FR3111072A1 - Hair coloring process using a lanthanide salt and a natural dye - Google Patents

Abstract

Hair treatment process using a lanthanide salt and a natural dye The present invention relates to a hair treatment process, comprising the application to the hair of at least one lanthanide salt and at least one natural coloring, applied together or separately.

Description

Hair coloring process using a lanthanide salt and a natural dye

The subject of the present invention is a process for coloring the hair with at least one lanthanide salt and at least one natural dye.

Two major modes of coloring human keratin fibres, and in particular the hair, are known.

One of these two modes is oxidation or permanent coloring. This coloring method uses one or more oxidation dye precursors, usually one or more oxidation bases possibly associated with one or more couplers. In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, give access to colored species. Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds. The variety of molecules involved in oxidation bases and couplers allows a rich palette of colors to be obtained. This type of coloring also makes it possible to obtain permanent coloring, but the use of oxidizing agents can lead to the degradation of keratin fibres.

The second coloring mode, called direct or semi-permanent coloring, includes the application of direct dyes which are molecules with an affinity for fibers and dyes even in the absence of an oxidizing agent added in the compositions containing them. Given the nature of the molecules used, these remain on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of precursors of oxidation dyes. The direct dyes generally employed are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used can be nonionic, anionic (acid dyes) or cationic (basic dyes). Direct dyes can also be natural dyes. However, the resulting colorations are colorations that can be particularly chromatic but temporary or semi-permanent because their desorption from the surface and/or the core of the fiber is responsible for their lack of dyeing power and their poor washability. .

The chromophores of natural dyes are also very often sensitive to pH, to light, to sweat, conferring a low level of tenacity, in particular to light and to sweat.

In the field of coloring using natural extracts such as ortho-diphenols (ODPs), it is also known to color keratin materials such as hair or skin using ODPs in the presence of a metal salt, in particular manganese (Mn) and/or zinc (Zn). In particular, the patent applications FR 2814943, FR 2814945, FR 2814946, FR 2814947 propose compositions for coloring the skin or keratin fibres, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides of Mn and/or Zn, alkalines of the hydrogen carbonate type in a particular Mn, Zn/hydrogen carbonate ratio and optionally an enzyme. According to these documents, it is possible to obtain colorations of keratin materials with the oxygen in the air or any system that generates oxygen. Other documents describe the use of ODPs associated with salts of Mn, Zn and other metal salts including titanium salts and a chemical oxidizing agent (FR2976793, WO2011/086284, WO2011/086282, and FR2951374). However, the colorations obtained from ODPs are insufficiently powerful, intense and/or are not very tenacious, particularly in the case of hair fibers.

In addition, it is known to use metals at an acid pH for the coloring of keratin fibers using a mordanting process, which consists in preparing the fibers before carrying out the dyeing in order to obtain tenacious colors (Ullmann's Encyclopedia " Metal and Dyes”, 2005 § 5.1, p 8). However, this process generally has the disadvantage of not always respecting the cosmetics of keratin fibres, going so far as to cause hair breakage by the use of pro-fentonic metals (Fe, Cu, etc.).

There is therefore a real need to develop coloring processes from natural dyes having improved dyeing or cosmetic properties in terms of build-up, tenacity and selectivity. More particularly, there is a need to obtain natural colorations which are tenacious and more homogeneous, i.e. having a low selectivity of the coloration between the root and the tip, while remaining powerful and/or chromatic and while respecting the integrity fiber.

This object is achieved by the present invention, the subject of which is a hair coloring process comprising the application to the hair of at least one lanthanide salt and at least one natural dye, applied together or separately.

According to a preferred embodiment, the subject of the invention is a hair dyeing process comprising:
a) a hair treatment step with at least one lanthanide salt;
b) a hair treatment step with at least one natural dye.

A second object of the present invention relates to a multi-compartment device comprising a first compartment comprising at least one lanthanide salt and a second compartment comprising at least one natural colorant. The multi-compartment device or “ kit ” is suitable for implementing the staining method according to the invention.

Another object of the invention is the use of a composition comprising at least one lanthanide salt and at least one natural dye for coloring the hair.

According to a particular embodiment, the hair coloring process according to the invention comprises several steps including a treatment step implemented from a composition comprising at least one lanthanide salt followed by the application of a composition comprising at least one natural colorant.

The method according to the invention has the advantage of coloring human keratin fibres, with powerful and particularly tenacious coloring results while preserving the integrity and cosmetics of the hair, in particular in terms of softness. In particular, the dyeing process according to the invention makes it possible to produce dyes that are resistant to washing, to perspiration, and to light without altering the fibres. In addition, the coloring process implemented makes it possible to induce “ a rise ”, a satisfactory chromaticity and/or intensity (power) of the coloring as well as a lower selectivity.

Other objects, characteristics, aspects and advantages of the present invention will appear even more clearly on reading the description and the examples which follow.

In the description, the term " at least one " is equivalent to one or more.

By “ rise ” in the color of the keratin fibres, is meant within the meaning of the present invention, the variation in coloring between locks of uncolored hair and locks of colored hair.

In the present application, unless otherwise indicated, when we speak of a compound, we also mean its optical isomers, its geometric isomers, its tautomers, its salts or its solvates, alone or as a mixture.

Within the meaning of the present invention and unless a different indication is given:
- The saturated or unsaturated rings, possibly condensed, can also be optionally substituted;
- the radicalsalkyl» are hydrocarbon radicals, saturated, linear or branched, generally C₁-VS₂₀, particularly in C₁-VS₁₀, preferably C-alkyl radicals₁-VS₆, such as methyl, ethyl, propyl, butyl, pentyl and hexyl;
- the radicalsalkenyl» are hydrocarbon radicals, linear or branched, unsaturated at C₂-VS₂₀; preferably comprising at least one double bond such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene;
- the radicalsaryl» are mono or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferably chosen from the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl;
- the radicalsalkoxy» are alkyl-oxy radicals with alkyl as defined above, preferably C₁-VS₁₀, such as methoxy, ethoxy, propoxy and butoxy;
- the radicalsalkoxy alkylare radicals (C₁-VS₂₀)alkoxy(C₁-VS₂₀)alkyl, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
- the radicalscycloalkyl» are C cycloalkyl radicals₄-VS₈, preferably the cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals can be cycloalkyl radicals substituted, in particular by alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups;
- the radicalsalkyl" Or "alkenyl"when they are"optionally substituted», may be substituted by at least one atom or group carried by at least one carbon atom, chosen from: i) halogen; ii) hydroxy; iii) (C₁-VS₂)alkoxy; iv) (C₁-VS₁₀)alkoxycarbonyl; v) (poly)hydroxy(C₂-VS₄)alkoxy; (vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) 5- or 6-membered heteroaryl optionally cationic, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl; ix) amino substituted by one or two alkyl radicals, identical or different, in C₁-VS₆optionally carrying at least: a) one hydroxy group, b) one amino group optionally substituted by one or two radicals (C₁-VS₃) optionally substituted alkyl, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen , c) a quaternary ammonium group -N⁺R'R''R''',M ^- for whichR',R'',R''', identical or different represent a hydrogen atom, or a C alkyl group₁-VS₄; AndM ^- represents the counter-ion of the corresponding organic or mineral acid or halide, d) or a 5- or 6-membered heteroaryl radical, optionally cationic, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl; x) acylamino (-N(R)-C(O)-R’) in which the radicalRis a hydrogen atom, a radical (C₁-VS₄)alkyl optionally carrying at least one hydroxy group and the radicalR'is a C alkyl radical₁-VS₂; a carbamoyl radical ((R)₂N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a radical (C₁-VS₄) alkyl optionally carrying at least one hydroxy group; xi) alkylsulfonylamino (R'-S(O)₂-N(R)-) in which the radicalRrepresents a hydrogen atom, a radical (C₁-VS₄)alkyl optionally carrying at least one hydroxy group and the radicalR'represents a radical (C₁-VS₄)alkyl, a phenyl radical; xii) aminosulfonyl ((R)₂N-S(O)₂-) in which the radicalsR, identical or not, represent a hydrogen atom, a radical (C₁-VS₄) alkyl optionally carrying at least one group chosen from a) hydroxy, b) carboxy –C(O)-OH in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); xiii) cyano; (xiv) nitro; xv) carboxy or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted by one or more hydroxy groups; xvii) glycosyloxy; and phenyl group optionally substituted by one or more hydroxy groups;
- the radicalsaryl" Or "heterocyclic» or the aryl or heterocyclic part of the radicals when they are « optionally substituted » can be substituted by at least one atom or group carried by at least one carbon atom, chosen from: (C₁-VS₁₀)alkyl, preferably C₁-VS₈, optionally substituted by one or more radicals chosen from hydroxy radicals, (C₁-VS₂)alkoxy, (poly)-hydroxyalkoxy C₂-VS₄, acylamino, amino substituted by two alkyl radicals, identical or different, in C₁-VS₄, optionally carrying at least one hydroxy group or, the two radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably from 5 or 6 members, optionally saturated or unsaturated substituted optionally comprising another heteroatom identical to or different from nitrogen; ii) halogen; iii) hydroxy; iv) C-alkoxy₁-VS₂; v) C-alkoxycarbonyl₁-VS₁₀; (vi) C-(poly)hydroxyalkoxy₂-VS₄; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix) 5- or 6-membered heteroaryl optionally cationic, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl; x) amino substituted by one or two identical or different C-C alkyl radicals₁-VS₆optionally carrying at least: a) one hydroxy group, b) amino optionally substituted by one or two C-alkyl radicals₁-VS₃optionally substituted, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen, c ) a quaternary ammonium group -N⁺R'R''R''', M^-for which R', R'', R''', which are identical or different, represent a hydrogen atom, or a C alkyl group₁-VS₄; and M^-represents the counter-ion of the corresponding organic or mineral acid or halide, d) a 5- or 6-membered heteroaryl radical, optionally cationic, preferably imidazolium, and optionally substituted by a radical (C₁-VS₄) alkyl, preferably methyl; xi) acylamino (-N(R)-C(O)-R') in which the R radical is a hydrogen atom, a C₁-VS₄optionally carrying at least one hydroxy group and the radical R' is a C alkyl radical₁-VS₂; xii) carbamoyl ((R)₂N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in C₁-VS₄optionally carrying at least one hydroxy group; xiii) alkylsulfonylamino (R’S(O)₂-N(R)-) in which the radical R represents a hydrogen atom, an alkyl radical in C₁-VS₄optionally carrying at least one hydroxy group and the radical R' represents a C alkyl radical₁-VS₄, a phenyl radical; xiv) aminosulfonyl ((R)₂N-S(O)₂-) in which the radicalsR, identical or not, represent a hydrogen atom, an alkyl radical in C₁-VS₄optionally carrying at least one hydroxy, xv) carboxy group in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferably trifluoromethyl; xix) a glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted by one or more hydroxy groups; xxi) a glycosyloxy group; and xxii) a phenyl group optionally substituted by one or more hydroxy groups;
- by radical "glycosyl», is meant within the meaning of the present invention a radical resulting from a mono or polysaccharide;
- the radicalscontaining one or more silicon atomsare preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane, stearoxy-dimethicone radicals;
- the radicalsheterocyclicare radicals comprising in at least one cycle one or more heteroatoms particularly chosen from O, N and S, preferably O or N, optionally substituted with in particular one or more alkyl, alkoxy, carboxy, hydroxy, amine or ketone groups. These rings can contain one or more oxo groups on the carbon atoms of the heterocycle; among the heterocyclic radicals that can be used, mention may in particular be made of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, thienyl groups; even more preferentially, the heterocyclic groups are condensed groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl groups, these groups possibly being substituted, in particular by one or more OH groups.

Lanthanide salt

The hair coloring process according to the invention uses at least one lanthanide salt.

The lanthanide salts are preferably soluble in water at a concentration greater than or equal to 0.1% by weight in water at 25° C., that is to say that they form, under these conditions, a solution isotropic transparent to the eye.

They preferably have a molecular weight of less than 5000 g/mol, even more preferably less than 2500 g/mol, even more preferably less than 500 g/mol.

Lanthanides are transition metals located between the elements of atomic numbers 57 (La) to 71 (Lu) inclusive.

The lanthanide salts are chosen from lanthanum salts, europium salts, gadolinium salts, ytterbium salts, erbium salts, cerium salts and mixtures thereof and more particularly the lanthanide salts are chosen from lanthanum salts, cerium salts and mixtures thereof, better still from lanthanum salts and mixtures thereof.

The lanthanide salts can be chosen from inorganic lanthanide salts or organic lanthanide salts.

Mention may be made, among the inorganic lanthanide salts, of the halides, in particular the chlorides, the sulphates, the nitrates, the carbonates, the phosphates and the lanthanide triflates.

Among the organic salts of lanthanides, mention may be made of lanthanide lactates and lanthanide citrates.

The lanthanum salts useful according to the invention can be chosen from lanthanum chloride, lanthanum triflate, lanthanum sulphate, lanthanum nitrate, lanthanum lactate, lanthanum citrate and mixtures thereof.

The lanthanum salts are preferably chosen from inorganic lanthanum salts, in particular lanthanum halides, more preferably lanthanum chloride.

According to one embodiment, the lanthanide salt(s) as defined above are applied from a composition containing the lanthanide salt(s) in a total content ranging from 0.01% to 20% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 10% by weight, better still from 0.5 to 8% by weight relative to the total weight of the composition containing them.

According to a preferred embodiment of the invention, the composition(s) used in step a) is or are aqueous. According to this embodiment, the pH of this (these) compositions is acidic, ie strictly less than 7.0. Preferably, the pH of this (these) compositions is between 2.5 and 6.9, better still 4 and 6.9.

The pH of these compositions can be adjusted to the desired value by means of acidic or alkaline agent(s) usually used in dyeing keratin fibers or even by means of known buffer systems. of the skilled person. In particular, citric lactic acid, an alkaline agent such as arginine, can be used.

natural dye

The hair coloring process according to the invention uses at least one natural dye.

In the context of the invention, the term " natural dye“, any dye or dye precursor from a natural source, in particular of plant origin. Natural dyes can in particular be obtained by extraction (and possibly purification) from a plant matrix, by grinding plants or parts of plants, roots, wood, bark, berries, lichens, leaves, flowers, nuts or seeds. Natural dyes can also be obtained by fermentation.

The natural dyes may in particular be chosen from lawsone, juglone, indigo, indirubine, isatin, hennotannic acid, alizarin, carthamine, morine, purpurine, carminic acid, kermesic acid, laccaic acid, purpurogalline, protocatechaldehyde, curcumin, spinulosin, apigenidin, orceins, carotenoids, betanin, chlorophylls, chlorophyllins, monascus, polyphenols or ortho-diphenols (also called ODPs in the remainder of the description) and all extracts rich in ODPs, or mixtures thereof.

According to a first embodiment of the invention, the useful natural dyes are chosen from ODPs.

By “ ODP(s) ” is meant compounds comprising one or more aromatic rings, at least one of which is a benzene ring substituted by at least two hydroxy (OH) groups carried by two adjacent carbon atoms.

The aromatic ring is more particularly a condensed aryl or condensed heteroaromatic ring i.e. optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indan, indene, anthracene, phenanthrene, indole , isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline; said aromatic ring comprising at least two hydroxy groups carried by two adjacent carbon atoms of the aromatic ring. Preferably, the aromatic ring of the orthodiphenol derivatives according to the invention is a benzene ring.

Preferably, the aromatic ring of the orthodiphenol derivatives according to the invention is a benzene ring.

By “ condensed ring ”, it is meant that at least two saturated or unsaturated rings, heterocyclic or not, have a common bond, that is to say that at least one ring is attached to another ring.

More particularly, the ODPs useful according to the invention are of formula (II) , or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or its solvates such as the hydrates:

in which :
R ¹ to R ⁴ , which are identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxy, iv) carboxy, v) (C ₁ -C ₂₀ ) carboxylate alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted (C ₁ -C ₂₀ )linear or branched alkyl, viii) optionally substituted (C ₂ -C ₂₀ )linear or branched alkenyl, ix ) optionally substituted cycloalkyl, x) (C ₁ -C ₂₀ )alkoxy, xi) (C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl, xii) (C ₁ -C ₂₀ )alkoxyaryl, xiii) aryl which may be optionally substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic, saturated or not, bearing or not a cationic or anionic charge, optionally substituted and/or optionally condensed with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted particularly by one or more hydroxy or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
or two of the substituents carried by two adjacent carbon atoms R ¹ - R ² , R ² - R ³ or R ³ - R ⁴ together with the carbon atoms carrying them form a saturated or unsaturated ring, aromatic or not, optionally containing a or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. Particularly, the compound of formula (II) comprises from one to four rings.

According to a particular embodiment, the ODPs correspond to ODP(s) of formula (II) of which two adjacent substituents R ¹ - R ² , R ² - R ³ or R ³ - R ⁴ can form with the carbon atoms which them carry 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 hydroxys.

As examples of ODPs useful according to the invention, mention may be made, it being understood that each of the following structures comprises at least two hydroxy groups in the ortho position:
- quinones such as naphthoquinones and anthraquinones, in particular dihydroxy and trihydroxyanthraquinone,
- neoflavonoids (4-phenylbenzopyrans), such as neoflavonols or neoflavonones,
- flavonoids (2-phenylbenzopyrans), such as flavans, flavonols, flavanols, flavones, dihydroflavonols or dihydroxyflavanonols, flavanones, flavan-3,4-diols, anthocyanidins,
- isoflavonoids (3-phenylbenzopyrans),
- hydroxybenzoates, for example salts of gallic acid,
- hydroxystilbenes, for example tetrahydroxy-3,3',4,5'-stilbene, optionally oxylated (for example glucosylated),
- dihydroxy- and trihydroxyphenylalanine,
- dihydroxycinnamic acids or their salts (dihydroxycinnamates), such as caffeic acid and chlorogenic acid,
- (iso)coumarins,
- (iso)coumarones,
- chalcones,
- the chromones,
- xanthones,
- dihydroxy- and trihydroxybenzene,
- tannic acid,
- gallic acid
- ellagic acid,
- and mixtures of the preceding compounds.

According to a particular embodiment of the invention, the ODPs of the invention are chosen from anthraquinone dyes and the extracts containing them. Examples include: 1,2-dihydroxyanthraquinone (alizarin), 1,2,3-trihydroxyanthraquinone (anthragallol) and 1,2,4-trihydroxyanthraquinone (purpurin, veratin , Smoke Brown G , CI 1037 , CI 58205 , CI 75410 , CI Natural Red 16 , CI Natural Red 8).

According to a preferred embodiment of the invention, the ODPs useful according to the invention are chosen from compounds belonging to the family of flavonoids. By compounds of the flavonoid family is meant: flavonoids (2-phenylbenzopyrans), isoflavonoids (3-phenylbenzopyrans) and neoflavonoids (4-phenylbenzopyrans).

According to this embodiment, the ODPs useful according to the invention can be chosen from neoflavonoids and more particularly from neoflavanols, neoflavanones or mixtures thereof.

Among the neoflavonoids, mention may be made of hematoxylin, hematein, brazilin and brazilein and their mixtures. Among the dyes of the invention of hematoxylin/hematein and braziline/brazilein type, mention may be made by way of example of hematoxylin (Natural Black 1 according to the INCI name) and braziline (Natural Red 24 according to the INCI name), dyes of the indochromane family, which are commercially available. The latter can exist in an oxidized form and be obtained synthetically or by extraction from plants or vegetables known to be rich in these dyes. These ODPs can be used in the form of extracts. The following plant extracts can be used: Haematoxylon campechianum, Hematoxylum braziletto, Schinopsis lorentsii, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extracting various parts of plants, such as for example the root, the wood, the bark or the leaf. According to a particular embodiment of the invention, these ODPs are derived from logwood, pernambuco wood, sappan wood and brazilwood.
Among the neoflavonoid compounds, mention may also be made of: Santaline A and B, Santarubine A, B and C, tetra-O-methylcantarubine. These ODPs can be used in the form of extracts. It is possible to use plant extracts of redwoods, generally grouping together the species of Asian and West African redwoods 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 even Baphia nitida. These woods can still be called padauk, sandalwood (Sandalwood), narrawood, camwood or even barwood. Thus, usable extracts can for example be obtained from red sandalwood (Pterocarpus santalinus), by aqueous basic extraction, such as the product sold under the trade name Santal Concentré SL 709C by the company COPIAA or by means of a 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 hydroalcoholic extract of powdered red sandalwood from the company ALBAN MULLER. Extracts also suitable for the present invention can be obtained from wood such as Camwood (Baphia nitida) or even Barwood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus fractionated and then ground: a conventional alcoholic extraction or by percolation is then carried out on this ground material in order to collect a powdery extract particularly suitable for the implementation of the present invention.

According to a particular embodiment of the invention, the ODPs useful according to the invention are chosen from 2-phenylbenzopyrans or mixtures thereof. The 2-phenylbenzopyrans useful according to the invention are chosen from: flavans, flavonols, flavanols, flavones, dihydroflavonols or dihydroxyflavanonols, flavanones, flavan-3,4-diols, anthocyanidins.

By way of example we can cite:
- flavanols such as catechin, pine bark extract, epichatechin gallate, and cocoa flavanols, in particular epichatechin, green tea flavan-3-ol, and their oligomers and polymers called proanthocyanidols or condensed tannins such as theaflavin, theaflavin 3'-O-gallate, theaflavin 3,3'-O-digallate, proanthocyanidins A1, A2, B1, B2, B3 and C1 such as profisetinidin and procyanidin. ;
- flavonols such as quercetin, luteolin, myricetol, fisetin, rhamnetin;
- flavones such as luteolin, their glycosides such as luteolol 7-O-glucoside, baicalin, orientin:
- dihydroflavonols or dihydroxyflavanonols such as dihydroquercetol, their glycosides such as dihydroquercetol 3-O-rhamoside;
- flavanones such as eriodictyol;
- flavan-3,4-diols or leucoanthocyanidins such as leucocyanidol or procyanidol);
- anthocyanidins (or anthocyanides, or anthocyanidins) such as cyanidol (or cyanidin), delphinidin, aurantinidin, luteolinidin, their heterosides such as dihydroxyanthocyanins (or dihydroxyanthocyanosides, or anthocyanins on the English model), their oligomers and polymers such as proanthocyanins, preferably anthocyanidins and in particular blueberry.

In particular, the ODPs useful according to the invention are chosen from: catechin, quercetin, brazilin, hematein, hematoxylin, chlorogenic acid, caffeic acid, gallic acid, L DOPA, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (- )-Epigallocatechin 3-gallate (EGCG), Isoquercetin, Pomiferin, Aesculetin, 6,7-Dihydroxy-3-(3-hydroxy-2,4-dimethoxyphenyl)coumarin, Santalin A and B, Mangiferin, Butein, Maritimetin, Sulfuretin, Robteine, Betanidin, Pericampylinone A., Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, Proanthocyanidin C1, Procyanidins DP 4-8, Tannic Acid, Purpurogalline, 5,6-Dihydroxy-2-methyl-1,4-naphthoquinone, Alizarin, Wedelolactone and the natural extracts containing them.

According to a preferred embodiment, the ODPs useful according to the invention are chosen from the neoflavonoids of formula (III) below, as well as its tautomeric and/or mesomeric forms, its stereoisomers, its addition salts with an acid or a base cosmetically acceptable, and its solvates such as hydrates:

in which :
- represents a carbon-carbon single bond or a carbon-carbon double bond, the sequence of these bonds denotes two carbon-carbon single bonds and two carbon-carbon double bonds, said bonds being conjugated,
- X represents a group:

- R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , identical or different, represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted acyloxy group .

The alkyl radicals cited in the previous definitions of the substituents are hydrocarbon radicals, saturated, linear or branched, generally C ₁ -C ₁₀ , preferably C ₁ -C ₆ , such as methyl, ethyl, propyl, butyl, pentyl and hexyl.

The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined previously, and the alkoxy radicals are preferably C ₁ -C ₆ radicals, such as methoxy, ethoxy, propoxy and butoxy.

Preferably, the ODP(s) of formula (III) are chosen from hematein, hematoxylin, brasilein, brasilin:

According to one embodiment, the ODPs useful according to the invention are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in their entirety or partially. In particular concerning plants, the extracts come from fruits including citrus fruits, vegetables, trees, shrubs.

Preferably, the ODPs useful according to the invention are derived from extracts of plants or parts of plants.

The extracts are obtained by extracting various parts of plants such as for example the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod, the peel.

Among the plant extracts, mention may be made of extracts of tea leaves, in particular of Japanese green tea, of rose.

Among the fruit extracts, mention may be made of apple, grape (in particular grape seed) extracts, or extracts of cocoa beans and/or pods.

Among the vegetable extracts, we can mention the extracts of potato, onion peels.

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

Dyes can be present in powder, ground or extract form.

Preferably, the ODP(s) useful according to the invention is (are) chosen from hematein, hematoxylin, brasilin, brasilein, the natural extracts containing them chosen from Haematoxylon campechianum, Hematoxylum braziletto, Schinopsis lorentsii, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis, logwood, pernambuco wood, sappanwood, brazilwood and mixtures thereof.

According to a second embodiment of the invention, the useful natural dyes are chosen from extracts, decoctions or ground materials obtained, for example, from pernambuco wood, logwood, sandalwood, sorrel, turmeric, madder, indigo plants such as indigo, plants of the 'isatis' genus such as isatis tinctoria , sorghum, carrots, annatto, brazilwood, safflower, henna and mixtures thereof.

In particular, the natural dyes can be chosen from the powder and/or an extract of indigo-bearing plant(s). (By “indigoferous plant extract” is meant within the meaning of the present invention a “coloring extract of indigoferous plant”).

As an indigo plant, we can cite many species from the genera:
- Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata Indigofera arrecta, Indigofera gerardiana, Indigofera argenta, Indigofera indica, Indigofera longiracemosa ;
- Isatis such as Isatis tinctoria;
- Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria) ;
- Wrightia such as Wrightia tinctoria ;
- Calanthe such as Calanthe veratrifolia; And
- Baphicacanthus such as Baphicacanthus cusia.

Preferably the indigo-bearing plant is of the genus Indigofera and more particularly is Indigofera tinctoria, Suffructicosa or argentea, preferably Indigofera tinctoria .

It is possible to use all or part (in particular the leaves, in particular for Indigofera tinctoria ) of the indigo-bearing plant.

The natural dyes useful according to the invention can be henna.

According to the present invention, “henna” means a henna plant powder and/or a coloring extract of a henna plant, preferably of a henna plant such as Lawsonia alba or Lawsonia inermis . The henna plant coloring powder and/or extract comprises in particular lawsone and/or one of its glucosylated precursors.

Preferably, the henna used according to the present invention is in powder form.

Preferably, the henna used in the invention is red henna ( Lawsonia inermis, alba ). Lawsone [83-72-7] (CI Natural Orange 6; CI 75420) also known as isojuglone, can be found in Henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably the henna is in powder form.

According to a preferred embodiment, the natural dyes useful according to the invention are chosen from ODPs as defined above, lawsone, henna extracts and/or powders, indigo, indigo plant extracts and/or powders , isatin and mixtures thereof.

According to this embodiment, the natural dyes useful according to the invention are chosen from hematein, hematoxylin, brasilin, brasiléin, the natural extracts containing them chosen from Haematoxylon campechianum, Hematoxylum braziletto, Schinopsis lorentsii, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis, logwood, pernambuco wood, sappanwood and brazilwood, lawsone, henna extracts and/or powders, indigo, extracts and/or or indigo plant powders, isatin and mixtures thereof.

The natural dyes as defined above are applied from a composition containing the natural dyes, preferably in a total content ranging from 0.05% to 50% by weight relative to the total weight of the composition in which they are find, preferably from 0.1 to 40% by weight, better still from 0.5 to 30% by weight relative to the total weight of the composition containing them .

According to one embodiment, the composition applied in step b) can be obtained by mixing at least 2 compositions, at least one comprising at least one natural dye.

According to this embodiment, the composition useful in step b) may comprise the natural dye(s) in a total content ranging from 0.5 to 100% by weight, preferably from 3 to 100% by weight, better still, from 10 to 100% by weight relative to the total weight of this composition.

According to a preferred embodiment of the invention, the composition used in step b) is aqueous and has a pH greater than or equal to 4, in particular, this pH is inclusively between 5 and 11, preferably between 6 and 10.

The pH of these compositions can be adjusted to the desired value by means of acidic or alkaline agent(s) usually used in dyeing keratin fibers or even by means of known buffer systems. of the skilled person. It is possible, in particular, to use lactic acid, citric acid, an alkaline agent such as arginine.

(Poly)saccharides

The method according to the invention can implement at least one (poly)saccharide.

The (poly)saccharide(s) can be applied in step (a) and/or (b) . Preferably, these (poly)saccharides are applied in step b) .

The saccharides can be chosen from mono, oligo or polysaccharides.

In particular, the saccharides or reduced saccharides useful in the process of the invention are solid, ie they are not liquids or syrups at ambient temperature (25° C.) and at atmospheric pressure (1.013×10 ⁵ Pa).

By “ monosaccharide ” is meant a sugar comprising only a single unit, ie not comprising a glycosidic covalent bond with another sugar.

Preferably, the "monosaccharides" useful in the process according to the invention are chosen from:
• " aldoses " or polyhydroxyaldehydes, preferably comprising between 4 and 6 carbon atoms such as erythose or threose (4 carbon atoms), ribose, arabinose, xylose or lyxose (5 carbon atoms) , allose, altrose, glucose, mannose, gulose, idose, galactose and talose (6 carbon atoms);
• " ketoses " or polyhydroxyketones preferably comprising between 4 and 6 carbon atoms such as erythrulose (4 carbon atoms), ribulose or xylulose (5 carbon atoms), psicose, fructose, sorbose and tagatose (6 carbon atoms); And
• the reduced forms of aldoses and ketoses as defined above are also called “sugar alcohols” or “alditols”. They are in particular chosen from erythritol, glucitol or sorbitol, mannitol and xylitol, preferably sorbitol.

By “ sugar alcohol ” is meant “ polyols ” generally obtained by reduction of aldose or ketose monosaccharides as defined above or of oligo or polysaccharide complexes as defined below in which the aldehyde or ketone group(s) of the monosaccharide units are reduced ie replaced by a hydroxy group.

Preferably, the sugars useful according to the invention and in particular the sugar alcohols are of plant origin.

It is understood that by aldoses, ketoses and sugar alcohols is also meant their optical isomers, their anomers and their L (levorotatory) and D (dextrorotatory) forms.

More preferably, the monosaccharides useful according to the invention contain 6 carbon atoms.

By “ oligosaccharide ” is meant a sugar in which the monosaccharides as defined above are joined together by a covalent glycosidic bond to lead to a simple polymer comprising from 2 to 10 monosaccharide units.

In particular, the oligosaccharides are chosen from disaccharides such as sucrose, trehalose and raffinose, lactose, cellobiose and maltose; cyclodextrins, and their reduced forms such as isomaltulose, trehalulose, isomalt, maltitol, and lactitol,

It is understood that by oligosaccharides is also meant their optical isomers, their anomers and their L (levorotatory) and D (dextrorotatory) forms.

By " polysaccharides " is meant oligosaccharides which have at least 11 monosaccharide units. Preferably, the polysaccharides of the invention comprise between 20 and 100,000 monosaccharide units.

The polysaccharides useful according to the invention can be chosen from those derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulphate; anhydrogalactose sulphate.

The polymers with sugar units of the invention can be natural or synthetic.

They can be non-ionic, anionic, amphoteric or cationic.

According to a particular embodiment, the saccharides useful according to the invention are chosen from native gums such as:
• 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); tragacanth (or tragacanth) gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
• gums from algae such as: agar (polymer from galactose and anhydrogalactose); alginates (polymers of mannuronic acid and glucuronic acid); carrageenans and furcellerans (polymers of galactose sulphate and anhydrogalactose sulphate);
• gums from seeds or tubers such as: 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);
• plant extracts such as: cellulose (polymer of glucose); and starch (polymer of glucose);
• microbial gums such as: xanthan gums (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid); gellan gums (polymer of partially acylated glucose, rhamnose and glucuronic acid); scleroglucan gums (polymer of glucose); pullulan gums, curdlar gums, grifolan gums, lentinan gums, schizophyllan gums, spirulinan gums and krestin gums.

Within the meaning of the present invention, the term " microbial gums " means substances synthesized by fermentation of sugars by microorganisms.

According to a preferred embodiment, the polysaccharides useful according to the invention are chosen from gums, better still, from microbial gums. Preferably, xanthan gums, scleroglucan gums, or mixtures thereof are used.

Preferably, the polysaccharides as described above are implemented from a composition comprising at least one metal salt.

The (poly)saccharides as defined above are preferably applied from a composition containing the (poly)saccharide(s) in a total content ranging from 0.01% to 10% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 8% by weight, better still from 0.3 to 5% by weight relative to the total weight of the composition containing them .

Solvents

The method according to the invention can be implemented from one or more composition(s) comprising the ingredients as described above and which may also contain one or more solvent(s), chosen from water and organic solvents.

The compositions used in the process according to the invention may contain a mixture of organic solvents or a mixture of water and one or more organic solvents.

By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.

The organic solvent(s) useful in the compositions of the invention is or are chosen from C ₁ -C ₄ lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol (1,2-propanediol), propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. Preferably, the organic solvents useful in the compositions of the invention are chosen from lower C ₁ -C ₄ alkanols; polyols and polyol ethers, aromatic alcohols and mixtures thereof, preferably chosen from: diols such as: butane-1,4-diol, butane-1,2-diol, butane-1,3-diol, butane- 2,3-diol, propane-1,2-diol (propylene glycol), pentane-1,2-diol, pentane-1,5-diol, pentane-2,4-diol, pentane-1,3-diol, hexane-1,6-diol, hexane-1,2-diol, hexane-2,5-diol, 2-methyl-2,4-pentanediol (hexylene glycol), diethylene glycol, dipropylene glycol, triethylene glycol; triols such as: hexane-1,2,6-triol, glycerol; tetraols such as erythriol; pantanols such as: lyxitol, xylitol, ribitol; hexols such as: sorbitol, mannitol; benzyl alcohol; phenoxyethanol; ethanol and mixtures thereof.

More preferably, the organic solvent(s) useful in the compositions of the invention is or are chosen from ethanol, benzyl alcohol, 1,2-pentanediol, sorbitol and their mixtures, even more preferably ethanol, benzyl alcohol and mixtures thereof.

Preferably, the composition comprising at least one lanthanide salt and/or the composition comprising at least one natural dye is (are) aqueous.

When present, the water is applied from a composition containing water in a content ranging from 10% to 99% by weight, preferably from 20 to 99% by weight, better still from 30 to 99 %, or even from 70 to 99% by weight relative to the total weight of the composition .

When present, the organic solvents as defined above are present in the composition(s), preferably in a total content ranging from 0.01% to 30% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 25% by weight, better still from 1 to 20% by weight relative to the total weight of the composition containing them .

According to a preferred embodiment, the subject of the invention is a hair dyeing process comprising:
a) a hair treatment step with at least one lanthanide salt, preferably with at least one lanthanum salt, more preferably with at least one lanthanum halide, better still with at least one lanthanum chloride;
b) a hair treatment step with at least one natural dye.

According to a more preferred embodiment, the subject of the invention is a hair dyeing process comprising:
a) a hair treatment step with at least one lanthanide salt, preferably with at least one lanthanum salt, more preferably with at least one lanthanum halide, better still with at least one lanthanum chloride;
b) a hair treatment step with at least one natural dye, at least one polysaccharide and at least one organic solvent.

Plants of the Cassia family

The process according to the invention can, in addition, implement in steps a) and/or b) , preferably, in step b) , plants of the Cassia family, in particular chosen from Cassia Angustifolia (senna ), or Cassia Auriculata or Cassia Italica, or mixtures thereof. Preferably, the method according to the invention uses a powder or a plant extract from the Cassia family, in particular from Cassia Angustifolia and/or Cassia Auriculata and/or Cassia Italica, preferably from Cassia Angustifolia.

Additive(s)

The compositions implemented by the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as surfactants, polymers other than polysaccharides as described above, thickening agents other than polysaccharides as described above, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives, opacifying agents.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties inherently attached to the composition or to the composition(s) useful in the treatment method in accordance with the invention are not not, or substantially not, altered by the contemplated addition(s).

The compositions used according to the process according to the invention may be in various galenic forms, such as a powder, a lotion, a foam, a cream, a gel or in any other form suitable for dyeing fibers keratins. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam.

Multi-step coloring process

According to one embodiment, the hair dyeing method according to the invention implements sequentially either step a) then step b) ; or step b) then step a).

According to a preferred embodiment, the hair dyeing process according to the invention implements step a) then step b) sequentially.

According to one embodiment, step b) can be implemented by a composition resulting from the mixture of a composition comprising at least one natural dye and of a composition comprising at least one (poly)saccharide and at least one solvent organic as previously described.

The method according to the invention may involve an exposure time for the composition of step a) and/or b) . According to a particular embodiment, the exposure time, on the hair, of the compositions useful according to steps a) and b) of the hair coloring process according to the invention, is between 1 minute and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 10 minutes and 45 minutes. The process according to the invention is implemented at a temperature generally comprised between 20°C and 80°C, preferably a temperature comprised between 25°C and 50°C.

According to one embodiment, the hair coloring method according to the invention implements between steps a) and b) an intermediate rinsing step.

More particularly, the method according to the invention implements step a) then an intermediate rinsing step, then step b) .

Step b) can be followed by one or more washing steps, followed by one or more rinsing of the hair with water and optionally followed by drying by heat treatment by heating to a temperature between 30° C and 90°C. It is also possible to use, both as means for heating and for straightening the hair, an iron heated to a temperature of between 100° C. and 220° C. and preferably between 120° C. and 200° C.

More particularly, the method according to the invention implements step a) then an intermediate rinsing step, then step b) , then a rinsing step, then a washing step.

In a variant of the process of the invention, composition C comprising at least one natural colorant applied in step b) is obtained from the extemporaneous mixing at the time of use of a composition C1 comprising at least one natural colorant with a composition C2 preferably aqueous.

In another variant of the process of the invention, composition C comprising at least one natural colorant applied in step b) is obtained from the extemporaneous mixing at the time of use of a composition C1 comprising at least one natural colorant with a composition C2 comprising at least one (poly)saccharide and at least one organic solvent.

Device or “kit”

Another object of the invention is a multi-compartment device or “kit” for hair treatment comprising at least 2 compartments.

According to a first variant, the multi-compartment device comprises at least one compartment comprising at least one lanthanide salt and a second compartment comprising at least one natural dye.

According to the second variant, the multi-compartment device comprises at least one compartment comprising a composition comprising at least one lanthanide salt, a second compartment comprising a composition comprising at least one natural dye and a third compartment comprising at least one (poly)saccharide and at least one organic solvent.

According to a variant, the device according to the invention further comprises an additional composition comprising one or more treatment agents.

The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by appropriate means of application, which are identical or different, such as paintbrushes, brushes or sponges.

The device mentioned above can also be equipped with a means making it possible to deliver the desired mixture to the hair, for example such as the devices described in patent FR 2586913.

Examples

Preparation of the compositions and application to keratin fibers

The following compositions were prepared in the proportions indicated in grams of active material per 100 g of composition, unless otherwise indicated:

▬Formulations A1 and A2

A1 (invention) A2 (comparative) Lanthanum(III) chloride 5 - Dihydroxybis(ammonium lactato) titanium(IV) - 5 90% lactic acid by weight in water - 8
(raw material) Water Qsp 100 Qsp 100 pH 6.8 2.4

▬C1 Compositions

C1 (invention) Extract of logwood oxide (hematoxylon campechianum) (HEMATEIN marketed by ICHIMARU PHARCOS) 40 Starch Qsp 100

▬Composition C2

C2 Benzyl alcohol 2 Denatured Absolute Ethyl Alcohol 8 scleroglucan gum 1.3 xanthan gum 0.7 Water Qsp 100

Compositions A 1 (invention) and A2 (comparison) were applied to locks of permed Caucasian hair with 90% white hair (BP) at a rate of 4 g of composition per gram of hair, and left on for 15 minutes at 30° under occlusion then rinsed with water.

Then, to the resulting locks, composition C resulting from the mixture of composition C1 and of composition C2 is applied in a C1:C2 ratio of 1:10. 4 g of this mixture are used per 1 g of locks. The mixture is left on for 30 minutes at 30° C. under occlusion, then rinsed and the locks are shampooed. The locks are then dried.

It was observed visually that the locks treated by the process of the invention (compositions A1 then C ) exhibit a more intense coloration than those treated by the comparative process (compositions A2 then C ).

Color assessment

These observations were supplemented with the colorimetric measurements below for the locks treated by the process without pretreatment (comparative), by the processA1ThenVS(invention) and by the processA2ThenVS(comparative).

The coloring of the hair is evaluated in the L*a*b* system, with a Minolta CM3600D spectro-colorimeter (illuminant D65, angle 10°, specular component included).

In this system, L* stands for clarity. The lower the value of L*, the darker and more powerful the color obtained. Chromaticity is measured by the a* and b* values, where a* represents the red/green axis and b* represents the yellow/blue axis.

The rise in color is represented by the color difference ΔE between the uncolored lock and the colored lock: the higher the value of ΔE, the greater the rise in color. This value is calculated from the following equation (i):

In equation (i), L*, a* and b* represent the values measured on locks of uncolored hair, and L ₀ *, a ₀ * and b ₀ * represent the values measured on locks of colored hair .

Colorimetric values and color rise ΔE are listed in the table below:

Process I* To* b* ΔE before coloring 64.3 1.7 16.0 - process C (comparative) 38.4 22.6 24.8 34.4 process A1 then C (invention) 23.0 5.1 1.8 43.8 process A2 then C (comparative) 27.2 2.7 1.8 39.7

It is found that the fibers treated by the process A1 then C according to the invention have a better rise in color (higher ∆E* value) and a more intense color (lower L* value) compared to the locks treated with composition C or by process A2 then C not using lanthanide salts.

Claims (14)

Hair coloring process comprising the application to the hair of at least one lanthanide salt and at least one natural dye, applied together or separately. Hair coloring process according to the preceding claim comprising:
a) a hair treatment step with at least one lanthanide salt;
b) a hair treatment step with at least one natural dye. Process for coloring the hair according to any one of the preceding claims, in which the lanthanide salts are chosen from lanthanum salts, europium salts, gadolinium salts, ytterbium salts, salts of erbium salts, cerium salts and mixtures thereof and more particularly lanthanide salts are chosen from lanthanum salts, cerium salts and mixtures thereof, better still from lanthanum salts and mixtures thereof. Process for coloring hair according to any one of the preceding claims, in which the lanthanide salts are chosen from lanthanum chloride, lanthanum triflate, lanthanum sulphate, lanthanum nitrate, lanthanum lactate, lanthanum citrate and mixtures thereof. Hair dyeing process according to any one of the preceding claims, in which the lanthanide salts are applied from a composition containing the lanthanide salt(s) in a total content ranging from 0.01% to 20% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 10% by weight, better still from 0.5 to 8% by weight relative to the total weight of the composition containing them. Hair dyeing process according to any one of the preceding claims, in which the natural dye(s) is(are) chosen from ODPs, lawsone, extracts and/or powders of henna, indigo, indigo plant extracts and/or powders, isatin and mixtures thereof. Hair dyeing process according to the preceding claim, in which the ODP(s) is (are) chosen from the ODPs of formula (II) , or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or solvates such as hydrates:

in which :
R ¹ to R ⁴ , which are identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxy, iv) carboxy, v) (C ₁ -C ₂₀ ) carboxylate alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted (C ₁ -C ₂₀ )linear or branched alkyl, viii) optionally substituted (C ₂ -C ₂₀ )linear or branched alkenyl, ix ) optionally substituted cycloalkyl, x) (C ₁ -C ₂₀ )alkoxy, xi) (C ₁ -C ₂₀ )alkoxy(C ₁ -C ₂₀ )alkyl, xii) (C ₁ -C ₂₀ )alkoxyaryl, xiii) aryl which may be optionally substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic, saturated or not, bearing or not a cationic or anionic charge, optionally substituted and/or optionally condensed with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted particularly by one or more hydroxy or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
or two of the substituents carried by two adjacent carbon atoms R ¹ - R ² , R ² - R ³ or R ³ - R ⁴ together with the carbon atoms carrying them form a saturated or unsaturated ring, aromatic or not, optionally containing a or more heteroatoms and optionally condensed 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, more particularly, R ² and R ³ form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring carrying the two hydroxy. Process for dyeing the hair according to any one of the preceding claims 6 or 7, in which the ODP(s) are chosen from hematein, hematoxylin, brasilin, brasilein, the natural extracts containing them chosen from Haematoxylon campechianum , Hematoxylum braziletto, Schinopsis lorentsii, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis, logwood, pernambuco wood, sappanwood, brazilwood and mixtures thereof. Process for coloring the hair according to any one of the preceding claims, in which the natural dyes are applied from a composition containing the natural dyes in a total content ranging from 0.05% to 50% by weight with respect to the total weight of the composition in which they are found, preferably from 0.1 to 40% by weight, better still from 0.5 to 30% by weight relative to the total weight of the composition containing them . Process for dyeing the hair according to any one of the preceding claims, in which at least (poly)saccharide is used, preferably chosen from gums, better still from microbial gums and preferably gums xanthan, scleroglucan gums or mixtures thereof. Hair dyeing process according to any one of the preceding claims, in which at least one organic solvent is used, preferably chosen from among C ₁ -C ₄ lower alkanols; polyols and polyol ethers; aromatic alcohols and mixtures thereof, preferably chosen from diols such as: butane-1,4-diol, butane-1,2-diol, butane-1,3-diol, butane-2,3-diol, propane- 1,2-diol (propylene glycol), pentane-1,2-diol, pentane-1,5-diol, pentane-2,4-diol, pentane-1,3-diol, hexane-1,6-diol, hexane-1,2-diol, hexane-2,5-diol, 2-methyl-2,4-pentanediol (hexylene glycol), diethylene glycol, dipropylene glycol, triethylene glycol; triols such as: hexane-1,2,6-triol, glycerol; tetraols such as erythriol; pantanols such as: lyxitol, xylitol, ribitol; hexols such as: sorbitol, mannitol; benzyl alcohol; phenoxyethanol; ethanol and mixtures thereof; more preferably chosen from ethanol, benzyl alcohol, 1,2-pentanediol, sorbitol and mixtures thereof, even more preferably ethanol, benzyl alcohol and mixtures thereof. Process for dyeing the hair according to any one of the preceding claims, implementing step a) of applying a composition comprising at least one lanthanide salt and then step b) of applying at least one natural dye. Hair dyeing process according to any one of the preceding claims, implementing between steps a) and b) an intermediate rinsing step. Multi-compartment device comprising at least one compartment comprising at least one lanthanide salt, a second compartment comprising at least one natural colorant.