FR3111814A1 - Process for dyeing keratin fibers from powder and / or coloring extract of indigoferous plants and compounds comprising at least one carbonyl group - Google Patents

Abstract

Process for dyeing keratin fibers from powder and/or extract of indigo-bearing plants and from compounds comprising at least one carbonyl group The subject of the invention is a process for dyeing keratinous fibres, comprising the application of at least one powder of indigo-bearing plants and/or a coloring extract of indigo-bearing plants and of at least one compound comprising at least one carbonyl group.

Description

Process for dyeing keratinous fibers from powder and/or coloring extract of indigo-bearing plants and from compounds comprising at least one carbonyl group

The subject of the invention is a process for dyeing keratin fibers, comprising the application to keratin fibers, in particular human keratin fibers such as the hair, of at least one powder and/or at least one coloring extract of indigo-bearing plants and of at least one compound comprising at least one carbonyl group.

A subject of the present invention is also the use of at least one compound comprising at least one carbonyl group for modulating the color of colored keratin fibers from a composition comprising at least one indigo plant powder and/or at least one coloring extract of indigo plants.

A further subject of the present invention is the use of at least one compound comprising at least one carbonyl group to suppress the yellow/green reflections provided by indigo on the day of the coloring and to stabilize the coloring over time the color of the keratin fibers colored from a composition comprising powder of indigo plants and/or a coloring extract of indigo plants.

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

The first, called oxidation coloring or permanent coloring, consists of using one or more oxidation dye precursors, more particularly one or more oxidation bases possibly associated with one or more couplers.

Usually, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, allow access, through an oxidative condensation process, to colored species which remain trapped inside the fiber.

Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of molecules involved in oxidation bases and couplers allows a rich palette of colors to be obtained.

The second mode of coloring, called direct or semi-permanent coloring, includes the application of direct dyes which are colored and coloring molecules, having an affinity for fibers. Given the nature of the molecules used, these remain on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of precursors of oxidation dyes. The advantage of this last type of coloring is that it does not require an oxidizing agent, which limits fiber degradation. The resulting colorations are generally chromatic but are however less tenacious than the colorations obtained by oxidation staining. The nature of the interactions which link the direct dyes to the keratinous fibres, as well as their desorption from the surface and/or from the core of the fibre, are responsible for their lower tenacity.

The first hair dyes were semi-permanent. One of the best-known natural dyes is indigo (see Ullmann's Encyclopedia of Industrial Chemistry , " hair preparation ", point 5.2.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; 10.1002/14356007.a12 571 .pub2). Indigo continues to be used to beautify women by coloring hair, nails, or to color fabrics (jeans), leather, silk and wool, etc. Indigo [482-89-3] is a natural blue dye and its isomer indirubin is red.

Their formula is: C ₁₆ H ₁₀ N ₂ O ₂ ; and their chemical structures are as follows:

The presence of these two isomers explains the presence of a more or less marked purplish indigo color depending on the respective proportion in the hair of the 2 isomers formed in the hair (in particular from violet to purple if the quantity of indirubin increases).

Indigo, derived from indican, can be prepared from different so-called indigo plants such as Indigofera tinctoria , Indigo suffruticosa , Polygonum tinctorium , etc. (see Kirk-Othmer Encyclopedia of Chemical Technology , updated on 04/17/ 2009, DOI: 10.1002/0471238961.0425051903150618.a01.pub2). Indigo plants are usually cut and soaked in hot water, heated, fermented and oxidized in air to release the mauve-blue colored indigo (see Chem. Rev. 2011, 111 , 2537–2561, p 2537-2561). Indigo is the result of the hydrolysis and then the oxidation of indican (glycosylated precursor).

Hair coloring from indigo leaves is however difficult because the kinetics of coloring in keratin fibers is variable. The coloring process from indigo leaf powder is difficult to control because of the competitive reaction of formation of indirubin (also involving an oxidation step with formation of isatin of intermediate yellow color) bringing yellow to purple reflections to brown hair over time.

The colorings resulting from indigo are therefore generally evolving over time in terms of color, they have a characteristic yellow/green coloring on the day of the coloring (unattractive "raw" color, little appreciated by coloring consumers) which evolves towards colorations sought after a few hours (48 hours), even a few days (one week). This color can also change over time, with the appearance of purplish red reflections, generally after two to three weeks.

To remedy this problem of unattractive coloring on the day of coloring and which evolves over time, it is known to add direct dyes to mask unwanted reflections. These direct dyes are generally those used in direct dyeing such as nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes (see for example EP 0 806 199). However, although it is masked, the reflection provided on the day of application does not prevent the color change over time.

There is therefore a real need to develop coloring processes based on natural dyes, in particular based on indigo and powders or extracts of indigo-bearing plants, which make it possible to obtain powerful colorings in terms of rise, aesthetics and with various shades (natural, chromatic and intermediate) from the end of the coloring which do not present unsightly yellow/green reflections and do not turn red over time.

These colorations must also have good resistance to external agents (light, bad weather, shampoos), while remaining tenacious and/or homogeneous.

This object is achieved with the present invention which relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to the keratin fibers of at least one powder and/or at least one extract dye of indigo-bearing plants and of at least one compound comprising at least one carbonyl group, applied together or separately.

According to a first embodiment, the process for dyeing keratin fibers, in particular human keratin fibers such as the hair according to the invention comprises a step of treating the keratin fibers with a composition comprising at least one compound comprising at least one carbonyl group and at least one powder and/or at least one coloring extract of indigo plants.

According to a second embodiment, the method for dyeing keratin fibers, in particular human keratin fibers such as the hair according to the invention comprises the following steps:
- the application to the keratinous fibers of a composition comprising one or more powder(es) of indigo plant(s) and/or one or more coloring extract(s) of indigo plant(s) s),
- the application to the keratin fibers of a composition comprising at least one compound comprising at least one carbonyl group.

Each step of the process according to the invention as described above can be preceded by one or more pre-treatment step(s) and/or followed by one or more post-treatment step(s) as described below.

The application of at least one compound comprising at least one carbonyl group makes it possible, in particular, to suppress the yellow/green reflections provided by the indigo on the day of coloring and to stabilize the coloring over time.

The coloring is powerful and aesthetic from the day of application, while remaining natural and preserving the integrity of the keratin fibres. In addition, the color has good resistance to external agents. It is also homogeneous.

A subject of the invention is also the use of at least one compound comprising at least one carbonyl group and/or of a composition comprising at least one compound comprising at least one carbonyl group to neutralize reflections and stabilize the color in the keratin fibers colored from a composition comprising at least one powder of indigo plants and/or at least one coloring extract of indigo plants. The color is free of yellow/green reflections on the day of application and does not change to red over time.

By “ natural dye ” is meant any dye or dye precursor originating from a natural source, in particular of plant origin. Natural dyes can in particular be obtained by extraction (and possibly purification) from a plant matrix, by grinding plants or parts of plants, roots, wood, bark, berries, lichens, leaves, flowers, nuts or seeds. Natural dyes can also be obtained by fermentation.

In the following, when a substance is said to be “ synthetic ”, we mean that it has no natural occurrence and that it is only obtained by chemical synthesis or hemisynthesis. In particular, it is a substance which is not obtained from a plant matrix.

In the present application, when compounds are mentioned, it is also meant their optical isomers, their geometric isomers, their tautomers, their salts and/or their solvates, alone or as a mixture.

In the present application, the term "alkyl" or "alk" radical or group means a hydrocarbon chain. This chain can be linear or branched, interrupted by atoms or groups of atoms. It may also contain substituents such as atoms or groups of atoms. It comprises a number of atoms which is indicated by the formula in Cx-Cy, with x and y respectively the minimum number and the maximum number that the longest linear chain comprises.

In what follows, and unless otherwise indicated, the limits of a range of values are included in this range, 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 ”.

Powder of indigo-bearing plants and/or coloring extract of indigo-bearing plant(s)

The method according to the invention uses at least one indigo plant powder and/or at least one coloring extract of indigo plant(s).

The " indigoferous plant powder " and the " indigoferous plant coloring extract " are distinguished in that the powder is a product originating from indigoferous plants, the said plants or parts of plants being reduced by grinding or other mechanical means, into fine particles and the extract is a product of maceration of indigo plants or parts of indigo plants in water or organic solvents or mixtures thereof.

Preferably, as useful indigo-bearing plant according to the invention, mention may be made of numerous species from the genera:
- Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata Indigofera arrecta, Indigofera gerardiana, Indigofera argentea, Indigofera indica, Indigofera longiracemosa ;
- Isatis such as Isatis tinctoria;
- Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria) ;
- Wrightia such as Wrightia tinctoria ;
- Calanthe such as Calanthe veratrifolia; And
- Baphicacanthus such as Baphicacanthus cusia.

Each indigo plant can be used alone or within the scope of the present invention, a mixture of indigo plants can be used. Preferably, a single indigo plant is used.

Preferably, the indigo-bearing plant is of the Indigofera genus and more particularly is chosen from Indigofera tinctoria , suffruticosa or argentea or their mixture, preferably Indigofera tinctoria.

All or part of the indigo plants can be used. In particular, the leaves are used, in particular, for Indigofera tinctoria .

The indigo plant(s) powder can be sieved.

According to a particular embodiment of the invention, the powder of indigo-bearing plant(s) consists of fine particles with particle sizes less than or equal to 500 μm, preferably inclusively between 50 and 300 μm and more preferably between 10 and 200 µm.

The indigo-bearing plant(s) particles preferably have a water content of between 0 to 10% by weight, relative to the total weight of plant(s) powder.

Among the dye extracts of indigo plants which are useful according to the process of the invention, mention may be made of indican and the natural extracts containing it.

When the method according to the invention uses indican and the natural extracts containing it, one or more enzyme(s) with glycosidase activity can also be used.

Preferably, indican and the natural extracts containing it, when they are present, are applied to the keratin fibers from a composition also comprising one or more enzyme(s) with glycosidase activity.

The enzyme(s) with glycosidase activity may be of plant, animal, fungal or bacterial origin.

The useful glycosidases according to the invention can come from plant powders, preferably chosen from apple seed powders, apricot kernel powders, almond powders, vanilla pod powders and mixtures thereof.

Preferably, the glycosidases of the invention are glucosidases and in particular β-glucosidases.

These enzymes carry out a hydrolysis of –O-glucoside bond in β-glucoside of a monosaccharide or oligosaccharide comprising a glucose part.

These enzymes are known under the names of gentiobiase, cellobiase, emulsin, elaterase, aryl-β-glucosidase, β-D-glucosidase, β-glucoside glucohydrolase, arbutinase, amygdalinase, p-nitrophenyl β-glucosidase, primeverosidase, amygdalase, linamarase, salicilinase, and β-1,6-glucosidase (EC number 3.2.1.21 - Locus Chr. 4 p15.31). These are also known as Amygdalin β-glucosidase, Prunasin β-glucosidase, Vicianin β-glucosidase, Glucosylceramidase, and cellulase-like enzymes produced primarily by fungi, bacteria, and protozoa that catalyze the hydrolysis of cellulose.

According to a preferred embodiment of the invention, the glycosidase(s), when they are present, represent from 0.0001% to 10% by weight approximately of the total weight of the composition(s) containing this or these glycosidases and also more preferably from 0.0005% to 0.1% by weight approximately.

Examples of glycosidases include, for example, O-Glycan-peptide hydrolase marketed by Sigma-Aldrich under the name O-Glycosidase (EC 3.2.1.97)

Examples of glucosidases include:
- β-primeverosidase, marketed by the company Amano under the name Aromase®;
- cellulase marketed by the company Amano under the name Cellulase DS®; And
- β-glucosidases marketed by DuPont under the names MULTIFECT® CX 15L and Optimase® CX 15L; glucosidases of natural origin such as β-glucosidases from almonds, such as in particular sweet almond glucosidase EC 3.2.1; β-Glucosidase from almonds marketed by Aldrich under the name 49290 SIGMA β-Glucosidase from almonds lyophilized, powder, ≥6 U/mg.

The powders of indigo plants and/or coloring extracts of indigo plant(s) as defined above are applied from a composition containing the powders of indigo plants and/or coloring extracts of indigo plant(s). ), preferably, in a total content ranging from 0.01% to 50% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 40% by weight, better still from 0, 5 to 30% by weight relative to the total weight of the composition containing them .

According to another embodiment, the method according to the invention can implement at least one powder of indigo plant(s) and/or at least one coloring extract of indigo plant(s), preferably an indigo-bearing plant powder and/or an extract of indigo-bearing plant(s) in a total content ranging from 1 to 100% by weight, preferably from 5 to 100% by weight, better still, from 10 to 50% by weight relative to the total weight of this composition.

Compound comprising at least one carbonyl group

The process according to the invention uses at least one compound comprising at least one carbonyl group.

The compounds containing at least one carbonyl group useful according to the invention can be natural or synthetic, preferably they are natural.

The natural compounds comprising at least one carbonyl group 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 oleoresin cassia , 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 and 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 compounds comprising at least one carbonyl group which are useful according to the invention can be chosen from the compounds comprising at least one aldehyde group, the compounds comprising at least one ketone group and their mixtures and more particularly the compounds comprising at least one carbonyl group are chosen from compounds containing at least one aldehyde group and mixtures thereof.

The compounds comprising at least one carbonyl group which are useful according to the invention are preferably chosen from the compounds of formulas(I),(II),(III)Or(IV)following and mixtures thereof:

In which :
R ¹ independently represents:
- 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);
- a radical -OCOAlk(C₁-VS₅₎
- a radical -COOAlk(C₁-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 represents independently, a hydrogen atom or a saturated or unsaturated alkyl radical in C₁-VS₆, optionally substituted by a hydroxyl radical;
notis an integer between 0 and 4 inclusively in the formula (I);
notis an integer between 0 and 3 inclusive in the formula (II)
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 comprised inclusively between 0 and 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 independently represents a saturated or unsaturated C alkyl radical₁-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 compound comprising at least one carbonyl group; 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 compound(s) comprising at least one carbonyl group useful according to the invention can be introduced pure or mixed with other compounds. By way of example, compounds comprising at least one carbonyl group can be present in natural extracts such as, for example, cinnamomum cassia oleoresin.

The compounds comprising at least one carbonyl group which are 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 heliotropin (1,3-benzodioxole-5-carbaldehyde), 2,4-dihydroxy-3-methylbenzaldehyde, syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde), phenylacetaldehyde, budgeal (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), 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-ammonium salts (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, divanillin salts (such as sodium and potassium salts ), and their mixtures, as well as the extracts containing it or them, such as Cinnamomum Cassia oleoresin.

Better still, the compounds containing at least one carbonyl group 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-toluene sulphonate 4-formylquinoline, 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 their mixtures, as well as the extracts containing it or them such as Cinnamomum Cassia oleoresin.

When the compounds comprising at least one carbonyl group 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 E configuration.

According to another preferred embodiment, the compoundsnaturalcomprising at least one carbonyl group 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.

The compounds comprising at least one carbonyl group as defined above are applied from a composition containing them, preferably in a total content ranging from 0.01% to 20% by weight relative to the total weight of the composition in which they are, preferably from 0.05 to 20% by weight, better still from 0.1 to 5% by weight relative to the total weight of the composition containing them .

Additional direct dyes

The process according to the invention can also implement one or more additional direct dye(s) different from the powder(s) and/or from the extract(s). s) indigo plant(s) dye(s).

When they are present, the additional direct dye(s) are preferably applied to the keratin fibers from a composition which also comprises at least one powder of indigo plants and/or at least one coloring extract of plant(s) indigo-bearing(s).

These additional direct dyes can be synthetic or natural.

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 natural direct dye(s) different from the powder(s) and from the dye(s) extract(s) of indigo-containing plant(s) are for example chosen from lawsone, juglone, indigo, leuco indigo, indirubin, isatin, hennotannic acid, alizarin, carthamine, morine, purpurin, carminic acid, kermesic acid, laccaic acid purpurogalline, protocatechaldehyde, curcumin, spinulosin, apigenidin, orceins, carotenoids, betanin, chlorophylls, chlorophyllins, monascus, polyphenols or orthodiphenols.

Among the useful ortho-diphenols according to the invention, mention may be made of: 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.

These additional direct dyes are preferably chosen from natural direct dyes different from the powder(s) and from the extract(s) dye(s) of indigo-bearing plant(s). s), more preferably chosen from indigo, leuco-indigo, lawsone and henna extracts and/or powders, even more preferably chosen from lawsone and henna extracts and/or powders.

These natural direct dyes different from the powder(s) and from the extract(s) dye(s) of indigo-bearing plant(s) can be added in the form of defined compounds, extracts, or parts of plants. The defined compounds of extracts, or parts of plants are preferably found in the form of powders, in particular fine ones, the particles of which have sizes identical to that of the powder of indigo-bearing plant(s) as defined previously.

By “henna” is meant a powder of a henna plant and/or a coloring extract of a henna plant, preferably of a henna plant such as Lawsonia alba or Lawsonia inermis . The powder and/or the coloring extract of the henna plant notably comprises lawsone and/or one of its glucosylated precursors and other derivatives such as THAP or 2,3,4,6-tetrahydroxyacetophenone and its glycosylated versions. Preferably, the henna used according to the present invention is in powder form. Preferably, the henna used in the invention is red henna ( Lawsonia inermis, alba ). Lawsone [83-72-7] (CI Natural Orange 6; CI 75420) also known as isojuglone, can be found in Henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably the henna is in the form of leaf powder.

The additional direct dyes different from the powder(s) and from the extract(s) dye(s) of indigo-containing plant(s) as defined above, when they are present, are preferably applied from a composition containing them in a total content ranging from 0.01% to 50% by weight relative to the total weight of the composition in which they are found, preferably from 0, 1 to 50% by weight, better still from 0.3 to 40% by weight relative to the total weight of the composition containing them .

Etchants

The process according to the invention can also implement one or more mordant or mordant agent(s) conventionally used in the textile industry and cosmetically acceptable.

The mordanting agent(s) useful according to the invention are metal salts, or else chemical agents making it possible to significantly improve the rise of the dyes.

The mordanting agent(s) useful according to the invention are preferably chosen from iron salts such as iron sulphate, iron gluconate, iron chloride, iron acetate; aluminum salts such as aluminum potassium sulphate; titanium salts such as potassium titanium oxalate; calcium salts such as calcium chloride, calcium gluconate; manganese salts such as manganese gluconate; copper salts such as copper sulphate, copper gluconate, copper chloride, copper acetate; zinc salts such as zinc gluconate, strontium salts such as strontium acetate, sodium salts such as sodium carbonate, magnesium salts and mixtures thereof, certain polymers such as tannins, chitosan of variable molecular weight, polyamines, polyvivnylpyridine.

The mordanting agent(s) useful according to the invention is (are) preferably chosen from zinc salts, iron salts, aluminum salts, manganese salts, titanium salts, tannins, chitosan and mixtures thereof.

The mordanting agents as defined above, when they are present, are preferably applied from a composition containing them in a total content ranging from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 10% by weight, better still from 0.3 to 8% by weight relative to the total weight of the composition containing them .

Reducing agents

The process according to the invention can also implement one or more reducing agent(s).

The reducing agent(s) useful according to the invention are preferably chosen from thiols, hydrides, sulfites, bisulfites, metabisulfites, sugars other than compounds comprising at least one carbonyl group useful according to the invention and phosphines.

Among the thiols, mention may be made of thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, thiomalic acid, 2,3-dimercaptosuccinic acid, cysteine, N-glycyl-L-cysteine, L-cysteinylglycine and their esters and salts, thioglycerol, cysteamine and its C ₁ -C ₄ acylated derivatives, N-mesylcysteamine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N-(mercapto- 2-ethyl) gluconamide, pantetheine, N-(mercaptoalkyl)-ω-hydroxy alkylamides, for example those described in patent application EP-A-354 835, N-mono or N,N-dialkylmercapto-4 butyramides for example those described in patent application EP-A-368 763, aminomercaptoalkylamides, for example those described in patent application EP-A-432 000, derivatives of N-(mercapto-alkyl)succinamic acids and N- (mercaptoalkyl)succinimides, for example those described in patent application EP-A-465,342, alkylamino mercaptoalkylamides, for example those described in s patent application EP-A-514 282, the azeotropic mixture of 2-hydroxypropyl thioglycolate and (2-hydroxy-1-methyl)ethyl thioglycolate as described in patent application FR-A-2 679 448 , mercaptoalkylaminoamides, for example those described in patent application FR-A-2,692,481, N-mercapto alkyl alkane diamides, for example those described in patent application EP-A-653,202.

Among the hydrides, mention may be made of sodium borohydride or potassium borohydride.

Among the sulfites or bisulfites, mention may be made of the sulfites or bisulfites of an alkali metal or alkaline-earth metal, of ammonium or of alkanolamine and in particular the sulfite or the bisulfite of sodium, the sulfite or the bisulfite of potassium, the sulfite or monoethanolamine bisulphite.

Among the metabisulfites, mention may be made of sodium metabisulfite or potassium metabisulfite.

Among the phosphorus derivatives, mention may be made of phosphines or phosphites such as those described in patent application FR2870119.

Among the sugars other than the compounds containing at least one carbonyl group which are useful according to the invention, mention may be made of galactose, xylose, glucose, lactose and fructose.

The reducing agent(s) useful according to the invention are preferably chosen from thiols and sugars, more preferably from thioglycolic acid and its salts, cysteine and its salts, sodium metabisulphite, potassium, galactose, xylose, glucose and mixtures thereof.

The reducing agents as defined above, when they are present, are preferably applied from a composition containing them in a total content ranging from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 10% by weight, better still from 0.3 to 8% by weight relative to the total weight of the composition containing them.

Oxidizing agents

The process according to the invention can also implement one or more oxidizing agent(s).

The oxidizing agent(s) useful according to the invention are preferably chosen from hydrogen peroxide or one or more hydrogen peroxide generator system(s).

Among the systems generating hydrogen peroxide, mention may be made of:
- urea peroxide;
- polymer complexes which can release hydrogen peroxide such as polyvinylpyrrolidone/H ₂ O ₂ in particular in the form of powders and the other polymer complexes described in US Pat. No. 5,008,093; US 3,376,110; US 5,183,901;
- oxidases producing hydrogen peroxide in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase), peroxidases such as HorseRadish peroxidase, laccases, uricases with their possible cofactors;
- metal peroxides generating hydrogen peroxide in the water, such as calcium peroxide, magnesium peroxide;
- persulphates, such as sodium persulphate, potassium persulphate, ammonium persulphate;
- perborates, such as sodium perborate; And
- percarbonates, such as sodium percarbonate, or potassium percarbonate.

The oxidizing agent useful according to the invention is preferably hydrogen peroxide, peroxidases such as horseradish peroxidase, laccases and uricases with their possible co-factors.

The oxidizing agents as defined above, when they are present, are preferably applied from a composition containing them in a total content ranging from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 10% by weight, better still from 0.1 to 8% by weight relative to the total weight of the composition containing them.

The oxidizing agent(s) useful according to the invention make it possible in particular to reveal the color. They are preferably applied to the keratin fibers in a post-treatment step, that is to say, after a step of applying to the keratin fibers a composition comprising at least one powder of indigo-bearing plants and / or at least one coloring extract of indigo-bearing plant(s) and optionally at least one compound comprising a carbonyl group.

Alkaline agents

The process according to the invention can also implement one or more alkaline, mineral(s), organic(s) or hybrid agent(s), preferably mineral.

Within the meaning of the present invention, the terms “ alkaline agent ” or “ alkalizing agent ” are used interchangeably.

The inorganic alkalizing agent(s) are preferably chosen from ammonia, alkali metal carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonate, alkali metal or alkaline metal phosphates. earthy materials such as sodium phosphates or potassium phosphates, sodium or potassium hydroxides and mixtures thereof.

The organic basifying agent(s) are preferably chosen from alkanolamines, amino acids, organic amines, oxyethylenated and/or oxypropylene ethylenediamines, 1,3 diaminopropane, 1,3 diamino 2 propanol, spermine, spermidine and their mixtures.

By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C ₁ -C ₈ alkyl groups carrying one or more hydroxyl radicals.

The organic amines chosen from alkanolamines such as mono-, di- or tri-alkanolamines, comprising one to three C ₁ -C ₄ hydroxyalkyl radicals, which may or may not be identical, are particularly suitable for carrying out the invention.

In particular, the alkanolamine(s) are chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1 -propanol, triisopropanol-amine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino- methane and their mixtures.

Advantageously, the amino acids are basic amino acids comprising an additional amine function. Such basic amino acids are chosen, preferably, from histidine, lysine, arginine, ornithine, citrulline.

The organic amine can also be chosen from organic amines of the heterocyclic type. Mention may in particular be made, in addition to the histidine already mentioned in the amino acids, of pyridine, piperidine, imidazole, triazole, tetrazole, benzimidazole. The organic amine can also be chosen from amino acid dipeptides. As amino acid dipeptides which can be used in the present invention, mention may in particular be made of carnosine, anserine and balenine. The organic amine can also be chosen from compounds comprising a guanidine function. As amines of this type different from arginine which can be used in the present invention, mention may in particular be made of creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.)

As hybrid compounds, it is possible in particular to use guanidine carbonate or monoethanolamine hydrochloride.

The alkaline agent(s) useful according to the invention is (are) preferably chosen from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; ammonia, carbonates or bicarbonates such as sodium (hydrogen)carbonate and potassium (hydrogen)carbonates and mixtures thereof.

The alkaline agents as defined above, when they are present, are preferably applied from a composition containing them in a total content ranging from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.1 to 15% by weight, better still from 0.3 to 10% by weight relative to the total weight of the composition containing them.

According to one embodiment, the pH of the composition comprising at least one alkaline agent is between 8 and 13; preferably between 8.0 and 12.

The pH of the composition can be adjusted to the desired value by means of acidic or alkaline agent(s) usually used in dyeing keratinous fibers or even by means of known buffer systems. of the skilled person.

The alkaline agent or agents useful according to the invention make it possible in particular to stabilize the color, so as to obtain, from the end of the coloring process according to the invention, a definitive coloring of the keratin fibres. They are preferably applied to the keratin fibers in a post-treatment step, that is to say, after a step of applying to the keratin fibers a composition comprising at least one powder of indigo-bearing plants and / or at least one coloring extract of indigo-bearing plant(s) and optionally at least one compound comprising a carbonyl group.

According to a first variant, the process for dyeing keratin fibres, in particular human keratin fibers such as the hair, according to the invention comprising at least one step of pretreating the keratin fibers using: at least one mordanting agent and/or at at least one reducing agent and/or at least one oxidizing agent as described above.

According to a second variant, the process for dyeing keratin fibers in particular human keratin fibers such as the hair according to the invention comprising at least one post-treatment step of the keratin fibers implementing: at least one alkaline agent and/or at least one mordanting agent and/or at least one oxidizing agent as described previously.

According to a third variant, the process for dyeing keratin fibres, in particular human keratin fibers such as the hair, according to the invention comprising at least one step of pretreating the keratin fibers using: at least one mordanting agent and/or at at least one reducing agent and/or at least one oxidizing agent as described above and at least one post-treatment step for the keratin fibers using: at least one alkaline agent and/or at least one mordanting agent and/or at least one oxidizing agent as described previously.

The pre-treatment step(s) and the post-treatment step(s) may, in addition, implement at least one compound comprising a carbonyl group useful according to the invention as described above.

According to a preferred variant, the process for dyeing keratin fibres, in particular human keratin fibers such as the hair according to the invention, comprises the following steps:
- the application to the keratin fibers of a composition comprising at least one powder and/or at least one coloring extract of indigo-bearing plants and at least one compound comprising at least one carbonyl group; followed by
- the application to the keratin fibers of a hair post-treatment composition using at least one alkaline agent.

According to this variant, preferably, the process for dyeing keratin fibres, in particular human keratin fibers such as the hair according to the invention, comprises the following steps:
- the application to the keratin fibers of a composition comprising at least one powder and/or at least one coloring extract of indigo-bearing plants and at least one compound comprising at least one carbonyl group and at least one natural direct dye chosen from: indigo, leuco-indigo, lawsone and henna extracts and/or powders, preferably chosen from lawsone and henna extracts and/or powders, followed by
- the application to the keratin fibers of a hair post-treatment composition using at least one alkaline agent.

The additives :

The compositions used in the process of the invention may also contain various adjuvants conventionally used in compositions for dyeing keratin fibers, in particular human keratin fibers such as the hair, and different compounds such as those described above which are useful according to the 'invention. These adjuvants are chosen in particular from mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, vitamins and pro-vitamins including panthenol, sun filters, mineral or organic pigments, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example ceramides, film-forming agents, preservatives, opacifying agents.

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

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or the poultice, as described below, useful in the coloring process in accordance with the invention are not, or substantially not, altered by the addition(s) envisaged.

Coloring process according to the invention

When the coloring process according to the invention uses a composition comprising both at least one indigo plant(s) powder and/or at least one coloring plant(s) extract(s) indigo(s) and at least one compound comprising at least one carbonyl group, the composition applied to the keratin fibers is obtained by mixing extemporaneously at the time of use the powder(s) of indigo(s) plant(s) (s) and/or the dye extract(s) of indigo-bearing plant(s) and of the compound(s) containing at least one carbonyl group with water or a composition comprising 'water. When the indigo plant(s) powder is compact, it is crumbled in water or in a composition comprising water. The aqueous composition thus obtained is in the form of a poultice.

This poultice can also result from the extemporaneous mixing at the time of use of a composition comprising at least one powder and/or at least one coloring extract of indigo-bearing plants, of a composition comprising at least one compound comprising at least one carbonyl group , with water or a composition comprising water.

The poultice previously described can be produced occlusively or not.

When the process for dyeing keratin fibres, in particular human keratin fibers such as the hair, according to the invention comprises the following steps: the application to the keratin fibers of a composition comprising at least one powder and/or at least one extract dye from indigo-containing plant(s) and the pre-treatment or post-treatment application to the hair of a composition comprising at least one compound comprising at least one carbonyl group, each of these compositions is applied in the form poultice.

Preferably, the poultices useful according to the invention are formed at a temperature of between 10°C and 100°C, better still between 25°C and 80°C, more preferentially between 30°C and 50°C.

According to a variant of the process according to the invention, a composition resulting from the extemporaneous mixing at the time of use of a composition comprising at least one compound comprising at least one carbonyl group and at least one powder and/or or at least one coloring extract of indigo-bearing plants with water or a composition comprising water, the mixing ratio preferably ranging from 0.01 to 10, preferably from 0.1 to 5, preferably from 0, 2 to 0.3.

According to another variant of the process according to the invention, a composition resulting from the extemporaneous mixing of a composition comprising at least one powder and/or at least one coloring extract of indigo plants, of a composition comprising at least one at least one compound comprising at least one carbonyl group, with water or a composition comprising water, the mixing ratio preferably ranging from 0.01 to 10, preferably from 0.1 to 5, preferably from 0 .2 to 0.3.

Preferably, the poultices useful according to the invention are produced less than 30 min before their application, preferably less than 15 min before application, better still less than 10 min before application.

According to a preferred variant, the composition applied contains at least one additional direct dye, preferably natural, more preferably chosen from indigo, leuco-indigo, lawsone and henna extracts and/or powders, better still chosen from lawsone and henna extracts and/or powders.

The pH of these poultices is generally between 3 and 9, preferably between 4 and 7. The pH of these poultices can be adjusted to the desired value by means of acidic or alkaline agent(s) usually used(s) in dyeing keratin fibers or alternatively with the aid of buffer systems known to those skilled in the art.

The useful composition according to the invention, once applied to the keratin fibres, in particular human keratin fibers such as the hair, is then left in place, preferably under occlusion, for a period usually ranging from 1 minute to 2 hours, preferably from 5 minutes to 1 hour 30, better from 10min to 1 hour.

It is possible, advantageously, after application of the coloring composition, to subject the keratin fibers to a heat treatment. In practice, this operation can be carried out using a hairdressing helmet, a hair dryer, an infrared ray dispenser and other conventional heating devices.

The temperature during the process is conventionally between room temperature (between 15 to 25°C) and 80°C, preferably between room temperature and 60°C, more preferably between 25°C and 45°C.

At the end of the treatment, the keratin fibres, in particular human keratin fibers such as the hair, are optionally rinsed with water, optionally subjected to washing with a shampoo followed by rinsing with water, before being wrung out. (mechanically with a towel, or absorbent paper, or by heat). Preferably, the hair is rinsed and then wrung out with an absorbent paper or a towel.

When the method according to the invention implements at least one post-processing step hair as described above, the application of the post-treatment composition(s) comprising at least one alkaline agent and/or at least one mordanting agent and/or at least one oxidizing agent as described above is applied, preferably on keratin fibers that are still damp.

The post-treatment composition, once applied to the keratin fibres, in particular human keratin fibers such as the hair, is then left in place, for a period usually ranging from 1 minute to 2 hours, preferably from 5 minutes to 1 hour. 30, better from 10min to 1hour.

It is possible, advantageously, after application of the post-treatment composition, to subject the keratin fibers to a heat treatment.

The temperature during the process is conventionally between room temperature (between 15 to 25°C) and 80°C, preferably between room temperature and 60°C, more preferably between 25°C and 45°C.

At the end of the treatment, the keratin fibres, in particular human keratin fibers such as the hair, are optionally rinsed with water, optionally subjected to washing with a shampoo followed by rinsing with water, before being dried (mechanically with a towel, or absorbent paper, or by heat) or left to dry. Preferably, the keratin fibers are rinsed and then dried using a helmet at a temperature of 40 to 45° C., for a period usually ranging from 1 minute to 1 hour, preferably from 2 minutes to 30 minutes, better from 5 minutes to 20 minutes.

The method as described above can be reproduced several times in succession, the compositions useful according to the invention are then applied several times to the keratin fibres, in particular human keratin fibers such as the hair with intermediate rinsing, that is to say say in “layering”. For example, a composition is applied to the keratin fibers comprising at least one powder of indigo-bearing plant(s) and/or at least one coloring extract(s) of indigo-bearing plant(s) and least one compound comprising at least one carbonyl group in the form of a poultice, the keratin fibers are rinsed, then a composition comprising at least one alkaline agent is applied to the keratin fibers, then the keratin fibers are rinsed again and the whole is repeated of these steps a second time on the keratin fibers already treated. Another example of applying to the keratin fibers a composition comprising at least one powder of indigo plant(s) and/or at least one coloring extract(s) of indigo plant(s) and at least a compound comprising at least one carbonyl group in the form of a poultice, the keratin fibers are rinsed, then a composition comprising at least one alkaline agent is applied to the keratin fibers, then the keratin fibers are rinsed again, then to the keratin fibers as well treated, a composition comprising at least one powder of indigo-bearing plant(s) and/or at least one coloring extract(s) of indigo-bearing plant(s) is applied in the form of a poultice free of compounds comprising at least one carbonyl group, then the keratin fibers are rinsed, then a composition comprising at least one alkaline agent is applied to the keratin fibers, then the keratin fibers are rinsed again.

Device or “kit”

Another object of the invention is a multi-compartment device or “kit” for treating keratin fibres, in particular human keratin fibers such as the hair, comprising at least 2 compartments.

According to the first variant, the device with several compartments comprises at least one compartment comprising a composition comprising one or more dye powders/extracts of the indigo-type type and the carbonyl compound(s) and a second compartment comprising a composition comprising at least the additional dyes.

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

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

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

Example 1

Coloring step

The following compositions from A 1 to A22 were prepared by mixing, at the time of use, the powders of natural dyes and the compounds comprising at least one carbonyl group with water at 25° C. in a mass ratio of 1:3. The whole is homogenized with a wooden spoon, or a 'maryse' type spatula in order to make a poultice. The proportions of the ingredients are indicated in grams of active material per 100 grams of composition, unless otherwise indicated.

The aldehyde contents in each of the poultices produced are indicated in number of molar equivalents relative to the indican content in the indigo powder (3.5g% of indican in the indigo powder).

The poultice obtained is applied to locks of natural Caucasian hair containing 90% white hair (BN) at the rate of 10 grams of composition per 1 g of hair on both sides of the locks. The locks are left to rest for 60 min at 33° C. in cellophane/food film. They returned after 30 minutes.

At the end of the exposure time, the locks are rinsed and then wrung out with an absorbent paper.

Neutralizing post-treatment step

The following post-treatment compositions B1 and B2 (pH 9.6-11.3) are prepared. The proportions of the ingredients are indicated in grams of active material per 100 grams of composition, unless otherwise indicated.

B1 B2 _{K2CO3 _} 5.4 13.8 KHCO ₃ 6.1 - xanthan gum 1 - water Qs 100 Qs 100

Compositions B1 and B2 are each applied to the colored locks prepared previously while still damp and positioned in a chute at the rate of 1 g of composition per gram of hair and left to stand for 20 min at 33° C. in cellophane.

At the end of the exposure time, the locks are rinsed with water at 37°C then dried using a helmet at 40°C for 10 minutes.

▬Staining results

The observed colors are listed in the table below:

Process Color A1 then B1 Dark blue A2 then B1 Red A3 then B2 Red A4 then B2 Purple A5 then B2 blue red A6 then B2 pink A7 then B2 Yellow orange A8 then B2 Yellow orange A9 then B2 Purple A10 then B2 Purple A11 then B1 Orange A12 then B1 Orange A13 then B2 warm brown A14 then BZ red brown A15 then B2 Pink A16 then B2 Chestnut A17 then B2 Orange A18 then B2 Orange-red A19 then B2 red brown A20 then B2 Light brown A21 then B2 Red A22 then B2 Chestnut

It was observed that on the day of application the hair treated by the process of the invention does not show yellow/green reflections and shows aesthetic nuances.

Thus, the method of the invention makes it possible to obtain an aesthetic coloring from the day of application and to stabilize the coloring containing indigo from the day of application of the coloring. The process of the invention therefore makes it possible to accelerate the development of the coloring from indigo in order to obtain the final coloring result from the day of application and to avoid intermediate unsightly reflections.

Example 2

Coloring step

The following compositions from A23 to A30 were prepared by mixing, at the time of use, the powders of natural dyes and the essential oils containing compounds containing at least one carbonyl group with water at 25° C. in a mass ratio of 1 : 3. The whole is homogenized with a wooden spoon, or a 'maryse' type spatula in order to make a poultice. The proportions of the ingredients are indicated in grams of active material per 100 grams of composition, unless otherwise indicated.

The poultice obtained is applied to locks of natural Caucasian hair containing 90% white hair (BN) at the rate of 10 grams of composition per 1 g of hair on both sides of the locks. The locks are left to rest for 60 min at 33° C. in cellophane/food film. They returned after 30 minutes.

At the end of the exposure time, the locks are rinsed and then wrung out with an absorbent paper.

Neutralizing post-treatment step

Composition B2 (Example 1) is applied to the colored locks prepared previously while still damp and positioned in a chute at the rate of 1 g of composition per gram of hair and left to rest for 20 min at 33° C. in cellophane.

At the end of the exposure time, the locks are rinsed with water at 37°C then dried using a helmet at 40°C for 10 minutes.

▬Staining results

The observed colors are listed in the table below:

Process Color A23 then B 2 Dark blue A24 then B2 Orange A25 then B2 Dark blue A26 then B2 Dark blue A27 then B2 Gray A28 then B2 gray brown A29 then B2 Blue grey A30 then B2 Chestnut

Example #3

Coloring step

The following composition A31 was prepared by mixing, at the time of use, the coloring natural dye powders (indigo powder 68.2 g%/Henna powder 26.2 g%) and the biomass of Cinnamomum cassia (5. 6g%), the latter containing a compound comprising at least one carbonyl group with water at 25° C. in a mass ratio of 1:3. The whole is homogenized with a wooden spoon, or a 'maryse' type spatula in order to make a poultice.

The poultice obtained is applied to locks of natural Caucasian hair containing 90% white hair (BN) at the rate of 10 grams of composition per 1 g of hair on both sides of the locks. The locks are left to rest for 60 min at 33° C. in cellophane/food film. They returned after 30 minutes.

At the end of the exposure time, the locks are rinsed and then wrung out with an absorbent paper.

Neutralizing post-treatment step

Composition B1 (Example 1) is applied to the previously prepared colored locks that are still damp and positioned in a chute at the rate of 1 g of composition per gram of hair and left to rest for 20 min at 33° C. in cellophane.

At the end of the exposure time, the locks are rinsed with water at 37°C then dried using a helmet at 40°C for 10 minutes.

▬Staining results

The observed colors are listed in the table below:

Process Color A31 then B1 Cool dark brown

Claims (14)

Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to the keratin fibers of at least one powder and/or of at least one coloring extract of indigo-bearing plants and of at least one containing at least one carbonyl group, applied together or separately. Dyeing process according to the preceding claim comprising a step of treating the keratin fibers with a composition comprising at least one powder and/or at least one coloring extract of indigo-bearing plants and at least one compound comprising at least one carbonyl group. Dyeing process according to any one of the preceding claims, in which the indigo plant powder(s) is (are) chosen from species of the genera:
- Indigofera such as Indigofera tinctoria , Indigo suffruticosa, Indigofera articulata Indigofera arrecta, Indigofera gerardiana, Indigofera argenta, Indigofera indica, or Indigofera longiracemosa ;
- Isatis such as Isatis tinctoria ;
- Polygonum or Persicaria such as Polygonum tinctorium or Persicaria tinctoria ;
- Wrightia such as Wrightia tinctoria ;
- Calanthe such as Calanthe veratrifolia ;
- Baphicacanthus such as Baphicacanthus cusia . Dyeing process according to any one of the preceding claims, in which the dye(s) powder(s) and/or the dye(s) extract(s) of indigo plants are applied from a composition containing the extract(s) and/or the powder(es) of indigo plants in a total content ranging from 0.01% to 50% by weight relative to the total weight of the composition in which they are found , preferably from 0.1 to 40% by weight, better still from 0.5 to 30% by weight relative to the total weight of the composition containing them . Dyeing process according to any one of the preceding claims, in which the compounds comprising at least one carbonyl group are chosen from compounds comprising at least one aldehyde group, compounds comprising at least one ketone group and mixtures thereof and more particularly compounds comprising at least one carbonyl group are chosen from compounds containing at least one aldehyde group and mixtures thereof. Dyeing process according to any one of the preceding claims, in which the compounds comprising at least one carbonyl group are chosen from the compounds of formulas(I),(II),(III)Or(IV)following and mixtures thereof:

in which :
R ¹ independently represents:
- 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);
- a radical -OCOAlk(C₁-VS₅₎
- a radical -COOAlk(C₁-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 represents independently, a hydrogen atom or a saturated or unsaturated alkyl radical in C₁-VS₆, optionally substituted by a hydroxyl radical;
notis an integer between 0 and 4 inclusively in the formula (I);
notis an integer between 0 and 3 inclusive in the formula (II)
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 comprised inclusively between 0 and 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 independently represents a saturated or unsaturated C alkyl radical₁-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 compounds comprising at least one carbonyl group 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 heliotropin (1,3-benzodioxole-5-carbaldehyde), 2,4-dihydroxy-3-methylbenzaldehyde, syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde) , phenylacetaldehyde, budgeal (3-(4- tert -butylphenyl)propanal), 2-phenylpropionaldehyde, cyclamen aldehyde, 2-(4-methylphenyl)acetaldehyde, lilial (3-(4-tert-butylphenyl)-2-methylpropanal), hexyl cinnamaldehyde, pyridoxal (3-hy droxy-5-(hydroxymethyl)-2-methylpyridine-4-carbaldehyde), pyridoxal phosphate (4-formyl-5-hydroxy-6-methylpyridin-3-yl)methyl dihydrogen phosphate), salts of 1-methyl-4- formylpyridinium (such as chloride and methylsulfate salts), 1-methyl-4-formylquinolinium salts (such as chloride, methylsulfate, and toluenesulfonate salts), geranial, neral, citronellal, 2,4,6- trihydroxybenzaldehyde, cuminaldehyde, retinal, hydroxyisohexyl-3-cyclohexene carboxaldehyde, (4-formylphenyl)-trimethyl-ammonium salts (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 the 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 compounds comprising at least one carbonyl group are applied from a composition containing the compound or compounds comprising at least one carbonyl group in a total content ranging from 0, 01% to 20% by weight relative to the total weight of the composition in which they are found, preferably from 0.05 to 10% by weight, better still from 0.1 to 5% by weight relative to the total weight of the composition containing them. Process for coloring the hair according to any one of the preceding claims comprising at least one additional direct dye, different from the powder(s) and from the dye extract(s) of indigo-containing plant(s), preferably chosen from synthetic direct dyes such as benzene, azo, hydrazono, nitro (hetero)aryl, tri(hetero)arylmethane, (poly)methine, carbonyl, azinic, porphyrinic, metalloporphyrinic, quinonic and in particular anthraquinonic, indoaminic, phthalocyanic; natural direct dyes chosen from indigo, leuco-indigo, lawsone and henna extracts and/or powders and mixtures thereof, more preferably chosen from natural direct dyes chosen from: indigo, leuco -indigo, lawsone and henna extracts and/or powders. Dyeing process according to any one of the preceding claims, comprising at least one hair pretreatment step using: at least one mordanting agent and/or at least one reducing agent and/or at least one oxidizing agent. Process for dyeing according to any one of the preceding claims, comprising at least one post-treatment step implementing: at least one alkaline agent and/or at least one mordanting agent and/or at least one oxidizing agent. Dyeing process according to any one of the preceding claims 10 or 11, in which the mordanting agent(s) is (are) chosen from metal salts such as iron salts, aluminum salts , titanium salts, calcium salts, manganese salts, copper salts, zinc salts, strontium salts, sodium salts, magnesium salts and mixtures thereof; the reducing agent(s) is (are) chosen from thiols, hydrides, sulfites, bisulfites, metabisulfites, sugars other than compounds containing at least one carbonyl group useful according to invention and phosphines; the oxidizing agent(s) is (are) chosen from hydrogen peroxide or one or more hydrogen peroxide generating system(s); the alkaline agent(s) is (are) chosen from mineral basifying agents such as ammonia, alkali carbonates or bicarbonates, alkali or alkaline earth metal phosphates such as phosphates sodium or potassium phosphates, sodium or potassium hydroxides; organic basifying agents such as alkanolamines, amino acids, organic amines, oxyethylenated and/or oxypropylene ethylenediamines, 1,3 diaminopropane, 1,3 diamino 2 propanol, spermine, spermidine and mixtures thereof. Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, in which a composition resulting from the extemporaneous mixing at the time of use of a composition comprising at least one compound comprising at least one carbonyl group and at least one powder and/or at least one coloring extract of indigo-bearing plants with water or a composition comprising water, the mixing ratio preferably ranging from 0.01 to 10, preferably from 0 ,1 to 5, preferably from 0.2 to 0.3 or of a composition resulting from the extemporaneous mixing of a composition comprising at least one powder and/or at least one coloring extract of indigo-bearing plants, of a composition comprising at least at least one compound comprising at least one carbonyl group, with water or a composition comprising water, the mixing ratio preferably ranging from 0.01 to 10, preferably from 0.1 to 5, preferably from 0 ,2 at 0.3. Use of at least one compound comprising at least one carbonyl group for suppressing the yellow/green reflections provided by indigo on the day of coloring and stabilizing the coloring over time the color of keratin fibers colored from a composition comprising powder of indigo plants and/or a coloring extract of indigo plants.