FR3117351A1 - Process for dyeing keratin fibers using: a polyphenol, an aldehyde and/or sugar, a manganese salt, a (hydrogen)carbonate, an extract and/or curry leaf powder. - Google Patents

Abstract

Process for dyeing keratin fibers using: a polyphenol, an aldehyde and/or sugar, a manganese salt, a (hydrogen)carbonate, an extract and/or curry leaf powder The invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair using: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts, one or more (hydrogen)carbonate, an extract and/or curry leaf powder.

Description

Process for dyeing keratin fibers using: a polyphenol, an aldehyde and/or sugar, a manganese salt, a (hydrogen)carbonate, an extract and/or curry leaf powder.

The invention relates to a process for dyeing keratin fibres, in particular human keratin fibers such as the hair, using: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts, one or more ( hydrogen)carbonate, an extract and/or curry leaf powder.

For a long time, many people have been looking to change the color of their hair, and in particular to hide their white hair.

To color human keratin fibres, there are mainly two methods.

The first type of coloring is so-called permanent or oxidation coloring, which uses dye compositions containing oxidation dye precursors, generally called oxidation bases. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise by a process of oxidative condensation to colored compounds.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers makes it possible to obtain a rich palette of colors.

The second type of coloring is so-called semi-permanent coloring or direct coloring, which consists in applying direct dyes which are colored and coloring molecules having an affinity for said fibers to the keratin fibers, leaving them to pause, then rinsing them. In order to produce these dyes, the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes, and natural dyes.

However, the implementation of these dye compositions can have a certain number of drawbacks.

In fact, after application to the keratin fibers, the tinctorial power obtained may not be entirely satisfactory, or even low, and lead to a restricted range of colors.

The colorings may also not be sufficiently tenacious in the face of external agents such as light, shampoos, perspiration and also be too selective, that is to say that the difference in coloring is too great along the same keratin fiber which is sensitized differently between its tip and its root.

On the other hand, there is a demand for coloring hair with natural compounds, especially of plant origin. Nevertheless, coloring with plant-based dyes generally offers less diversity in terms of color than more conventional colorings, which can hinder their use.

Thus, there is a real need to provide a process for dyeing keratin fibres, in particular human keratin fibers such as the hair, which does not have the drawbacks mentioned above, that is to say which is capable to lead to good color build-up while having low selectivity and good tenacity, and which makes it possible to obtain a diversity of color to meet consumer demands.

These aims and others are achieved by the present invention, the subject of which is therefore a process for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising the following successive steps:
a) the application to the keratin fibers of a composition (A) comprising: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts;
b) the application to the keratin fibers of a composition (B) comprising one or more (hydrogen)carbonates;
c) the application to the keratin fibers of a composition (C) comprising an extract and/or curry leaf powder.

The composition according to the invention makes it possible in particular to lead to chromatic colorations, powerful, intense and not very selective, that is to say colorations which are homogeneous along the fiber. It also makes it possible to achieve different shades in a very wide color palette. In addition, it allows a good build-up of the color.

This composition also allows stubborn colorations, persistent to external agents (such as light or sweat) and to shampoos.

The invention also relates to a kit comprising in a first compartment a composition (A) as defined in step a) , in a second compartment a composition (B) as defined in step b) and in a third compartment, a composition (C) as defined in step c) .

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

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “included between” and “ranging from … to …”.

Furthermore, the expression “at least one” used in the present description is equivalent to the expression “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.

By " successive steps " is meant steps implemented in the order indicated.

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, in C₂-VS₂₀having ethylenic unsaturation; 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; preferentially, the aryl radical is chosen from 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(W)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: i) (VS₁-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(W)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 ring 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.

Membership (A)

Polyphenols

The process of the invention comprises the application to the keratin fibers of a composition (A) comprising one or more polyphenol(s).

These polyphenols are preferably chosen from ortho-diphenols (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.

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 (I) , or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or its solvates such as the hydrates:
(I)

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) 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 groups hydroxy or glycosyloxy, 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 (I) comprises from one to four rings.

According to a particular embodiment, the ODP(s) correspond to ODP(s) of formula (I) of which two adjacent substituents R ¹ - R ² , R ² - R ³ or R ³ - R ⁴ can form with the atoms carbon bearing 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 trihydroxyanthraquinones,
- 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 ODPs of the invention of hematoxylin/hematein and brazilin/brazilein type, mention may be made by way of example of hematoxylin (Natural Black 1 according to the INCI name) and brazilin (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, the ODPs are derived from logwood, pernambuco wood, sappan wood and brazilwood, in particular logwood.
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, extracts that can be used 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 even 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, myricetol, fisetin, rhamnetin;
- flavones such as luteolin, their glycosides such as luteolol 7-O-glucoside, baicalin, orientin:
- dihydroflavonols or flavanonols 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 (II) 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:
(II)
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 (II) 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, sappanwood, brazilwood and mixtures thereof.

The total content of polyphenols as defined above preferably varies from 0.05% to 30% by weight, more preferably from 0.1 to 20% by weight, better still from 0.5 to 5% by weight relative to the total weight of composition (A) .

The total content of ODPs as defined above preferably varies from 0.05% to 30% by weight, more preferably from 0.1 to 20% by weight, better still from 0.2 to 5% by weight relative to the total weight of composition (A) .

Additional direct dyes

The process according to the invention can also implement one or more additional direct dye(s) different from ODPs.

When present, the additional direct dye(s) are preferably included in composition (A) .

These additional direct dyes are preferably synthetic.

By " direct dye " is meant colored species. These are dyes that will diffuse superficially on the fiber.

These synthetic additional direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and/or non-aromatic dyes in common use such as nitrobenzene, azo, hydrazono, nitrated ( hetero)aryl, tri(hetero)arylmethane, (poly)methine, carbonyl, azine, porphyrin, metalloporphyrine, quinone and in particular anthraquinone, indoamine, phthalocyanine and mixtures thereof.

Among the additional nitrobenzene direct dyes, mention may be made of: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-β-hydroxyethylaminobenzene; 1-amino-2-nitro-4-bis(β-hydroxyethyl)-aminobenzene; 1,4-bis(β-hydroxyethylamino)-2-nitrobenzene; 1-β-hydroxyethylamino-2-nitro-4-bis-(β-hydroxyethylamino)-benzene; 1-β-hydroxyethylamino-2-nitro-4-aminobenzene; 1-β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxyethyl)-aminobenzene; 1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene; 1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene; 1,2-diamino-4-nitrobenzene; 1-amino-2-β-hydroxyethylamino-5-nitrobenzene; 1,2-bis-(β-hydroxyethylamino)-4-nitrobenzene; 1-amino-2-tris-(hydroxymethyl)-methylamino-5-nitrobenzene; 1-Hydroxy-2-amino-5-nitrobenzene; 1-Hydroxy-2-amino-4-nitrobenzene; 1-Hydroxy-3-nitro-4-aminobenzene; 1-Hydroxy-2-amino-4,6-dinitrobenzene; 1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene; 1-Methoxy-2-β-hydroxyethylamino-5-nitrobenzene; 1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene; 1-β,γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene; 1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene; 1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene; 1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene; 1-β-hydroxyethylamino-3-methyl-2-nitrobenzene; 1-β-aminoethylamino-5-methoxy-2-nitrobenzene; 1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene; 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene; 1-Hydroxy-6-bis-(β-hydroxyethyl)-amino-3-nitrobenzene; 1-β-hydroxyethylamino-2-nitrobenzene; 1-Hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Additional Azo Direct Dyes include: Basic Red 51, Basic Orange 31, Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Yellow 57, Acid Yellow 36, Acid Orange 7 , Acid Red 33, Acid Red 35, Acid Yellow 23, Acid Orange 24, Disperse Black 9, Basic Brown 16, Basic Brown 17.

Among the additional hydrazono direct dyes, mention may be made of: Basic Yellow 87.

Among the additional nitro aryl direct dyes, mention may be made of: HC Blue 2, HC Yellow 2, HC Red 3, 4-hydroxypropylamino-3-nitrophenol, N,N' -bis-(2-hydroxyethyl)-2-nitro-phenylenediamine .

Among the additional direct dyes triarylmethane, we can mention: Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

Quinone additional direct dyes include: Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62 , Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, as well as the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-aminopropylamino-4-methylaminoanthraquinone, 1-aminopropylamino-anthraquinone, 5-β-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylamino-anthraquinone, 1,4-bis-(β,γ-dihydroxypropylamino)-anthraquinone, Acid Blue 25, Acid Blue 43, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Mordant Red 3, Acid Black 48, HC Blue 16.

Among the additional azine direct dyes, mention may be made of: Basic Blue 17, Basic Red 2.

Among the additional indoamine direct dyes, we can mention: 2-β-hydroxyethylamino-5-[bis-(β-4'-hydroxyethyl)amino]anilino-1,4-benzoquinone, 2-β-hydroxyethylamino-5-(2 '-methoxy-4'-amino)anilino-1,4-benzoquinone, 3-N(2'-chloro-4'-hydroxy)phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine, 3-N( 3'-Chloro-4'-methylamino)phenyl-ureido-6-methyl-1,4-benzoquinone imine, 3-[4'-N-(ethyl,carbamylmethyl)-amino]-phenyl-ureido-6-methyl- 1,4-benzoquinone imine.

The total content of additional direct dyes , when present, varies, preferably 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 20 % by weight, better still from 0.3 to 10% by weight relative to the total weight of composition (A) .

Aldehydes

Composition (A) also comprises one or more aldehydes.

The useful aldehydes according to the invention can be natural or synthetic, preferably they are natural.

The aldehydes useful according to the invention can be those present in essential oils or in natural extracts or parts of plants, or bacteria or fungi such as: vanilla pods, Cinnamomum cassia , Cinnamomum cassia oleoresin, Cinnamonum Poria cocos , Cuminum cyminum , bacteria of the genus Vibrio, leaves and flowers of Inula viscosa (L.), essential oil of cinnamon, volatile oil of Belamcanda chinensis (L.), Alpinia oxyphylla Miq. , Stenoloma chusanum , bergamot leaves, Clerodendranthus spicatus , Fructus cinnamomi cassiae immaturi , Artemisia annua , Salvia miltiorrhiza , Radix Adenophorae oil , cassia bark, lemongrass oil, litsea cubeba oil, backoussia oil, bourbon geranium oil , Filipendula vestita leaf essential oil, Dalbergia latifolia heartwood, Bidens tripartite aerial parts, Mimusops elengi flowers, Alpinia galangal ginger, Ascochyta lentis var. lathyri, leaves of Michelia figo , whole plants of Gueldenstaedtia verna , fruit of Lycium barbarum , ethanolic extract of goji, seeds of Nepeta Lamiaceae teydea Webb et Berth. teydea , Agrobacterium rhizogenes ATCC-15834, root of Morus australis , fungus Stereum insigne CGMCC5.57, leaves of Clausena lansium Skeels Rutaceae, plant of Ixeris chinensis colletrotrichum gloeosporioides, leaves of Sabicea cineria sacleuxii Micromonospora sp. RV43, fruits of Maclura tricuspidata , Cudrania tricuspidata , bark of Citrus grandis , Porodaedalea pini Brot., Internal strain number BCRC 35384, Phellinus pini , fruits of Psoralea corylifolia L. , Psoraleae fructac , roots of Fructacum coreanum ; stems of Michelia fuscata , herbs of Kalimeris indica , Hedyotis uncinella , roots of Caragana sinica , aerial parts of Lindera akoensis , fruits of Morus alba , cultivation of Aspergillus sp. SCSIO41002 of mangrove sediments, the plant Dendrobium moniliforme, the culture of the fungus Phoma herbarum PSU-H256; leaf of Hevea brasiliensis , twigs and leaves of Tara Caesalpinia spinosa Kuntze, roots of D. versipellis , branches and leaves of Pyrus pashia , whole plant of Dendrobium tortile , Petrosimonia sibirica , whole plant of Artemisia austro-yunnanensis, flowers of Chimonanthus praecox L. , rhizomes of Bletilla formosana , root bark of Cudrania tricuspidata , aqueous ethanolic extract of bamboo shoots, leaves of Cyrtopodium paniculatum , pseudobulbs of Cyrtopodium paniculatum , roots of Coixlachryma-jobi L. , whole plants of Phaius mishmensis ; upper part of dried Clinacanthus nutans , leaves of Amomum siamensis , seeds of Coix lachryma-jobi L. , flesh of argan trees, stems of Capsicum annuum , red pepper, strain filtrate of Diaporthe gulyae , Aspergillus versicolor , Lobaria quercizans , fruits of Pandanus tectorius , roots of Michelia compressa , flowers of Edgeworthia gardneri , stem of Erythrophleum suaveolens , aerial parts of Portulaca oleracea L. , rhizomes of Miscanthus floridulus , Pestalotiopsis vaccinii cgmcc3.9199, endophytic fungus, Zhuyeqing liqueur, Vanilla planolia , stems of Michelia compressa , root barks of Moringa oleifera , aerial parts of Inula falconeri , rhizomes and roots of Smilax scobinicaulis , Aletris Spicata , leaves of Citrus reticulate, rhizomes of Dioscorea nipponica , endophytic fungus Dothideomycete sp. CRI7, roots of Ficus beecheyana , rice bran, Bethencourtia hermosae , Morinda umbellate , extract from the culture of the fungus associated with the marine sponge Aspergillus similanensis , whole plants of Dendrobium devonianum , rhizome of Sparganium stoloniferum , roots of Citrus hystrix , pseudostems of 'Alpinia conchigera , rhizomes of Alpinia conchigera , Pleione bulbocodioides , aerial parts of Dracocephalum ruyschiana L. , Ainsliaea macrocephala , stems of Machilus philippinensis , whole plant of Croton tonkinensis , aerial parts of Triosteum pinnatifidum Linn. , Rhizomes of Smilax glabra Roxb. , Roots of angoliaceae Scrophularia ningpoensena , leaves or aerial parts of Tanacetum ptarmiciflorum , whole plant of Salvinia molesta , root of Cremanthodium lineare , whole plant of Chrozophora plicata , Claoxylon longifolium , aerial parts stems of Dendrobium antennatum , fruits of Serenoa repens , Annulohypoxylon ilanense , roots of Alyxia schlechcaria Unlense , leaves of Leptoderris fasciculata , shells of Carya cathayensis , aerial parts of Diplomorpha canescens , leaves of Syzygium aqueum , stems of Wikstroemia scytophylla , roots of Cucumis sativus , Acalypha australis L. , aerial parts of Cardamine komarovii , aerial parts aerial parts of Senecio cannabifolius , aerial parts of Euphorbia mellifera , bracts of rhizomes , leaves and twigs of Litsea szemaois , leaves of Cinnamomum reticulatum , stems and roots of Pisonia aculeate , roots of Cinnamomum reticulatum , rhizomes of Gastrodia elata Blume , stem bark of ' Ailanthus alt issima , Dracaena cambodiana stems, Zanthoxylum nitidum stem wood, Coix lachryma-jobi seeds, Cynodon dactylon whole plant, Abies nephrolepis aerial parts, Archangel root, Cinnamomum cassia extract, essential oils bergamot, litsea cubeba, cinnamon, lemongrass, geranium bourbon, lemongrass, lemon balm and backoussia.

The useful aldehydes according to the invention are preferably chosen from the compounds of formulas(III),(IV),(V)Or(VI)following and mixtures thereof:

In which :
R ¹ same or different independently represent:
- a C alkyl or alkenyl radical₁-VS₁₂, optionally substituted by one or more identical or different radicals chosen from a hydroxyl radical, a phosphate radical, an -NH radical₂;
- a hydroxyl radical;
- a C alkoxy radical₁-VS₄;
- a carboxyl radical (-COOH);
- an -OCOAlkyl(C) radical₁-VS₅₎
- a -COOAlkyl(C) radical₁-VS₅);
- a radical (hydroxy)(di)(alkyl)amino -NR^ToR^bOrR ^To ,R ^b , identical or different, representing, independently of one another, a hydrogen atom, a saturated C₁-VS₁₂optionally substituted by a hydroxyl radical;
- an ammonium radical –N⁺(R^vs)₃, Year^-, OrR ^vs , identical or different, represent independently of each other, a saturated alkyl radical in C₁-VS₆,Year-represents an anionic counterion or a mixture of anionic counterions, guaranteeing the electroneutrality of the molecules;
R ² identical or different represent independently, a hydrogen atom or a saturated or unsaturated alkyl radical in C₁-VS₆, optionally substituted by a hydroxyl radical;
notis an integer ranging from 0 to 4 in the formula (III);
notis an integer ranging from 0 to 3 in the formula (IV)
xrepresents a carbon atom, a nitrogen atom or a –N group⁺(R^d), Year^-OrR ^d represents a C alkyl radical₁-VS₆, optionally substituted by a hydroxyl radical,Year-represents an anionic counterion or a mixture of anionic counterions, guaranteeing the electroneutrality of the molecules;
pis an integer ranging from 0 to 4;
whenR ¹ represents a C alkyl radical₁-VS₄andnotis 2, these two substituents can be adjacent and can form an aromatic ring with 5 or 6 carbon atoms;
R ³ identical or different represent represents independently, a saturated or unsaturated alkyl radical in C₁-VS₁₂, optionally substituted by a hydroxyl radical or an amino radical;
thererepresents a -NR group^dOrR ^d represents a C alkyl radical₁-VS₆, optionally substituted by a hydroxyl radical;
zrepresents a carbon atom or a nitrogen atom;
mis an integer of 0, 1 or 2;
R ⁴ represented
- a hydrogen atom; Or
- a hydrocarbon radical, linear or branched, in C₁-VS₁₆, saturated or unsaturated, when it is unsaturated, it comprises a number of ethylenic unsaturations between 1 and 3; said radical being optionally substituted by 1 to 3 radicals, identical or different, chosen from a hydroxyl radical, a C alkoxy radical₁-VS₂, a C (poly)hydroxyalkoxy radical₁-VS₄, an –NH radical₂, a C (di)alkylamino radical₁-VS₂, a carboxyl radical in salified form or not, an aminosulfonyl radical, a (poly)hydroxyalkylamino radical in C₂-VS_4,a halogen atom such as chlorine atom, fluorine atom or bromine atom; said radical possibly being interrupted by a saturated or unsaturated 5- or 6-membered, preferably 6-membered, ring, optionally substituted by 1 to 3 identical or different radicals chosen from a C alkyl radical₁-VS₁₂, a C hydroxyalkyl radical₁-VS₁₀or a C alkoxy radical₁-VS₂;
- a phenyl radical, optionally substituted by 1 to 3 identical or different radicals chosen from a C alkyl radical₁-VS₁₂, a C hydroxyalkyl radical₁-VS₁₀, a hydroxyl radical or an alkoxy radical in C₁-VS₂;
R ⁵ represents a hydrogen atom or a hydrocarbon radical, linear or branched, in C₁-VS₁₆, saturated or unsaturated.

By “ anionic counter-ion ” is meant an anion or an anionic group derived from an organic or mineral acid counterbalancing the cationic charge of the aldehyde; more particularly the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including C ₁ -C ₆ alkylsulfonates: Alk-S(O) ₂ O— such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulphonates: Ar-S(O) ₂ O- such as benzene sulphonate and toluene sulphonate or tosylate; v) Alk-C(O)-OH carboxylates with Alk representing a (C ₁ -C ₆ )alkyl group optionally substituted by one or more hydroxy or carboxylate groups such as citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-OS(O)O- such as methysulphate and ethyl sulphate; x) arylsulphates: Ar-OS(O)O- such as benzene sulphate and toluene sulphate; xi) alkoxy sulphates: Alk-OS(O) ₂ O- such as methoxy sulphate and ethoxy sulphate; xii) aryloxysulphates: Ar-OS(O) ₂ O-, xiii) phosphates O=P(OH) ₂ -O-, O=P(O-) ₂ -OH O=P(O-) ₃ , HO -[P(O)(O-)]wP(O)(O-) ₂ with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, and xvii) disulfate (O=)2S(O-) ₂ or SO ₄ ^2- and monosulfate HSO ₄ ^- .

The aldehyde(s) useful according to the invention can be introduced pure or mixed with other compounds. By way of example, aldehydes can be present in natural extracts such as, for example, cinnamomum cassia oleoresin.

The aldehydes useful according to the invention are more preferably chosen from the following compounds: benzaldehyde, cinnamaldehyde, coniferaldehyde, sinapaldehyde, caffealdehyde (3,4-Dihydroxycinnamaldehyde), vanillin, ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde), isovanillin ( 3-hydroxy-4-methoxybenzaldehyde), anisaldehyde (4-methoxybenzaldehyde), 4-formylbenzoic acid, methyl 4-formylbenzoate ( methyl 4-formylbenzoate), p -dimethylaminobenzaldehyde, p -di(hydroxyethyl)aminobenzaldehyde, p -di(hydroxymethyl )aminobenzaldehyde heliotropine (1,3-benzodioxole-5-carbaldehyde), 2,4-dihydroxy-3-methylbenzaldehyde, syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde), phenylacetaldehyde, bud (3-(4- tert -butylphenyl )propanal), 2-phenylpropionaldehyde, cyclamen aldehyde, 2-(4-methylphenyl)acetaldehyde, lilial ( 3-(4-tert-butylphenyl)-2-methylpropanal), hexyl cinnamaldehyde, pyridoxal (3-hydroxy-5-(hydroxymethyl )-2-methylpyridine-4-carbaldehyde), pyridoxal phosphate (4 -formyl-5-hydroxy-6-methylpyridin-3-yl)methyl dihydrogen phosphate), 1-methyl-4-formylpyridinium salts (such as chloride and methylsulfate salts), 1-methyl-4-formylquinolinium salts (such as chloride, methylsulfate and toluene sulfonate salts), geranial, neral, citronellal, 2,4,6-trihydroxybenzaldehyde, cuminaldehyde, retinal, hydroxyisohexyl-3-cyclohexene carboxaldehyde, (4-formylphenyl)-trimethyl salts -ammonium (such as chloride and methylsulfate salts), 3,4,5-trihydroxybenzaldehyde, myristic aldehyde ( n -tetradecanal), mentha-1,3-dien-7-al, p -mentha-1,3- dien-7-al, salicylaldehyde, procatechuic aldehyde (3,4-dihydroxybenzaldehyde), indole-3-carboxaldehyde, divanillin, salts of divanillin (such as sodium and potassium salts), and mixtures thereof, as well as extracts le or containing them such as Cinnamomum Cassia oleoresin.

Better still, the aldehydes useful according to the invention, which are particularly preferred, are chosen from the following compounds: benzaldehyde, cinnamaldehyde, vanillin, ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde), 1-methyl-4-formylquinoline toluene sulphonate, acid 4 -formylbenzoic acid, methyl 4-formylbenzoate (methyl 4-formylbenzoate), p -dimethylaminobenzaldehyde, p -di(hydroxyethyl)aminobenzaldehyde, p -di(hydroxymethyl)aminobenzaldehyde, pyridoxal (3-hydroxy-5-(hydroxymethyl)-2-methylpyridine -4-carbaldehyde), divanillin and mixtures thereof, as well as extracts containing it or them, such as Cinnamomum Cassia oleoresin.

When the aldehydes useful according to the invention comprise one or more double bond(s) between two carbon atoms, this or these double bond(s) (or alkene(s)) is or are, preferably of configuration E.

According to another preferred embodiment, the aldehydes useful according to the invention can be contained in essential oils or natural extracts, preferably contained in vanilla pods, extract ofCinnamomum cassia, Oleoresin ofCinnamomum cassia, essential oils of bergamot, litsea cubeba, cinnamon, lemongrass, geranium bourbon, lemongrass, lemon balm and backoussia.

Sugars

In a manner known per se, the term “sugar” designates oxygenated hydrocarbon compounds which have several alcohol functions, with or without aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

By " monosaccharide » means a sugar comprising only a single unit i.e. not comprising a covalent glycosidic 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.

As sugars suitable for the process according to the invention, mention may be made, for example, of sucrose (or sucrose), fructose, maltose, cellobiose, glucose, ribose, lactose, trehalose, arabinose, and their derivatives in particular alkylated, such as methylated derivatives such as methylglucose.

Preferably, maltose is used.

These compounds can be of natural or synthetic origin. Preferably they are of natural origin or occurrence. They may be present in plant extracts containing them.

The total content of aldehydes and/or sugars preferably varies from 0.01 to 20% by weight, more preferably from 0.05% to 15% by weight, better still from 0.1 to 10% by weight, relative to the weight of the composition (A) .

Manganese salts

Composition (A) also comprises one or more manganese salts.

Within the meaning of the present invention, the term “salts” means the salts themselves in ionized form. These salts can be solvated, in particular hydrated.

Specifically, the salts of the invention are of oxidation state 2.

The manganese salt or salts are advantageously chosen from chlorides, fluorides, iodides, bromides, sulphates, phosphates, nitrates, perchlorates, carbonates, carboxylates, and mixtures thereof.

The carboxylates which can be used in the invention also include salts of carboxylic acids comprising one or more hydroxy radicals such as gluconates.

Examples of carboxylates include, for example: acetate, tartrate, lysinate, glutamate, lactate, glycinate, aspartate, stearate, acetylacetate.

The manganese derivatives can be introduced in solid form into composition (A) or alternatively be introduced in the form of an aqueous solution such as natural, mineral or thermal water, rich in these ions or even sea water (dead sea notably). They can also come from mineral compounds such as earths, ochres such as clays (green clay for example) or even from plant extracts containing them (cf. for example document FR 2 814 943).

Among the manganese salts, manganese chloride, manganese carbonate, manganese difluoride, manganese acetate tetrahydrate, manganese lactate trihydrate, manganese phosphate, manganese iodide, manganese nitrate, manganese trihydrate, manganese bromide, manganese perchlorate tetrahydrate, manganese sulfate monohydrate, manganese gluconate, manganese glycinate, and mixtures thereof.

Preferably, the process of the invention uses one or more manganese salts of oxidation state 2 or (II).

Even more preferentially, the manganese salt or salts are chosen from manganese (II) carboxylates, in particular manganese gluconate and manganese (II) halides, such as manganese (II) chloride and mixtures thereof.

Better still, the manganese salt or salts are chosen from manganese(II) chloride, manganese(II) gluconate and mixtures thereof.

The total content of manganese salts varies, preferably, from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, better still, from 0.1 to 2% by weight relative to the weight of the composition (A) .

(hydrogen)carbonates

Composition (B) comprises one or more (hydrogen)carbonate(s).

The (hydrogen)carbonate(s) useful in the process of the invention are chosen in particular from the compounds of the following formulas:
- R' ⁺ , HCO ₃ ^- with R' representing a hydrogen atom, an alkali metal, an ammonium group R'' ₄ N ⁺ - or phosphonium R'' ₄ P ⁺ - where the R'' groups, identical or different, represent a hydrogen atom, an optionally substituted (C ₁ -C ₆ )alkyl group such as hydroxyethyl; when R' represents a hydrogen atom, the hydrogen carbonate is then called dihydrogen carbonate (CO ₂ , H ₂ O); And
- Met' ²⁺ (HCO ₃ ^- ) ₂ with Met' representing an alkaline-earth metal.

More particularly, the (hydrogen)carbonate(s) are chosen from alkali hydrogen carbonates, alkaline-earth hydrogen carbonates, ammonium hydrogen carbonates and mixtures thereof; and more preferably from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates and mixtures thereof.

Better still, the hydrogen carbonates are chosen from sodium, potassium, magnesium and calcium hydrogen carbonates and mixtures thereof, and in particular sodium hydrogen carbonate and potassium hydrogen carbonate. Even more preferably, the hydrogen carbonate used in the process of the invention is potassium hydrogen carbonate.

These (hydrogen)carbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, water from Badoit (cf. patent for example document FR 2 814 943). In particular, mention may be made of potassium carbonate K ₂ CO ₃ , potassium hydrogen carbonate or potassium bicarbonate KHCO ₃ .

These hydrogen carbonates can also be generated in situ by any method making it possible to generate an HCO ₃ ^- salt.

The total content of the (hydrogen) carbonate(s) as defined above varies, preferably, from 0.01% to 20% by weight, and more preferably from 0.05% to 10% by weight, better still, from 0.1 at 8% by weight, relative to the total weight of composition (B) .

According to a preferred embodiment of the invention, composition (B) is aqueous and has a pH greater than or equal to 7, particularly this pH ranges from 8 to 11, preferably this pH ranges from 9 to 11.

The pH of composition ( B ) 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 buffer systems known to those skilled in the art. It is possible, in particular, to use lactic or citric acid, dilute hydrochloric acid, an alkaline agent such as arginine, ammonia, monoethanolamine, sodium or potassium (bi)carbonate.

Extracts and/or curry leaf powder

Composition (C) comprises a curry leaf extract and/or powder.

From the Rutaceae Murraya koenigii family, Curry or Caloupilé leaves are dried or not beforehand and then ground to obtain a dark yellow powder. A powder is then obtained, the size of the ground particles of which varies between 50 nm and 500 microns, preferably between 150 nm and 250 microns.

Curry leaves, once dried, can also be extracted using a protic polar solvent such as water or ethanol, preferably water. After filtration, evaporation of the solvent and drying, a curry leaf extract in powder form can be obtained.

These extracts can also be commercial extracts. Among the commercial extracts of curry leaf, mention may in particular be made of the extracts marketed by the company Pfannenschmidt.

The total content of the curry leaf extract and/or powder as defined above varies, preferably, from 0.001% to 40% by weight, and more preferably from 0.01% to 30% by weight, better still, from 0.05 to 5% by weight for the curry leaf extract and preferably 0.001% to 40% by weight, and more preferably 0.01% to 30% by weight, more preferably 0.05 to 15 % by weight for the curry leaf powder, relative to the total weight of the composition (C) .

According to a preferred embodiment of the invention, composition (C) is aqueous and has a pH greater than or equal to 2, particularly, this pH ranges from 2 to 11, preferably this pH ranges from 3 to 10.

The pH of composition (C) 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 buffer systems known to those skilled in the art. It is possible, in particular, to use lactic acid, citric acid, dilute hydrochloric acid, an alkaline agent such as arginine, ammonia, monoethanolamine, sodium or potassium (bi)carbonate, hydroxide sodium.

Surfactants

The method according to the invention can, in addition, implement one or more surfactants. These can be chosen from anionic surfactants, amphoteric or zwitterionic surfactants, nonionic surfactants and cationic surfactants and/or mixtures thereof.

Preferably, composition (A) comprises at least one surfactant.

Preferably, composition (B) comprises at least one surfactant.

The term “ anionic surfactant ” is understood to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups CO2H, CO2-, SO3H, SO3-, OSO3H, OSO3-, H2PO3, HPO3-, PO32-, H2PO2, HPO2-, PO22-, POH and PO-.

As examples of anionic surfactants that can be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylarylpolyether sulfates, monoglyceride-sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-alkyl(C1-C4)-N -acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, salts of D-galactoside-uronic acids, salts of alkyl ether-carboxylic acids, salts of alkyl aryl ether acids -carboxylic acids, salts of alkyl amidoether-carboxylic acids; and the corresponding unsalified forms of all these compounds; the alkyl and acyl groups of all these compounds (unless otherwise mentioned) generally comprising from 6 to 24 carbon atoms and the aryl group generally designating a phenyl group.

These compounds can be oxyethylenated and then preferably contain from 1 to 50 ethylene oxide units.

The salts of C ₆ -C ₂₄ alkyl monoesters and of polyglycoside-polycarboxylic acids can be chosen from C ₆ -C 24 alkyl polyglycoside-citrates, C ₆ -C ₂₄ alkyl polyglycoside-tartrates ₂₄ and C ₆ -C ₂₄ alkyl polyglycoside sulfosuccinates.

When the anionic surfactant(s) are in salt form, they can be chosen from alkali metal salts such as sodium or potassium and preferably sodium salt, ammonium salts, amine salts and in particular of amino alcohols or salts of alkaline-earth metals such as the magnesium salt.

By way of example of aminoalcohol salts, mention may in particular be made of mono-, di- and triethanolamine salts, mono-, di- or tri-isopropanol-amine salts, 2-amino 2-methyl 1-propanol, 2-amino 2-methyl 1,3-propanediol and tris(hydroxymethyl)amino methane.

Salts of alkali or alkaline earth metals and in particular sodium or magnesium salts are preferably used.

Any anionic surfactants present may be mild anionic surfactants, that is to say without sulphate function.

As regards mild anionic surfactants, mention may be made in particular of the following compounds and their salts, as well as their mixtures: polyoxyalkylenated alkyl ether carboxylic acids; polyoxyalkylenated alkylaryl ether carboxylic acids; polyoxyalkylenated alkylamido ether carboxylic acids, in particular those comprising 2 to 50 ethylene oxide groups; alkyl D galactoside uronic acids; acylsarcosinates, acylglutamates; and carboxylic alkylpolyglycoside esters.

Very particularly, it is possible to use polyoxyalkylenated alkyl ether carboxylic acids such as, for example, lauryl ether carboxylic acid (4.5 EO) marketed for example under the name AKYPO RLM 45 CA from KAO.

Among the anionic surfactants mentioned above, sulphated surfactants such as alkyl sulphates or alkyl ether sulphates, and acylglutamates , more preferably alkyl ether sulphates, are preferably used.

The amphoteric or zwitterionic surfactant(s) which can be used in the present invention may in particular be derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group.

Mention may in particular be made of (C ₈ -C ₂₀ )alkylbetaines, sulfobetaines, (C ₈ -C ₂₀ alkyl)amido(C ₃ -C ₈ alkyl)betaines or (C ₈ -C ₂₀ alkyl) )amido(C ₆ -C ₈ alkyl)sulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made of the compounds of the following structures ( A1 ), ( A2 ) and ( A3 ), respectively:
- Ra-CONHCH ₂ CH ₂ -N+(R _b )(R _c )(CH2COO-) ( A1 )
in which: Ra represents a C ₁₀ to C ₃₀ alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl group; Rb represents a beta-hydroxyethyl group, and Rc represents a carboxymethyl group;
- R'a-CONHCH2CH2-N(B)(B') ( A2 )
in which: B represents -CH ₂ CH ₂ OX', B' represents -(CH ₂ )z-Y', with z = 1 or 2, X' represents the group -CH ₂ -COOH, CH ₂ -COOZ', -CH ₂ CH ₂ -COOH, -CH ₂ CH ₂ -COOZ', or a hydrogen atom, Y' represents –COOH, –COOZ', the group -CH ₂ -CHOH-SO ₃ H or CH ₂ -CHOH -SO ₃ Z', Z' represents an ion resulting from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine, R'a represents an alkyl or alkenyl group in C ₁₀ at C ₃₀ of an R'a-COOH acid preferably present in coconut oil or in hydrolyzed linseed oil, an alkyl group, in particular C ₁₇ and its iso form, an unsaturated C ₁₇ group;
- Ra''-NHCH(Y'')-(CH ₂ )nCONH(CH ₂ )n'-N(Rd)(Re) ( A3 )
in which: Y'' represents the group –COOH, -COOZ'', -CH ₂ -CH(OH)SO ₃ H or the group -CH ₂ CH(OH)SO ₃ -Z''; Rd and Re , independently of one another, represent a C ₁ -C ₄ alkyl or hydroxyalkyl radical; Z'' represents a cationic counter ion derived from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; Ra'' represents a C ₁₀ -C ₃₀ alkyl or alkenyl group of an acid Ra''-COOH preferably present in coconut oil or in hydrolyzed linseed oil; n and n' , independently of each other, designate an integer ranging from 1 to 3.

These compounds of formula ( A1 ) or ( A2 ) are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid, cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate marketed by the company RHODIA under the trade name MIRANOL® C2M concentrate.

Among the compounds of formula (A3), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and marketed by the company CHIMEX under the name CHIMEXANE HB.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C ₈ -C ₂₀ alkyl)betaines such as cocobetaine, (C ₈ -C ₂₀ alkyl)amido(C ₃ -C ₈ alkyl ) betaines such as cocoamidopropyl betaine, and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactant(s) are chosen from cocoamidopropyl betaine and coco betaine.

The nonionic surfactant(s) that can be used in the composition of the present invention are described in particular, for example, in “Handbook of Surfactants” by M.R. PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178.

As examples of nonionic surfactants, mention may be made of the following compounds, alone or as a mixture:
- oxyalkylenated (C ₈ -C ₂₄ )alkylphenols;
- C ₈ to C ₄₀ alcohols, saturated or not, linear or branched, oxyalkylenated or glycerolated, they preferably contain one or two fatty chains;
- C ₈ to C ₃₀ fatty acid amides, saturated or not, linear or branched, oxyalkylenated;
- esters of C ₈ to C ₃₀ acids, saturated or not, linear or branched, and of polyethylene glycols;
- esters of C ₈ to C ₃₀ acids, saturated or not, linear or branched, and of sorbitol, preferably oxyethylenated;
- esters of fatty acids and sucrose,
- C ₈ -C ₃₀ fatty acid esters and sorbitan,
- (C ₈ -C ₃₀ )alkyl (poly)glucosides, (C ₈ -C ₃₀ )alkenyl (poly)glucosides, optionally oxyalkylenated (0 to 10 oxyalkylenated units) and comprising from 1 to 15 glucose units, esters of (C ₈ -C ₃₀ )alkyl (poly)glucosides,
- oxyethylenated vegetable oils, saturated or not;
- ethylene oxide and/or propylene oxide condensates;
- N -alkyl(C ₈ -C ₃₀ )glucamine and N -acyl(C ₈ -C ₃₀ )-methylglucamine derivatives;
- amine oxides.

They are chosen, in particular, from alcohols, alpha-diols, (C ₁ -C ₂₀ )alkylphenols, these compounds being ethoxylated, propoxylated or glycerolated, and having at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging in particular from 1 to 200 and the number of glycerol groups possibly ranging in particular from 1 to 30.

Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; ethoxylated fatty amides preferably having from 1 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4, fatty acid esters of sorbitan containing from 1 to 30 ethylene oxide units, sucrose fatty acid esters, polyethylene glycol fatty acid esters, (C ₆ -C ₂₄ alkyl)polyglycosides, oxyethylenated vegetable oils, N-(C ₆ -C ₂₄ alkyl)glucamine derivatives, amine oxides such as (C10-C14 alkyl)amine oxides or N-(C ₁₀ -C ₁₄ acyl)- aminopropylmorpholine.

The nonionic surfactant(s) are preferably chosen from (C ₆ -C ₂₄ alkyl)polyglycosides and mixtures thereof.

The cationic surfactant(s) which can be used in the composition according to the invention are generally chosen from primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated, quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C ₈ -C ₃₀ hydrocarbon chain. Among the fatty amines which can be used according to the invention, mention may be made, for example, of stearyl amidopropyl dimethylamine and distearylamine.

As quaternary ammonium salts, mention may in particular be made, for example:

- those corresponding to the general formula (VII) next :
(VII)
in which the groups R₈to R₁₁, which may be identical or different, represent an aliphatic group, linear or branched, containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R₈to R₁₁comprising from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms. The aliphatic groups can comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens.
The aliphatic groups are for example chosen from C1-C30 alkyl groups, C alkoxy groups₁-VS₃₀, polyoxyalkylene (C₂-VS₆), C-alkylamide₁-VS₃₀, alkyl(C₁₂-VS₂₂)amidoalkyl(C₂-VS₆), alkyl(C₁₂-VS₂₂)acetate, and hydroxy-C₁-VS₃₀,X ^- is an anion selected from the group consisting of halides, phosphates, acetates, lactates, alkyl(C₁-VS₄)sulfates, alkyl(C₁-VS₄)- or (C₁-VS₄)aryl sulfonates.
Among the quaternary ammonium salts of formula (VII), preference is given on the one hand to tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium , cetyltrimethylammonium, benzyldimethylstearylammonium or, on the other hand, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or, finally, palmitylamidopropyltrimethylammonium chloride or marketed stearamidopropyldimethyl-(myristylacetate)-ammonium chloride under the name CERAPHYL® 70 by the company VAN DYK.

- the quaternary ammonium salts of imidazoline, such as for example those of formula ( VIII ) below:
( VIII )
in which R12 represents an alkenyl or alkyl group having from 8 to 30 carbon atoms, for example derived from tallow fatty acids, R13 represents a hydrogen atom, a C ₁ -C ₄ alkyl group or an alkenyl or alkyl group containing from 8 to 30 carbon atoms, R14 represents a C ₁ -C ₄ alkyl group, R15 represents a hydrogen atom, a C ₁ -C ₄ alkyl group, X ^- is an anion chosen from the group of halides , phosphates, acetates, lactates, alkyl(C ₁ -C ₄ )sulfates, alkyl(C ₁ -C ₄ )- or alkyl(C ₁ -C ₄ )aryl sulfonates.
Preferably, R12 and R13 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R14 denotes a methyl group, R15 denotes a hydrogen atom. Such a product is for example marketed under the name REWOQUAT® W 75 by the company REWO.

- di- or tri-quaternary ammonium salts in particular of formula ( IX ) below:
( IX )
in which R16 denotes an alkyl group comprising approximately 16 to 30 carbon atoms optionally hydroxylated and/or interrupted by one or more oxygen atoms, R17 is chosen from hydrogen or an alkyl group comprising 1 to 4 carbon atoms or a -(CH2)3-N+(R16a)(R17a)(R18a), R16a, R17a, R18a, R18 , R19 , R20 and R21 group, which are identical or different, are chosen from hydrogen or an alkyl group comprising 1 to 4 carbon atoms, and X- is an anion selected from the group consisting of halides, acetates, phosphates, nitrates, alkyl(C1-C4)sulfates, alkyl(C1-C4)- or alkyl(C1-C4)aryl- sulfonates, in particular methyl sulfate and ethyl sulfate.
Such compounds are, for example, Finquat CT-P offered by the company FINETEX (Quaternium 89), Finquat CT offered by the company FINETEX (Quaternium 75).

- quaternary ammonium salts containing one or more ester functions, such as, for example, those of formula ( X ) below:
( X )
wherein: R22 is selected from C1-C6 alkyl groups and C1-C6 hydroxyalkyl or dihydroxyalkyl groups; R23 is chosen from: the –C(O)R26 group, C1-C22 hydrocarbon R27 groups, linear or branched, saturated or unsaturated, the hydrogen atom; R25 is chosen from: the –C(O)R28 group, C1-C6 hydrocarbon R29 groups, linear or branched, saturated or unsaturated, the hydrogen atom; R24, R26 and R28, which are identical or different, are chosen from C7-C21 hydrocarbon groups, linear or branched, saturated or unsaturated; r, s and t, identical or different, are integers ranging from 2 to 6; r1 and t1, identical or different, are 0 or 1; r2 + r1 = 2 r and t1 + t2 = 2 t, y is an integer ranging from 1 to 10, x and z, identical or different, are integers ranging from 0 to 10, X- is a simple or complex anion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0 then R23 denotes R27 and that when z is 0 then R25 denotes R29.
The R22 alkyl groups can be linear or branched and more particularly linear.
Preferably, R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
Advantageously, the sum x + y + z is from 1 to 10.
When R23 is a hydrocarbon R27 group, it can be long and have 12 to 22 carbon atoms, or short and have 1 to 3 carbon atoms.
When R25 is a hydrocarbon R29 group, it preferably has 1 to 3 carbon atoms.
Advantageously, R24, R26 and R28, identical or different, are chosen from C11-C21 hydrocarbon groups, linear or branched, saturated or unsaturated, and more particularly from C11-C21 alkyl and alkenyl groups, linear or branched, saturated. or unsaturated.
Preferably, x and z, identical or different, are worth 0 or 1.
Advantageously, y is equal to 1.
Preferably, r, s and t, which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
The anion X- is preferably a halide, preferably chloride, bromide or iodide, an alkyl (C1-C4) sulphate, alkyl (C1-C4)- or alkyl (C1-C4) aryl-sulphonate. It is however possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.
The anion X − is even more particularly chloride, methyl sulphate or ethyl sulphate.
The ammonium salts of formula (XIII) in which: R22 denotes a methyl or ethyl group, x and y are equal to 1, z is equal to 0 or 1, r , s and t are equal to 2; R23 is chosen from: the –C(O)R26 group, methyl, ethyl or C14-C22 hydrocarbon groups, the hydrogen atom, R25 is chosen from: the –C(O)R28 group, the of hydrogen, R24, R26 and R28, identical or different, are chosen from C13-C17 hydrocarbon groups, linear or branched, saturated or unsaturated, and preferably from C13-C17 alkyl and alkenyl groups, linear or branched , saturated or unsaturated.
Advantageously, the hydrocarbon groups are linear.
Mention may be made, for example, among the compounds of formula (XIII) of the salts, in particular the chloride or the methyl sulphate of diacyloxyethyldimethylammonium, of diacyloxyethylhydroxyethyl methylammonium, of monoacyloxyethyldihydroxyethylmethylammonium, of triacyloxyethylmethylammonium, of monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably have 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm or sunflower oil. When the compound contains several acyl groups, the latter may be the same or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or optionally oxyalkylenated alkyldiisopropanolamine on fatty acids or on mixtures of fatty acids of plant or animal origin, or by transesterification of their methyl esters. This esterification is followed by quaternization using an alkylating agent, such as an alkyl halide, preferably methyl or ethyl, a dialkyl sulfate, preferably methyl or ethyl, methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin.
Such compounds are for example marketed under the names DEHYQUART® by the company HENKEL, STEPANQUAT® by the company STEPAN, NOXAMIUM® by the company CECA, REWOQUAT® WE 18 by the company REWO-WITCO.
The composition according to the invention may contain, for example, a mixture of mono-, di- and triester quaternary ammonium salts with a majority by weight of diester salts.
It is also possible to use the ammonium salts containing at least one ester function described in patents US-A-4874554 and US-A-4137180.
It is also possible to use behenoylhydroxypropyltrimethylammonium chloride, for example, offered by the company KAO under the name Quartamin BTC 131.
Preferably, the ammonium salts containing at least one ester function contain two ester functions.
Among the cationic surfactants, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.

Preferably, the surfactant(s) are chosen from anionic surfactants and mixtures thereof, preferably from sulphated anionic surfactants, such as alkyl sulphates, alkyl ether sulphates and mixtures thereof.

When the method uses one or more surfactants, preferably, the total content of surfactant(s) in the composition preferably varies from 0.01 to 15% by weight, more preferably from 0.1 to 25% by weight. , better still from 0.5 to 20% by weight, even better still from 1 to 15% by weight relative to the total weight of the composition containing them.

Oil

The process according to the invention can, in addition, implement one or more oils.

Preferably, composition (B) comprises at least one oil.

By “ oil ” is meant within the meaning of the invention a “ fatty substance ” which is liquid at a temperature of 30° C. and at atmospheric pressure (760 mm Hg). The viscosity at 25° C. is preferably less than 1200 cps, better still less than 500 cps (defined for example from the Newtonian plateau determined using an ARG2 rheometer from TA Instruments equipped with a mobile of cone-plane geometry d a diameter of 60 mm and an angle of 2 degrees over a shear stress range from 0.1 Pa to 100 Pa).

The term “ fatty substance ” is understood to mean an organic compound that is insoluble in water at ordinary temperature (25° C.) and at atmospheric pressure (760 mm Hg) (solubility less than 5% by weight and preferably 1% by even more preferably at 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THF), vaseline oil or decamethylcyclopentasiloxane.

The term “ non-silicone oil or fatty substance ” means an oil or a fatty substance not containing Si—O bonds and a “ silicone oil or fatty substance ” means an oil or a fatty substance containing at least one Si—O bond.

More particularly, the useful oils according to the invention are chosen from non-silicone oils and in particular C ₆ -C ₁₆ hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes; triglyceride oils of plant origin; essential oils ; glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides.

Preferably, the useful oils according to the invention are not (poly)oxyalkylenated or (poly)glycerolated ethers.

Preferably the useful oils according to the invention are not fatty acids in salified form giving water-soluble soaps.

It is recalled that within the meaning of the invention, the alcohols, esters and fatty acids have more particularly at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising 6 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds can comprise one to three carbon-carbon double bonds, conjugated or not.

As regards the C ₆ -C ₁₆ liquid hydrocarbons, the latter are linear, branched, optionally cyclic and preferably are alkanes. By way of example, mention may be made of hexane, cyclohexane, undecane, dodecane, isododecane, tridecane, isoparaffins such as isohexadecane, isodecane, or mixtures thereof. The linear or branched hydrocarbons, of mineral or synthetic origin, comprising more than 16 carbon atoms, are preferably chosen from paraffin or petroleum jelly oils, polydecenes, hydrogenated polyisobutene such as Parléam®, or mixtures thereof.

Among the triglycerides of plant or synthetic origin, mention may be made of liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soy, pumpkin, grapeseed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, coconut, caprylic/capric acid triglycerides such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel, jojoba oil, shea butter oil.

The liquid fatty alcohols suitable for the implementation of the invention are more particularly chosen from saturated or unsaturated, linear or branched alcohols, comprising from 6 to 30 carbon atoms, preferably from 8 to 30 carbon atoms. Mention may be made, for example, of 2-octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleic alcohol, linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol, or mixtures thereof.

As regards the liquid esters of fatty acids and/or fatty alcohols, different from the triglycerides mentioned above; mention may in particular be made of esters of saturated or unsaturated aliphatic mono or polyacids, linear C ₃ -C ₂₉ or branched C ₄ -C ₃₀ and of saturated or unsaturated aliphatic mono or polyalcohols, linear C ₃ -C ₂₉ or branched C ₄ -C ₃₀ , the total carbon number of the esters being greater than or equal to 6, more advantageously greater than or equal to 10. Fatty acid and/or fatty alcohol esters can be used, such as, for example, Purcellin's oil (stearyl octanoate), isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl, 2-hexyldecyl laurate, 2-octyldecyl palmitate, myristate or 2-octyldodecyl lactate.

Among the essential oils contained in the composition of the invention, mention may be made of those mentioned in Ullmann's Encyclopedia of Industrial Chemistry (" Flavors and Fragrances ", Karl-Georg Fahlbusch et al., Published Online: 15 JAN 2003, DOI: 10.1002/ 14356007.a11_141).

According to a preferred variant of the invention, the oil or oils are chosen from C ₆ -C ₁₆ alkanes, polydecenes, liquid fatty acid and/or fatty alcohol esters, in particular triglycerides of vegetable or synthetic, liquid fatty alcohols or mixtures thereof. Better still, the fatty substance is chosen from liquid fatty acid and/or fatty alcohol esters, triglycerides of plant or synthetic origin, or mixtures thereof; more preferably from triglycerides of vegetable or synthetic origin.

According to another very particularly preferred embodiment of the invention, the oils are chosen from oils of natural origin, more particularly oils of vegetable origin, preferably oils of jojoba, babassu, sunflower, olive, coconut , brazil nuts, marula, corn, argan, soy, squash, grapeseed, flax, sesame, hazelnut, apricot, macadamia, arara, coriander, castor, avocado, shea butter oil as well as rapeseed, borage, evening primrose, pomegranate, mango, palm, cottonseed oil, or mixtures thereof.

More particularly, the oils of plant origin are chosen from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, or mixtures thereof, better use avocado oil.

When the process uses one or more oils, preferably, the total content of oil(s) in the composition preferably varies from 0.001 to 99% by weight, more preferably from 0.01 to 90% by weight, better from 5 to 90% by weight, even better from 10 to 90% by weight relative to the total weight of the composition containing them.

Thickening agent

The method according to the invention can, in addition, implement one or more thickening agents.

Preferably, composition (A) comprises at least one thickening agent.

Within the meaning of the present invention, thickening agent means an agent which, by its presence in the composition, makes it possible to increase the viscosity of said composition from at least 10 cPs, preferably by at least 200 cPs, to 25 °C and at a shear rate of 1s ^-1 . This viscosity can be measured using a cone/plane viscometer (Haake R600 rheometer or the like).

The thickening agent(s) may, in particular, be chosen from sodium chloride, fatty acid amides obtained from C ₁₀ -C ₃₀ carboxylic acid (monoisopropanol-, diethanol- or monoethanol-amide of coconut oil, monoethanolamide of oxyethylenated alkyl ether carboxylic acid), polymeric thickeners and in particular nonionic cellulosic polymers (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), guar gum and its nonionic derivatives (hydroxypropylguar), gums of microbial (xanthan gum, scleroglucan gum), crosslinked or non-crosslinked homo- and copolymers based on acrylic acid, methacrylic acid or acrylamidopropanesulfonic acid, as described below, and mixtures thereof.

When the process uses one or more thickening agents, preferably, the total content of thickening agent(s) in the composition preferably varies from 0.01 to 15% by weight, more preferably from 0.1 to 10% by weight, better still from 0.5 to 8% by weight, even better still from 0.5 to 6% by weight relative to the total weight of the composition containing them.

According to a particular embodiment, the process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
a) the application to the keratin fibers of a composition (A) comprising: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts, one or more surfactants, one or more thickening agents;
b) the application to the keratin fibers of a composition (B) comprising one or more (hydrogen)carbonates, one or more surfactants, one or more oils;
c) the application to the keratin fibers of a composition (C) comprising an extract and/or curry leaf powder.

In the method according to the present invention, it is essential that steps a) , b) and c) are successive, that is to say that step c) is implemented after step b) and that step b) is implemented after step a) . The method may comprise one or more additional steps between steps a) and b) and between steps b) and c) but even in such an embodiment, step c) is always implemented after step b ) and step b) is always implemented after step a) .

Step c) can be implemented directly after step b) and step b) can be implemented directly after step a) .

Additives

The compositions useful according to the invention may optionally comprise one or more additives, different from the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric polymers or their mixtures, different from those mentioned above, the anti-dandruff agents, anti-seborrhoeic agents, anti-hair loss and/or regrowth agents, vitamins and pro-vitamins including panthenol, sunscreens, mineral or organic pigments, plasticizers, solubilizing agents, opacifying or pearlescent agents , antioxidants, hydroxy acids, fragrances, preservatives.

Of course, those skilled in the art will take care to choose this or these possible additional compounds in such a way that the advantageous properties inherently attached to the composition according to the invention are not, or substantially not, altered by the addition(s) envisaged. .

The above additives may generally be present in an amount comprised for each of them between 0 and 20% by weight, relative to the total weight of the composition containing them.

The essays

The compositions used in the present invention may be in any form compatible with application to keratin fibers and in particular the hair.

In particular, the compositions (A) , (B) and (C) useful in the invention can be in the form of liquid compositions, pastes or powders. According to a preferred embodiment, the compositions (A) , (B) and (C) are in the form of liquid compositions, such as solutions.

They may be aqueous solutions, in particular hydroalcoholic solutions. They generally comprise water or a mixture of water and one or more solvents, for example chosen from C ₁ to C ₄ lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerol, propylene glycol, 1,3-propanediol and polyethylene glycols; and their mixtures.

When they are present, the total amount of the solvent(s) preferably ranges from 0.01% to 50% by weight, and more preferably from 0.05 to 30% by weight, relative to the weight of each composition. container.

When the composition which contains the metal salt(s) is in the form of a solution, the latter must not flocculate. Depending on the metal salt, the person skilled in the art will choose the appropriate pH to avoid flocculation of the composition.

Process

According to the process of the invention, the compositions (A) , (B) and (C) , described above, are applied to dry or wet keratin fibres.

According to a preferred embodiment, composition (A) and then composition (B) are applied successively. According to this embodiment, composition (C) is applied after composition (B) .

Preferably, the process comprises the application to the keratin fibers of composition (A) , then of composition (B) ; preferably with a pause time between the application of composition (A) and of composition (B) , which can vary from 30 seconds to 1 hour, preferably from 1 min to 40 min.

Preferably, the process comprises the application to the keratin fibers of composition (B) , then of composition (C) ; preferably with a pause time between the application of composition (B) and of composition (C) , which can vary from 30 seconds to 1 hour, preferably from 1 min to 40 min.

Preferably, a pause time of the composition (C) can vary from 30 seconds to 30 min, preferably from 1 min to 15 min. During this pause time, the keratin fibers can be kneaded.

The method of the invention may also comprise a rinsing step after the application of the compositions (A) , (B) and/or (C) .

Preferably, in the process of the invention, steps a) , b) and c) are implemented without an intermediate rinsing step.

More preferably, the method comprises a single final rinsing step. In other words, the keratin fibers are rinsed only after the application of the last composition (C) .

In addition, after applying composition (B) , the keratin fibers can, before applying composition (C), be blotted with absorbent paper in order to remove the excess of compositions (A) and (B ) .

Preferably, the compositions (A) , (B) and/or (C) are applied to the keratin fibers in a mass ratio composition: keratin fibers of 2:1.

Compositions (A) , (B) and/or (C) can be applied using accessories known to those skilled in the art, such as paintbrushes, maryses, brushes or sponges.

Preferably, the compositions (A) , (B) and/or (C) are applied to the keratin fibers at a temperature of between 25° C. and 60° C., preferably between 25° C. and 45° C., more preferably at a temperature between 25°C and 40°C.

set

Another object of the invention is a device with several compartments, preferably three compartments, for coloring keratin fibres, said device comprising at least a first compartment containing the composition (A) as described previously, a second compartment containing composition (B) as described above and a third compartment containing composition (C) as described above.

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.

The following examples serve to illustrate the invention without, however, being of a limiting nature.

Examples

In the examples which follow, all the quantities are indicated in mass percentage of active ingredient (AM) relative to the total weight of the composition (unless otherwise stated).

Coloring composition

Example 1

Composition A1 according to the present invention was prepared from the ingredients whose contents are indicated in the table below:

A1 Logwood extract (35% hematoxylin by weight) 0.52 Vanillin 1.5 Maltose 2.5 manganese gluconate 0.21 Sodium lauryl ether sulfate 5 Guar gum 1 Water QSP 100

Composition B1 was prepared from the ingredients whose contents are indicated in the table below:

B1 Avocado oil 83 Sodium lauryl ether sulfate (70% in water) 9.94 Potassium bicarbonate 3 Water QSP 100

Composition C1 was prepared from the ingredients whose contents are indicated in the table below:

C1 Curry leaf extract
(Company Pfannenschmidt-Hamburg – product ref 13561 FerroPlant®Curry Leaf Extract) 3 pH agent Qs pH (3.2; 4.5; 7 (spontaneous pH) or 8.4) Water QSP 100

The pH agents are:

pH 3.2: dilute hydrochloric acid solution (0.1N); this pH is also achieved with lactic acid.

pH 4.5: dilute hydrochloric acid solution (0.1N)

pH 8.4: dilute sodium hydroxide (0.1M); this pH can also be reached using an ammonia solution.

Staining protocol

Composition A1 was applied using a brush at the rate of 1 ml of composition to a 0.5 g lock of 90% natural white (BN) Caucasian hair. Then the lock was left to stand at 40° C. for 30 minutes.

Then 1 ml of composition B1 was applied to the 0.5 g lock. Then the lock was left to stand at 40° C. for 30 minutes.

The lock of hair was blotted with an absorbent paper to remove the excess of compositions A1 and B1 .

1 g of composition C1 at pH 7 was applied per 0.5 g lock. The lock was kneaded for 5 minutes then rinsed with water and washed with a commercial shampoo, rinsed and dried.

This protocol is repeated identically using compositions C1 having pH values of 3.2; 4.5 or 8.4.

Results

- Hair coloring is evaluated in the L*a*b* system, with a Minolta Spectrophotometer CM2600D spectro-colorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

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.

- Resistance to washing
The lock is washed 5 times using a commercial shampoo. The locks are rinsed with water after each wash. Then the locks are dried and the colorimetric measurements are again carried out using the Minolta Spectrophotometer CM2600D colorimeter.

- Resistance to sweat

The 1 g lock colored according to the method described above is immersed in a closed vial containing 20 ml of artificial sweat. Leave to incubate for 48 hours at 37°C. We take out the wick, we rinse it, and we dry it.

Composition of artificial sweat: sodium chloride: 0.5g; lactic acid: 0.1g; pure urea: 0.1g, albumin: 0.1g, pure water: qs 100g, ammonium hydroxide: qs pH 6.5.

Then the colorimetric measurements are again carried out using the Minolta Spectrophotometer CM2600D colorimeter.

- Light fastness

The colored lock according to the protocol described above was exposed to light according to the following protocol: the colored lock is exposed to light from a Xenotest 150S from Atlas at an average level of illumination from a 1600 Watt Xenon UV lamp. The humidity level is set at 60%. The duration of the exhibition is 2 hours 40 minutes. The color of the lock is measured before and after exposure.

The results are shown in the table below:

These results show that the method according to the invention makes it possible to obtain colorations with various shades.

In addition, the method according to the invention leads to powerful colorations, which are persistent to sweat, to washings and to light, as shown by the results indicated in the table below. The ΔE calculated correspond to the difference in color observed between the dyed hair (Process A1 then B1 then C1) and the color observed after studying the resistance to sweat, washing and light.

Example 2 Comparative

Composition C2 was prepared from the ingredients whose contents are indicated in the table below:

C2 pH agent pH 4.5; 8.4 Water Qs 100

Staining protocol

Composition A1 of Example 1 was applied using a brush at the rate of 1 ml of composition to a 0.5 g lock of 90% natural white (BN) Caucasian hair. Then the lock was left to stand at 40° C. for 30 minutes.

Then 1 ml of composition B1 of Example 1 was applied to the 0.5 g lock. Then the lock was left to stand at 40° C. for 30 minutes.

The lock of hair was blotted with an absorbent paper to remove the excess of compositions A1 and B1 .

1 g of composition C2 (which does not comprise curry leaf extract and/or powder) was applied per 0.5 g lock. The lock was kneaded for 5 minutes then rinsed with water and dried.

This protocol is implemented identically using C2 compositions having pH values of 4.5 (by addition of lactic acid as a pH agent) and 8.4 (by addition of hydroxide sodium as a pH agent).

Results

Hair coloring is assessed as described in Example 1.

The results are shown in the table below:

I* To* b* ΔE Before treatment 59.79 0.07 11.72 Process A1 then B1 then C2 (pH 4.5) 50.61 8.49 25.12 18.29* Process A1 then B1 then C2 (pH 8.4) 16.46 1.54 -0.06 44.9* Resistance to washing pH 8.4 58.01 5.17 10.87 43.11**

* The calculated ΔE correspond to the difference in color observed between the native hair (undyed) and after application of the A1 then B1 then C2 process.

** The calculated ΔE corresponds to the difference in color observed between the dyed hair (Process A1 then B1 then C2 at pH 8.4) and the color observed after studying the washing resistance.

The comparative processA1ThenB1ThenC2(pH 4.5) results in a very weak and unsatisfactory build-up for those skilled in the art of hair dyes. A color close to that of the control lock is obtained.

The comparative process A1 then B1 then C2 (pH 8.4) leads to a deep black coloration. However, after a shampoo, there is almost total loss of color. The initial color of the hair is almost recovered (**ΔE=43.11 after shampooing), unlike the protocol using the curry leaf extract in step C 1 (ΔE=1.98 after shampooing). Thus, the process for coloring the hair according to the invention, using extracts and/or curry leaves, makes it possible to obtain more intense and more persistent colorings in shampoos.

Comparative example 3

Staining protocol

Composition C1 was applied to locks of hair as indicated in Example 1 (compositions A1 and B1 are not applied beforehand).

Results

Hair coloring is assessed as described in Example 1.

The results are shown in the table below:

I* To* b* ΔE Before treatment 59.79 0.07 11.72 - Process C1 (pH 4.5) 61.44 0.35 16.92 5.46 Process C1 (pH 8.4) 57.77 1.46 16.76 5.60 Process C1 (pH 7) 51.31 -0.17 10.35 8.59

The calculated ΔE corresponds to the difference in color observed between the native hair (not dyed) and the color observed after application of the composition C1 .

The comparative process which only uses the compositionC1(at pH 4.5, 8.4 or 7) leads to a very slight and totally unsatisfactory change in hair color for those skilled in the art.

Thus, the method, using only extracts and/or powders of curry leaves, does not make it possible to color the hair satisfactorily.

Claims (21)

Process for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising the following successive steps:
a) the application to the keratin fibers of a composition (A) comprising: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts;
b) the application to the keratin fibers of a composition (B) comprising one or more (hydrogen)carbonates;
c) the application to the keratin fibers of a composition (C) comprising an extract and/or curry leaf powder. Dyeing process according to any one of the preceding claims, in which the polyphenols are chosen from ortho-diphenols (ODPs), that is to say compounds comprising one or more aromatic rings, preferably benzene rings, comprising at least two hydroxy (OH) groups carried by two adjacent carbon atoms of the same aromatic ring. Dyeing process according to any one of the preceding claims, in which the polyphenols are chosen from the ODPs of formula ( I ) below, or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or its solvates such as hydrates:
( I )
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) 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 groups hydroxy or glycosyloxy, 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 (I) 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. Dyeing process according to any one of the preceding claims, in which the polyphenols are ODPs 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. Dyeing process according to any one of the preceding claims, in which the total content of polyphenols varies from 0.05% to 30% by weight, preferably from 0.1 to 20% by weight, better still from 0.2 to 5% by weight relative to the total weight of composition (A) . Dyeing process according to any one of the preceding claims, in which the aldehydes are chosen from the compounds of formulas(III),(IV),(V)Or(VI)following and mixtures thereof:

in which :
R ¹ same or different independently represent:
- a C alkyl or alkenyl radical₁-VS₁₂, optionally substituted by one or more identical or different radicals chosen from a hydroxyl radical, a phosphate radical, an -NH radical₂;
- a hydroxyl radical;
- a C alkoxy radical₁-VS₄;
- a carboxyl radical (-COOH);
- an -OCOAlkyl(C) radical₁-VS₅₎
- a -COOAlkyl(C) radical₁-VS₅);
- a radical (hydroxy)(di)(alkyl)amino -NR^ToR^bOrR ^To ,R ^b , identical or different, representing, independently of one another, a hydrogen atom, a saturated C₁-VS₁₂optionally substituted by a hydroxyl radical;
- an ammonium radical –N⁺(R^vs)₃, Year^-, OrR ^vs , identical or different, represent independently of each other, a saturated alkyl radical in C₁-VS₆,Year-represents an anionic counterion or a mixture of anionic counterions, cosmetically acceptable, guaranteeing the electroneutrality of the molecules;
R ² identical or different represent independently, a hydrogen atom or a saturated or unsaturated alkyl radical in C₁-VS₆, optionally substituted by a hydroxyl radical;
notis an integer ranging from 0 to 4 in the formula (III);
notis an integer ranging from 0 to 3 in the formula (IV)
xrepresents a carbon atom, a nitrogen atom or a –N group⁺(R^d), Year^-OrR ^d represents a C alkyl radical₁-VS₆, optionally substituted by a hydroxyl radical,Year-represents an anionic counterion or a mixture of anionic counterions, cosmetically acceptable, guaranteeing the electroneutrality of the molecules;
pis an integer ranging from 0 to 4;
whenR ¹ represents a C alkyl radical₁-VS₄andnotis 2, these two substituents can be adjacent and can form an aromatic ring with 5 or 6 carbon atoms;
R ³ identical or different represent independently, a saturated or unsaturated alkyl radical in C₁-VS₁₂, optionally substituted by a hydroxyl radical or an amino radical;
thererepresents a -NR group^dOrR ^d represents a C alkyl radical₁-VS₆, optionally substituted by a hydroxyl radical;
zrepresents a carbon atom or a nitrogen atom;
mis an integer of 0, 1 or 2;
R ⁴ represented :
- a hydrogen atom; Or
- a hydrocarbon radical, linear or branched, in C₁-VS₁₆, saturated or unsaturated, when it is unsaturated, it comprises a number of ethylenic unsaturations between 1 and 3; said radical being optionally substituted by 1 to 3 radicals, identical or different, chosen from a hydroxyl radical, an alkoxy radical in C₁-VS₂, a C (poly)hydroxyalkoxy radical₁-VS₄, an –NH radical₂, a C (di)alkylamino radical₁-VS₂, a carboxyl radical in salified form or not, an aminosulfonyl radical, a (poly)hydroxyalkylamino radical in C₂-VS_4,a halogen atom such as chlorine atom, fluorine atom or bromine atom; said radical possibly being interrupted by a saturated or unsaturated 5- or 6-membered, preferably 6-membered, ring, optionally substituted by 1 to 3 identical or different radicals chosen from a C alkyl radical₁-VS₁₂, a C hydroxyalkyl radical₁-VS₁₀or a C alkoxy radical₁-VS₂;
- a phenyl radical, optionally substituted by 1 to 3 identical or different radicals chosen from a C alkyl radical₁-VS₁₂, a C hydroxyalkyl radical₁-VS₁₀, a hydroxyl radical or an alkoxy radical in C₁-VS₂;
R ⁵ represents a hydrogen atom or a hydrocarbon radical, linear or branched, in C₁-VS₁₆, saturated or unsaturated. Dyeing process according to any one of the preceding claims, in which the aldehydes are chosen from the following compounds: benzaldehyde, cinnamaldehyde, coniferaldehyde, sinapaldehyde, caffealdehyde (3,4-Dihydroxycinnamaldehyde), vanillin, ethyl vanillin (3-ethoxy- 4-hydroxybenzaldehyde), isovanillin (3-hydroxy-4-methoxybenzaldehyde), anisaldehyde (4-methoxybenzaldehyde), 4-formylbenzoic acid, methyl 4-formylbenzoate (methyl 4-formylbenzoate), p -dimethylaminobenzaldehyde, p -di(hydroxyethyl) aminobenzaldehyde, p -di(hydroxymethyl)aminobenzaldehyde heliotropine (1,3-benzodioxole-5-carbaldehyde), 2,4-dihydroxy-3-methylbenzaldehyde, syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde), phenylacetaldehyde, bud (3 -(4- tert -butylphenyl)propanal), 2-phenylpropionaldehyde, cyclamen aldehyde, 2-(4-methylphenyl)acetaldehyde, lilial (3-(4-tert-butylphenyl)-2-methylpropanal), hexyl cinnamaldehyde, pyridoxal (3 -hydroxy-5-(hydroxymethyl)-2-methylpyridine-4- carbaldehyde), pyridoxal (4-formyl-5-hydroxy-6-methylpyridin-3-yl)methyl dihydrogen phosphate phosphate), 1-methyl-4-formylpyridinium salts (such as chloride and methylsulfate salts), salts 1-methyl-4-formylquinolinium (such as chloride, methylsulfate and toluene sulfonate salts), geranial, neral, citronellal, 2,4,6-trihydroxybenzaldehyde, cuminaldehyde, retinal, hydroxyisohexyl-3-cyclohexene carboxaldehyde, salts (4-formylphenyl)-trimethyl-ammonium (such as chloride and methylsulfate salts), 3,4,5-trihydroxybenzaldehyde, myristic aldehyde ( n -tetradecanal), mentha-1,3-dien-7-al, p -mentha-1,3-dien-7-al, salicylaldehyde, procatechuic aldehyde (3,4-dihydroxybenzaldehyde), indole-3-carboxaldehyde, divanillin, salts of divanillin (such as sodium and potassium salts), and their mixtures, as well as the extracts containing it or them, such as Cinnamomum Cassia oleoresin; more preferably chosen from the following compounds: benzaldehyde, cinnamaldehyde, vanillin, ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde), 1-methyl-4-formylquinoline toluene sulfonate, 4-formylbenzoic acid, methyl 4-formylbenzoate (methyl 4 -formylbenzoate), p -dimethylaminobenzaldehyde, p -di(hydroxyethyl)aminobenzaldehyde, p -di(hydroxymethyl)aminobenzaldehyde, pyridoxal (3-hydroxy-5-(hydroxymethyl)-2-methylpyridine-4-carbaldehyde), divanilline and mixtures thereof, as well as the extracts containing it or them, such as Cinnamomum Cassia oleoresin. Dyeing process according to any one of the preceding claims, in which the sugars are chosen from monosaccharides, oligosaccharides and polysaccharides; preferably from sucrose, fructose, maltose, cellobiose, glucose, ribose, lactose, trehalose, arabinose, and their in particular alkylated derivatives, and more preferably maltose. Dyeing process according to any one of the preceding claims, in which the total content of aldehydes and/or sugars varies from 0.01% to 20% by weight, preferably from 0.05 to 15% by weight, better from 0.1 to 10% by weight relative to the total weight of composition (A) . Dyeing process according to any one of the preceding claims, in which the manganese salts are chosen from chlorides, fluorides, iodides, bromides, sulphates, phosphates, nitrates, perchlorates, carbonates, carboxylates , and mixtures thereof. Dyeing process according to any one of the preceding claims, in which the manganese salts are chosen from Mn(II) salts, preferably chosen from manganese (II) carboxylates, manganese (II) halides and their mixtures, and more preferably from among manganese (II) chloride, manganese (II) gluconate and mixtures thereof. Dyeing process according to any one of the preceding claims, in which the total content of the manganese salts varies from 0.001% to 10% by weight, preferably from 0.01 to 5% by weight, better still from 0.1 to 2 % by weight relative to the total weight of composition (A) . Dyeing process according to any one of the preceding claims, in which the (hydrogen)carbonates are chosen from the compounds of the following formulas:
- R' ⁺ , HCO ₃ ^- with R' representing a hydrogen atom, an alkali metal, an ammonium group R'' ₄ N ⁺ - or phosphonium R'' ₄ P ⁺ - where the R'' groups, identical or different, represent a hydrogen atom, an optionally substituted (C ₁ -C ₆ )alkyl group such as hydroxyethyl; when R' represents a hydrogen atom, the hydrogen carbonate is then called dihydrogen carbonate (CO ₂ , H ₂ O); And
- Met' ²⁺ (HCO ₃ ^- ) ₂ with Met' representing an alkaline-earth metal;
and preferably from alkaline hydrogen carbonates, alkaline-earth hydrogen carbonates, ammonium hydrogen carbonates and mixtures thereof; and more preferably from alkaline hydrogen carbonates, alkaline earth hydrogen carbonates and mixtures thereof;
and better still, from sodium hydrogen carbonates, potassium hydrogen carbonates, magnesium hydrogen carbonates, calcium hydrogen carbonates and mixtures thereof;
and even better, from sodium hydrogen carbonates, potassium hydrogen carbonates and mixtures thereof. Dyeing process according to any one of the preceding claims, in which the total content of (hydrogen)carbonates varies from 0.01% to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1 to 8% by weight relative to the total weight of the composition(B). Coloring process according to any one of the preceding claims, in which the total content of the curry extracts and/or powders preferably varies from 0.001% to 40% by weight, and more preferably from 0.01% to 30% by weight, better, from 0.05 to 5% by weight for the curry leaf extract and preferably, from 0.001% to 40% by weight, and more preferably from 0.01% to 30% by weight, better, 0.05 to 15% by weight for the curry leaf powder, relative to the total weight of composition (C) . Dyeing process according to any one of the preceding claims, in which steps a) , b) and c) are carried out without an intermediate rinsing step. Dyeing process according to any one of the preceding claims, in which the pH of the composition (C) is aqueous and has a pH greater than or equal to 2, in particular, this pH ranges from 2 and 11, preferably this pH ranges from 3 to 10. Dyeing process according to any one of the preceding claims, comprising the use of at least one surfactant. Coloring process according to any one of the preceding claims, comprising the use of at least one oil. Dyeing process according to any one of the preceding claims, comprising the use of at least one thickening agent. Device with several compartments, preferably three compartments, for coloring keratin fibres, at least one first compartment containing the composition(AT)comprising: one or more polyphenols, one or more aldehydes and/or sugars, one or more manganese salts, a second compartment containing the composition(B)comprising one or more (hydrogen)carbonate and a third compartment containing the composition(VS)comprising a curry leaf extract and/or powder.