mentioned include hematoxylin (Natural Black 1 according to the INCI name) and brazilin (Natural Red 24 according to the INCI name), dyes of the indochroman family, which are commercially available. The latter dyes may exist in an oxidized form and may be obtained synthetically or by extraction of plants or vegetables known to be rich in these dyes.

[0048] The ODPs described previously may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa and Caesalpinia brasiliensis.

[0049] The extracts are obtained by extracting various plant parts, for instance the root, the wood, the bark or the leaves.

[0050] According to a particular embodiment of the invention, the ODP(s) are

obtained from logwood, pernambuco wood, sappan wood and Brazil wood.

[0051 ] Use may also be made of plant extracts of red woods, bringing together

generally the species of red woods from Asia and West Africa of the genus Pterocarpus and of the genus Baphia. These woods are, for example,

Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or else Baphia nitida. These woods may also be called padauk, sandalwood, narra wood, camwood or else barwood.

[0052] Thus, extracts that may be used, containing ODPs, may be obtained, for example, from red sandalwood ( Pterocarpus santalinus) by aqueous basic extraction, such as the product sold under the trade name Santal Concentre SL 709C by the company COPIAA, or also by means of solvent extraction of sandalwood powder, such as the product sold under the trade name Santal Poudre SL PP by the same company COPIAA. Mention may also be made of the aqueous/alcoholic extract of powdered red sandalwood from Alban Muller.

[0053] Extracts that are also suitable for use in the present invention may be

obtained from woods such as camwood (Baphia nitida) or barwood ( Pterocarpus soyauxii, Pterocarpus erinaceus ): the latter is thus split up and then ground: a conventional alcoholic extraction or an extraction by percolation is subsequently performed on this ground material in order to collect a pulverulent extract that is particularly suitable for the implementation of the present invention.

[0054] In particular, the ODPs are chosen from catechin, quercetin, brazilin, hematein, hematoxylin, chlorogenic acid, caffeic acid, catechol, gallic acid, L- DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (-)- epigallocatechin 3-gallate (EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3-hydroxy-2,4-dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin, pericampylinone A, theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin C 1 , procyanidins DP 4-8, tannic acid, purpurogallin, 5,6-dihydroxy-2-methyl-1 ,4- naphthoquinone, anthraquinones (carminic acid, kermesic acid or laccaic acid, alizarin, purpurin, pseudopurpurin, munjistin, rubiadin, lucidin, anthragallol, morindone), indigoids (indigo, isoindigo, indirubin, diosindigo), wedelolactone, variegatic acid, gomphidic acid, xerocomic acid and carnosol, and natural extracts containing same.

[0055] Preferably, the ODPs of the invention are chromenes or chromans and are chosen from hematein, hematoxylin, brazilein, brazilin and santalin A.

[0056] According to one embodiment, the natural ODPs are derived from extracts of animals, bacteria, fungi, algae, plants and fruits, used in their entirety or partially. In particular regarding plants, the extracts are derived from fruit, including citrus fruit, from vegetables, from trees and from shrubs.

[0057] Preferably, the natural ODP(s) that are of use in the invention are derived from extracts of plants or plant parts.

[0058] The extracts are obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.

[0059] Among the extracts of plants, mention may be made of extracts of rose or tea leaves.

[0060] Among the extracts of fruit, mention may be made of extracts of apple,

extracts of grape (in particular of grape seed) or extracts of cocoa beans and/or pods. [0061 ] Among the extracts of vegetables, mention may be made of extracts of potato or of onion peel.

[0062] Among the extracts of tree wood, mention may be made of extracts of pine bark and extracts of logwood.

[0063] Preferentially, the natural dye(s) that are of use in the invention are chosen from hematoxylin, hematein, brazilin and brazilein; preferentially brazilin, the following plant extracts (genus and species): Haematoxylon campechianum, extract of oxidized logwood ( Haematoxylon campechianum), brasiletto

( Hematoxylum braziletto, rich in brazilin and protosappanin), anthocyanidols, preferably anthocyanidols from blueberry and 3-deoxyanthocyanidins from sorghum, polyene natural dyes such as curcumin, demethoxycurcumin and bisdemethoxycurcumin, preferably curcumin.

[0064] Preferably, the natural dye(s) are present in composition (B) in a total content ranging preferably from 0.001 % to 30% by weight, preferably from 0.5% to 25% by weight, preferably from 1 % to 20% by weight.

[0065] One or more fatty ethers

[0066] The process according to the invention uses one or more solid fatty ethers of formula R-O-R' in which R and R', which may be identical or different, denote a linear or branched alkyl or alkenyl radical, R and R' comprising at least 12 carbon atoms. The fatty ether that is of use in the present invention is a solid fatty ether.

[0067] The term“solid fatty ether” means a fatty ether that is solid at room

temperature and at atmospheric pressure (25°C, 1 atm).

[0068] Preferably, the ether is chosen from compounds for which the radicals R and R', which may be identical or different, denote a linear or branched C12-C40, preferably C12-C30, more preferentially C14-C24 alkyl or alkenyl radical.

[0069] In accordance with a particular embodiment of the invention, the radicals R and R', which may be identical or different, are radicals derived from oleyl alcohol (C18), lauryl alcohol (C12), palmityl alcohol (C16), myristyl alcohol (C14), behenyl alcohol (C22), stearyl alcohol (C18), linoleyl alcohol (C18), linolenyl alcohol (C18) and arachidyl alcohol (C20). [0070] Preferably, R and R' represent a linear C12-C40, preferably C12-C30 and preferentially C14-C24 alkyl radical.

[0071 ] More particularly, R and R' are identical.

[0072] Preferentially, R and R' are identical and represent a linear C14-C24 alkyl radical; better still, R and R' denote a linear C16-C22 alkyl radical and better still a stearyl radical.

[0073] Preferentially, the ethers that may be used according to the invention are saturated.

[0074] More preferentially, the ethers that may be used according to the invention have a melting point above 50°C.

[0075] The fatty ethers that may be used according to the invention may be soluble or insoluble in the compositions, but are preferably insoluble.

[0076] These compounds may be prepared according to the process described in patent application DE 41 27 230.

[0077] According to a particular embodiment, the ether is distearyl ether or

dioctadecyl ether, and corresponds to the above formula in which R and R' represent a CH3(CH2)i7- group.

[0078] The solid fatty ether(s) according to the invention are preferably present in a total content of between 0.1 % and 40% by weight relative to the weight of the composition containing them, preferably between 1 % and 25% by weight, preferentially between 5% and 15% by weight relative to the weight of the composition containing them.

[0079] According to one embodiment of the process of the invention, the fatty ether may be present in a separate composition or in one or other of the compositions (A) and (B) or in both.

[0080] According to a particular embodiment, the fatty ether(s) are present in one or other of the compositions (A) or (B) or in both, preferably in composition A.

[0081 ] According to a particular embodiment, compositions (A) and/or (B) contain one or more polymers of polysaccharide type. According to a particular embodiment, the polysaccharide(s) are present in composition (A) and in composition (B).

[0082] The polymers of polysaccharide type that are of use for the invention are polymers that may be of natural or synthetic origin.

[0083] Preferably, the polymers of polysaccharide type are thickening polymers. The term“thickening polymer 1 ' means a polymer which, when introduced at 1 % by weight into an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or into an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s 1 . This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like).

[0084] The polysaccharide polymers that are of use in the invention are cationic, nonionic, anionic or amphoteric polymers, preferably cationic, nonionic or anionic polymers.

[0085] The term“ olysaccharide polymers " means polymers bearing sugar units.

[0086] For the purposes of the present invention, the term "sugar unit" means a unit derived from a carbohydrate of formula C n (H20) n -i or (CH20) n , which may be optionally modified by substitution and/or by oxidation and/or by dehydration.

[0087] The sugar units of the polymers that are of use in the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.

[0088] Polysaccharide polymers that may notably be mentioned include those

derived from native gums such as:

a) tree or shrub exudates, including:

- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);

- ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);

- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); - gum tragacanth (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);

b) gums derived from algae, including:

- agar (polymer derived from galactose and anhydrogalactose);

- alginates (polymers of mannuronic acid and of glucuronic acid);

- carrageenans and furcellerans (polymers of galactose sulfate and of

anhydrogalactose sulfate);

c) gums derived from seeds or tubers, including:

- guar gum (polymer of mannose and galactose);

- locust bean gum (polymer of mannose and galactose);

- fenugreek gum (polymer of mannose and galactose);

- tamarind gum (polymer of galactose, xylose and glucose);

- konjac gum (polymer of glucose and mannose);

d) microbial gums, including:

- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);

- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);

- scleroglucan gum (glucose polymer);

e) plant extracts, including:

- cellulose (glucose polymer);

- starch (glucose polymer) and

- inulin, and

- pectin.

[0089] These polymers may be physically or chemically modified. As physical

treatment, mention may notably be made of the temperature.

[0090] Chemical treatments that may be mentioned include esterification,

etherification, amidation or oxidation reactions. These treatments make it possible to produce polymers that may notably be nonionic, anionic or amphoteric.

[0091 ] Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses. [0092] The nonionic guar gums that may be used according to the invention may be modified with C1-C6 (poly)hydroxyalkyl groups.

[0093] Among the C1-C6 (poly)hydroxyalkyl groups, mention may be made, by way of example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

[0094] These guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

[0095] The degree of hydroxyalkylation preferably varies from 0.4 to 1.2 and

corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functional groups present on the guar gum.

[0096] Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60,

Jaguar HP105 and Jaguar HP120 by the company Rhodia Chimie.

[0097] The polysaccharide polymers may be cellulose-based polymers.

[0098] Thus, the cellulose-based polymers may be chosen from unsubstituted

celluloses, including those in a microcrystalline form, and cellulose ethers.

[0099] Among these cellulose-based polymers, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

[0100] Among the cellulose esters are inorganic esters of cellulose (cellulose

nitrates, sulfates, phosphates, etc.), organic esters of cellulose (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates,

acetatepropionates or acetatetrimellitates), and mixed organic/inorganic esters of cellulose, such as cellulose acetatebutyrate sulfates and cellulose

acetatepropionate sulfates. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

[0101 ] Among the nonionic cellulose ethers not bearing a C10-C30 fatty chain, i.e. which are "nonassociative", mention may be made of (Ci-C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example, Ethocel standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci-C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example, Natrosol 250 HHR provided by Aqualon) and hydroxypropylcelluloses (for example, Klucel EF from Aqualon); mixed (poly)hydroxy(Ci-C4)alkyl(Ci-C4)alkylcelluloses, such as hydroxypropylmethylcelluloses (for example, Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example,

Bermocoll E 481 FQ from AkzoNobel) and hydroxybutylmethylcelluloses.

[0102] Among the anionic cellulose ethers, mention may be made of

(poly)carboxy(Ci-C4)alkylcelluloses and salts thereof. Examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and

carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.

[0103] Among the cationic cellulose ethers, mention may be made of cationic

cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in patent US 4 131 576, such as (poly)hydroxy(Ci-C4)alkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted notably with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® FI 100 by the company National Starch.

[0104] Preferably, the polysaccharide(s) according to the invention are chosen from microbial gums.

[0105] The microbial gums may be chosen from scleroglucan gums, gellan gums, pullulan gums, curdlan gums, xanthan gums, grifolan gums, lentinan gums, schizophyllan gums, spirulinan gums and krestin gums.

[0106] Mention may notably be made of the scleroglucan gums produced by

Sclerotium rolfsii, the gellan gums produced by Pseudomonas elodea or

Sphingomonias, the pullulan gums produced by Aureobacidium pullulens, the curdlan gums produced by alcaligenes of Faecalis myxogenes type, the xanthan gums produced by numerous organisms, including Leuconostoc mesenteroides and Leuconostoc dextrantum, the grifolan gums produced by Grifola frondara, the lentinan gums produced by Lentinus edodes, the schizophyllan gums produced by Schizophyllum commine, the spirulinan gums produced by Spirulina sybsyla and the krestin gums produced by Coriates versicolor.

[0107] More preferentially, the polysaccharide(s) according to the invention are

chosen from scleroglucan gums.

[0108] The scleroglucans used in accordance with the invention are neutral

polysaccharides preferably corresponding to formula (I):

where the degree of polymerization n ranges from 500 to 1600.

[0109] According to the invention, use is advantageously made of scleroglucans of microbial origin, obtained, for example, by aerobic fermentation of a glucose- containing medium by a fungus of the Sclerotium type and having the structure of a D-glucopyranose homopolymer.

[0110] Examples of scleroglucan gums that may be used in the present invention are, in a nonlimiting manner, the products sold under the name Actigum CS, in particular Actigum CS 11 by the company Sanofi Bio Industries and under the name Amigum or Amigel by the company Alban MCiller International.

[0111 ] Other scleroglucans, such as that treated with glyoxal described in French patent application No. 2 633 940, may also be used.

[0112] Use will be made in particular of the scleroglucan gums having the INCI name Sclerotium gum.

[0113] Preferably, the polysaccharide(s) according to the invention are chosen from microbial gums, hydroxyalkyl guars and (hydroxy)(Ci-C 6 )alkyl cellulose.

[0114] The polysaccharide polymer(s) are generally present in the composition

according to the invention containing them in a total content ranging from 0.001 % to 10% by weight, preferably from 0.05% to 5%, more preferentially from 0.1 % to 3% by weight and better still from 0.5% to 2.5% by weight relative to the total weight of the composition.

[0115] According to another variant, composition (A) comprises one or more

carboxylic acids.

[0116] The term " carboxylic acid" means a compound comprising at least one

carboxylic acid -C(0)-OH group, preferably of formula (I) as defined previously, preferably comprising between 1 and 4 carboxylic acid groups, such as 1 or 2; or chosen from: i) (Ci-Cio)alkyl-[C(0)-OH]n and ii) het-[C(0)-OH]n, with n an integer between 1 and 4 inclusive, preferably between 1 and 2, het representing a heterocyclic group, such as pyrrolidone, it being possible for the alkyl or het group to be optionally substituted with one or more groups chosen notably from OH and (di)(Ci-C 6 )(alkyl)amino.

[0117] According to an advantageous variant, the dyeing process also uses one or more carboxylic acids of formula (I) as defined previously.

[0118] More preferentially, the carboxylic acid(s) are chosen from glycolic acid, citric acid and lactic acid, or a salt thereof. It is preferably different from the carboxylic acids complexed to the Ti salts.

[0119] For example, if the carboxylic acid complexed to the titanium salt is lactic acid or the carboxylate salt thereof (lactate), the second acid of composition (A) is other than lactic acid or lactate, and may be, for example, glycolic acid.

[0120] The acid salts of formula (I) may be salts of organic or mineral bases or

basifying agents. Preferably, the salts are sodium, ammonia or potassium salts or salts of organic amines such as alkanolamines.

[0121 ] The acids of formula (I) or salts thereof are present in composition (A) in a content ranging from 0.1 % to 20% by weight relative to the total weight of said composition (A).

[0122] According to a particular embodiment, composition (B) also comprises one or more basifying agents. [0123] These basifying agents are bases that can increase the pH of the composition(s) in which they are present. The basifying agent is a Bnzsnsted, Lowry or Lewis base. It may be mineral or organic.

[0124] In particular, this alkaline agent is chosen from aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine or triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (III) below:

in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; R a , R b , Rc and R d , which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.

[0125] According to a particular embodiment, the basifying agent(s) are chosen from aqueous ammonia, alkanolamines and amino acids.

[0126] According to a preferred embodiment, the basifying agent(s) are chosen from organic alkaline agents, preferably from alkanolamines and amino acids, preferably arginine.

[0127] When they are present, the basifying agent(s) as defined previously represent from 0.001 % to 10% by weight relative to the weight of the composition(s) (B) containing them, more particularly from 0.005% to 8% by weight of the

composition.

[0128] According to a particular embodiment of the invention, composition b) of the invention may be mixed at the time of use with a chemical oxidizing agent.

[0129] The term“chemical oxidizing agent' means an oxidizing agent other than atmospheric oxygen.

[0130] More particularly, the oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, peroxygenated salts, for instance

persulfates or perborates, peracids and precursors thereof and alkali metal or alkaline-earth metal percarbonates. [0131 ] The oxidizing agent is advantageously hydrogen peroxide.

[0132] The concentration of oxidizing agents may range more particularly from 0.1 % to 20% by weight, even more preferentially from 0.5% to 15% by weight and better still from 1 % to 10% by weight relative to the weight of the composition.

[0133] According to one variant, composition (B) comprises one or more additional dyes.

[0134] In particular, the dyeing process may use, in composition (B) used in step ii) of the process, one or more synthetic direct dyes, chosen from anionic, cationic and nonionic species, preferably cationic or nonionic species, in addition to the natural dye(s) described above.

[0135] More particularly, the additional synthetic direct dyes are chosen from azo direct dyes; nitro 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, alone or in the form of mixtures.

[0136] When they are present, the direct dye(s) more particularly represent from

0.001 % to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

[0137] According to a particularly preferred embodiment, composition (B) contains only natural dyes.

[0138] Compositions (A) and (B) or the composition comprising the fatty ether, when it is present, are compositions comprising a cosmetically acceptable medium. For the purposes of the present invention, the term“cosmetically acceptable medium’’means a medium that is compatible with keratin fibers, and in particular human keratin fibers such as the hair.

[0139] These compositions generally comprise water and/or one or more organic solvents.

[0140] The water content generally ranges from 10% to 99% by weight, preferably from 20% to 98% by weight and better still from 50% to 95% by weight relative to the total weight of the composition.

[0141 ] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol or phenoxyethanol; polyols or polyol ethers such as ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof such as propylene glycol monomethyl ether, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, and also diethylene glycol alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, or alternatively glycerol; and also mixtures thereof.

[0142] The organic solvents are present in proportions preferably of between 1 % and 40% by weight approximately and even more preferentially between 5% and 30% by weight approximately, relative to the total weight of the dye composition.

[0143] The adjuvants:

[0144] The compositions of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, polymers other than the polymers that are useful in the present invention and which may be anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or nonvolatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.

[0145] The adjuvants are preferably chosen from surfactants such as anionic or

nonionic surfactants or mixtures thereof and mineral or organic thickeners.

[0146] The above adjuvants are generally present in an amount for each of them of between 0.01 % and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition.

[0147] Needless to say, a person skilled in the art will take care to select this or these additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that are useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s). [0148] The cosmetic composition(s) of the invention may be in various presentation forms, such as a powder, a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibers.

[0149] pH of the compositions:

[0150] Composition (A)

[0151 ] Preferably, composition (A) is an aqueous composition. Preferably, the pH of the cosmetic composition (A) is acidic, i.e. it has a pH of less than 7.0, preferably less than 6, in particular between 1.5 and 5, more particularly between 2 and 4, or even between 2 and 3.

[0152] Composition (B)

[0153] Composition (B) is preferably an aqueous composition. The pH of composition (B) is preferably acidic, i.e. it has a pH of between 2 and 10, preferably between 2 and 8, more particularly between 3 and 6.8, and better still between 5 and 6.8.

[0154] The pH of compositions (A) and (B) may be adjusted to the desired value by means of basifying agents as defined previously or by using acidifying agents usually used in the dyeing of keratin fibers, or alternatively by means of standard buffer systems. Among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids as defined previously, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

[0155] Multi-step dyeing process

[0156] According to different variants, the keratin fiber dyeing process of the

invention involves:

- either the application to the fibers of composition (A), followed by the application to the fibers of composition (B);

- or the application to the fibers of composition (B), followed by the application to the fibers of composition (A).

[0157] The process according to the invention may comprise at least one or more rinsing steps, notably an intermediate rinsing step, i.e. a rinsing step between the step of applying to the keratin fibers composition (A) as defined previously and (B) as defined previously and/or a rinsing step after application of composition (B).

[0158] According to one embodiment of the invention, water is preferably used during the rinsing steps. More preferentially, the intermediate rinsing is performed with tap water until the residual water is visually clear and transparent. According to a particular embodiment, when said rinsing is performed after the application of the dye composition (B), or when the intermediate rinsing is performed after the application of composition (A), said rinsing is performed for 1 second to 5 minutes, better still for 5 seconds to 1 minute.

[0159] According to a particular embodiment of the invention, the dyeing process involves the application to the fibers of composition (A) as defined previously, followed by rinsing of said fibers, preferably with water, followed by the

application to the fibers of composition (B) as defined previously.

[0160] According to another particular embodiment of the invention, the dyeing

process involves the application to the fibers of composition (B) as defined previously, followed by rinsing of said fibers, preferably with water, followed by the application to the fibers of composition (A) as defined previously.

[0161 ] Preferably, the dyeing process involves the application to the fibers of

composition (A) as defined previously, followed by the application to the fibers of composition (B) as defined previously.

[0162] More preferentially, the keratin fiber dyeing process of the invention involves the application to the fibers of composition (A), followed by at least one rinsing of said fibers, preferably with water, in particular with tap water, followed by the application to the fibers of composition (B).

[0163] In particular, in the dyeing process of the invention, the leave-on time of

composition (A) as defined previously on the keratin fibers is between 1 minute and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 10 and 45 minutes. Preferentially, the leave-on period of composition (A) on the keratin fibers takes place at a temperature of between 20°C and 50°C, more preferentially between room temperature (20-25°C) and 45°C.

[0164] After applying the compositions (A), the optional rinsing of the keratin fibers and the application of composition (B), and vice versa in the case where composition (B) is used before composition (A), the dyeing process of the invention may involve one or more shampoo washes, followed by rinsing the keratin fibers with water one or more times, optionally followed by drying via a heat treatment by heating to a temperature of between 30 and 60°C.

[0165] One particular embodiment of the invention relates to a dyeing process that is performed at room temperature (20-25°C).

[0166] Preferentially, the process is performed with a composition (A) chosen from those of formula (l-A), (l-B) or the dihydroxybis(lactato)titanium(IV) salts as defined previously.

[0167] A subject of the invention is also a composition comprising at least one

titanium salt as defined previously, at least one fatty ether that is solid at room temperature and at atmospheric pressure as defined previously, and also the use of this composition for treating keratin fibers, notably the hair.

[0168] Another subject of the invention is a multi-compartment dyeing device or "kit".

Advantageously, this kit comprises, in at least one of the compartments, composition (A) as defined above, and, in a separate compartment, composition (B) as defined above, it being understood that at least one of the compositions (A) or (B) or a separate composition comprises at least one fatty ether that is solid at room temperature and at atmospheric pressure as defined above.

[0169] The examples that follow serve to illustrate the invention without, however, being limiting in nature.

Example

[0170] The following compositions are prepared (amounts in g% of active material):

[01711 Example 1

- Treatment composition:

[0172] [Tables 1 ]

- Dye composition:

[0173] [Tables 2]

[0174] The treatment composition 1 was applied in a proportion of 4 g of composition per gram of lock to permanent-waved hair containing 90% of white hairs. After a leave-on time of 15 minutes at 33°C, the locks are rinsed.

[0175] Next, compositions A1 or B1 or C1 are applied to the previously treated locks, in a proportion of 2.5 g of composition per 1 g of hair. The leave-on time is then 20 minutes at 40°C on a hotplate, and then 25 minutes at 33°C.

[0176] The locks are rinsed for 30 seconds, shampooed and dried.

[0177] Very shiny and very soft locks dyed a vivid brown are obtained.

[01781 Example 2

[0179] The following compositions are prepared:

- Treatment composition: [0180] [Tables 3]

- Dye composition:

[0181 ] [Tables 4]

[0182] Locks of natural hair containing 90% of white hairs were treated with the compositions 2 (invention), 2C (comparative), 3C (comparative) and 4C

(comparative) for 15 minutes at 33°C on a plate. The locks were then rinsed.

[0183] Composition A2 was applied to each of the locks thus treated and left on for 45 minutes at 40°C on a hotplate. The locks were then rinsed and dried.

[0184] Matt cream compositions, which are difficult to apply and of granular,

inhomogeneous appearance, were obtained with comparative compositions 2C and 3C, in contrast with composition 2 of the invention which has a very smooth cream texture, is very shiny and is very easy to apply by brush. [0185] Composition 2 is moreover very easy to rinse off and leaves the hair soft, in contrast with comparative composition 2C which is difficult to rinse off and leaves a tacky feel on rinsing.

[0186] Appearance of the compositions after application to a watch glass and to hair:

[0187] [Tables 5]

0188] Colorimetric results:

[0189] The colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0190] In this system, L* represents the lightness. The smaller the value of L* the darker and more powerful the coloring obtained.

[0191 ] The color build-up is represented by the color difference DE between the non- dyed lock and the dyed lock: the greater the value of DE, the greater the color build-up. This value is calculated from equation (i) below:

[0192] In equation (i), L* a* and b* represent the values measured on undyed locks of hair and LO* aO* and bO* represent the values measured on dyed locks of hair.

[0193] The results are given in the table below.

[0194] The colorimetric measurements show that the process of the invention makes it possible to obtain a more intense color (L* significantly smaller) with a better build-up (DE significantly larger) in the case of the presence of fatty ether in the composition.

[0195] [Tables 6]

Ό1961 Example 3

[0197] The following compositions were produced:

[0198] [Tables 7]

[0199] Locks of natural hair were treated with composition 1 of Example 1 for 15 minutes at 33°C on a hotplate.

[0200] The locks were then rinsed and treated with composition A3 for 20 minutes at 40°C, and then for 25 minutes at 33°C on a hotplate.

[0201 ] The locks were then rinsed, shampooed and dried.

[0202] Very shiny and very soft locks dyed a vivid brown are obtained.

[0203] Example 4:

[0204] The following compositions were produced:

[0205] [Tables 8]

[0206] Locks of natural hair were treated with composition 1 of Example 1 for 15 minutes at 33°C on a hotplate.

[0207] The locks were then rinsed and treated with compositions A4 and B4 for 20 minutes at 40°C, and then for 25 minutes at 33°C on a hotplate.

[0208] The locks were then rinsed, shampooed and dried.

[0209] A cream dye composition that is very smooth, very shiny and very easy to apply by brush was obtained with composition A4 according to the invention. Composition A4 according to the invention has an opaque nature allowing better positioning of the product on the roots of white hairs and a creamy texture, affording care and facilitating its spreading on the hair strands.

[0210] In contrast, the dye composition having a gel texture, difficult to position on the hair due to its transparent nature and affording less care, was obtained with comparative composition B4.

[0211 ] Composition A4 is moreover very easy to rinse off and leaves the hair soft, in contrast with comparative composition B4 which is difficult to rinse off and leaves a tacky feel on rinsing.

[0212] Very shiny and very soft locks dyed a vivid black are obtained with

composition A4.

[0213] Example 5:

[0214] The following compositions were produced:

[0215] [Tables 9]

[0216] Locks of permanent-waved hair were treated with composition 1 of Example 1 for 15 minutes at 33°C on a hotplate.

[0217] The locks were then rinsed and treated with compositions A5 and B5 for 20 minutes at 40°C, and then for 25 minutes at 33°C on a hotplate.

[0218] The locks were then rinsed, shampooed and dried.

[0219] Matt cream dye compositions, which are difficult to apply and of granular, inhomogeneous appearance, were obtained with comparative composition B5, in contrast with composition A5 of the invention which has a very smooth cream texture, is very shiny and is very easy to apply by brush.

[0220] Composition A5 is moreover very easy to rinse off and leaves the hair soft, in contrast with comparative composition B5 which is difficult to rinse off and leaves a tacky feel on rinsing.

[0221 ] Appearance of the compositions after application to a watch glass and to hair:

[0222] [Tables 10]

0223] Colorimetric results : [0224] The evaluation of the coloring was performed as described previously. The results are given in the table below.

[0225] The colorimetric measurements below show that the process of the invention makes it possible to obtain a more intense color (L* significantly smaller) with a better build-up (DE significantly larger).

[0226] [Tables 11 ]