FR3075643A1 - PROCESS FOR COLORING MULTI-STAGE KERATIN FIBERS FROM INDIGOFERE (S) PLANT POWDER AND ACID PROCESSING COMPRISING A PARTICULATE COLOR - Google Patents

Abstract

The subject of the invention is (I) a process for staining keratinous fibers, in particular human keratinous fibers, such as the hair, in which said fibers are treated in several steps, comprising at least one staining step E1) of said fibers implementing a dyeing cosmetic composition comprising powder and / or extract of indigestible plant (s) i) and possibly henna ii); at least one treatment step E2) of said fibers employing an aqueous cosmetic composition B whose pH is less than 7, and comprising one or more particular natural dye (s) iii) and one or more agents acidifying; it being understood that the composition A is implemented first on the keratin fibers; and that the composition B is implemented on the keratinous fibers after application of the composition A and (II) the use of an aqueous composition B whose pH is less than 5 and comprising one or more particular natural dyes iii), to accelerate the color stabilization of the colored fibers from indigo and possibly henna over time and improve the intensity and / or the rise of the color and / or the holding of the color.

Description

PROCESS FOR COLORING KERATINIC FIBERS IN SEVERAL STEPS FROM INDIGOFERED PLANT POWDER (S) AND ACID TREATMENT COMPRISING A PARTICULAR DYE The subject of the invention is (I) a process for coloring keratin fibers, in particular human keratin fibers, such as the hair, in which said fibers are treated in several stages, comprising at least one coloring step E1) of said fibers using a coloring cosmetic composition A comprising i) of plant powder (s) indigofere (s) and / or a coloring extract of indigofere plant (s) and possibly henna ii); at least one post-treatment step E2) of said fibers using an aqueous cosmetic composition B whose pH is less than 7, comprising one or more natural dye (s) iii) particular, different from henna and indiqoïdes and iv) one or more acidifying agents; composition A preferably being applied first to the keratin fibers; and composition B being applied to the keratin fibers after application of composition A and (II) the use of an acidic aqueous composition B, comprising one or more particular natural dyes, to accelerate the stabilization of the color of the colored fibers to start with indigo and possibly henna over time (the day the coloring process is implemented) and improve its intensity, the color increase and / or the color hold.

In fact, the colorings from indigo and possibly henna are generally evolutionary over time in terms of color, they exhibit a characteristic yellow / green coloration on the day of application (i.e. the day of coloring). This “raw” color, not very aesthetic, little appreciated by users of coloration) which evolve towards the desired colourations after a few hours (48H to 1 week) and can change color over time (appearance of purplish red reflections after generally 2 to Three weeks). There is therefore a need to stabilize this coloration in order to obtain an aesthetic coloration on the day of application (example brown free of yellow / green reflections) which changes little over time (without color change) and while respecting the integrity of the keratin fibers.

Two main modes of coloring human keratin fibers, and in particular the hair, are known.

The first, called oxidation or permanent coloring, consists in 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 nuances obtained with these oxidation bases are varied by associating 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 the oxidation bases and couplers allows obtaining a rich palette of colors.

The second mode of coloring, called direct or semi-permanent coloring, involves the application of direct dyes which are colored and coloring molecules, having an affinity for fibers. Given the nature of the molecules used, they rather remain on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of oxidation dye precursors. The main advantages of this type of coloring is that it does not require an oxidizing agent which limits the degradation of the fibers and that it does not use dyes with a certain reactivity, hence limiting the risks of intolerance.

The first hair dyes were semi-permanent. One of the most well-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.a 12 571 .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 indomer isomer is red, Their crude formulas is: C16H10N2O2; and their chemical structures are as follows:

Depending on the oxidation, over oxidation, isatin can give either indogotine or indirubin. (Maugard et al, 2001). The presence of these two isomers explains the purplish color of indigo more or less marked depending on the respective proportion in the hair of the 2 isomers formed in the hair (in particular purple to purple if the amount of indirubin increases). Indigo is from the Indian can be prepared from different plants called indigofere 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 air oxidized to release the purple blue indigo (see Chem. Rev. 2011,111,2537-2561, p. 2537-2561). Indigo is the result of hydrolysis and then oxidation of the indican (glycosylated precursor).

The problem is that coloring from indigo leaf is difficult because the kinetics

color in the keratin fibers is variable. In addition, the coloring process is unstable. Indigo theoretically provides a blue coloration with white hair, and a "cold" ash-like color. However, the coloring process from indigo is difficult to control because of the competitive reaction of indirubin formation (also involving an oxidation step with the formation of isatin of intermediate yellow color) providing reflections yellow to purple complementary to brown hair over time.

The colors resulting from the mixtures of indigo and henna are therefore generally generally evolutionary over time in terms of color, they exhibit a characteristic yellow / green coloration on the day of the coloration (“raw” color which is not very aesthetic, little appreciated by consumers of coloration) which evolve towards the desired colourations after a few hours (48H to 1 week) and can change color over time (appearance of purplish red reflections after generally 2 to 3 weeks). There is therefore a need to stabilize this coloring in order to obtain aesthetic coloring on the day of the application (example brown free of yellow / green reflections) which changes little over time (without color change).

To remedy this problem of unattractive coloring on the day of coloring and of color development if it is known to "boost" the coloring by adding direct dyes to mask the undesirable reflections, these dyes being generally used in direct coloring such than the benzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct nitro dyes (see for example EP 0 806 199). This option has the drawback for users of natural products, or those who favor "natural / organic", that the coloring is partly carried out using synthetic dyes. However, the reflection provided on the day of the application does not prevent the color change over time (evolution of the yellow reflection still present in the fiber, although masked, towards red).

Furthermore, the colors obtained from indigo are not always homogeneous between the root and the tip or from one fiber to another (The Science of Hair Care, C. Bouillon, J. Wilkinson, 2d Ed. , CRC Press, Taylor & Francis Group; Boca Raton, London, p. 236-241 (2005)).

Finally, indigo as a molecule is insoluble in water, so when a mixture of indigo and henna, which is soluble in it, is used, this leads to significant inhomogeneities in the rise in color between the root and the peak (selectivity).

There is therefore a real need to develop coloring methods which make it possible to obtain powerful, aesthetic and natural colorings at the end of the application, while respecting the cosmetic properties of keratin fibers and which in particular make it possible to obtain colorings fast, whose coloration obtained does not present yellow / green reflections which are considered unsightly by the user, having an improved color rise and less aggressive for the hair and at the same time which resist external agents (light, bad weather , shampoos), which are tenacious and / or homogeneous while remaining powerful and / or chromatic, which does not turn over time (in particular towards red reflections).

This object is achieved by the present invention which relates to a process for dyeing keratin fibers, in particular human keratin fibers, such as the hair, in which said fibers are treated in several stages, comprising: - at least one stage of coloration E1) of said fibers using a coloring cosmetic composition A comprising powder and / or extract of indigofere plant (s) i) and optionally henna ii); - At least one step of treatment E2) of said fibers using an aqueous cosmetic composition B whose pH is less than 7, and comprising one or more natural dye (s) iii) chosen from: iii-i ) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, and / or kermesic acid; iii-ii) betalains, preferably betanine; iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols), preferably of formula (Vg) which comprise at least three hydroxy groups 7 preferably chosen from cyanidine, delphinidine, pelargonine, malvidine, peonidine, petunidine , and mixtures thereof; iii-iv) carthamine; iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxy groups, preferably chosen from alkanine (also called Orcanette) and / or shikokine; - and their mixtures; and iv) one or more acidifying agents; - it being understood that preferably composition A is applied first to the keratin fibers; and that composition B is applied to the keratin fibers after application of composition A; the process preferably using at least one rinsing step, and / or one washing step between the coloring step using the composition A and the treatment step using the application of the composition B .

Thus, according to a preferred embodiment, the dyeing method according to the invention implements a first step of dyeing keratin fibers by applying a dye composition A to the fibers comprising powder and / or extract of indigofere plant (s) and possibly henna, then a treatment step with an aqueous composition B whose pH is less than 7, comprising one or more particular natural dyes as defined above and one or more acidifying agents, c that is to say in post-processing.

According to another embodiment, the coloring process according to the invention implements a treatment step with an aqueous composition B whose pH is less than 7, comprising one or more particular natural dyes as defined above and one or more acidifying agents, then a step of coloring the keratin fibers via the application of a coloring composition A on the fibers comprising powder and / or extract of indigofere plant (s) and optionally henna. The invention also relates to the use of an aqueous composition B whose pH is less than 7, comprising one or more natural dye (s) iii) particular, as defined above and iv) one or more acidifying agents, to accelerate the stabilization of the color of the colored fibers from indigo, and possibly henna, over time and improve the intensity and / or the rise of the color and / or the color fastness.

The process for dyeing keratin fibers according to the invention has the advantage of dyeing said fibers, in particular human keratin fibers, in particular the hair, with natural coloring results without yellow / green reflections, and / or powerful, chromatic dyes, resistant to washing, perspiration, sebum and to light and more durable without alteration of the fiber. In addition, the colors obtained from the process are homogeneous from the root to the tip of a fiber (low color selectivity). The treated keratin fibers have very good cosmetic properties, in particular, their integrity is respected with a high level of gloss.

The compositions used according to the invention are cosmetic compositions i.e. which are cosmetically acceptable therefore suitable for use for application to keratin fibers, in particular for application to human keratin fibers, such as the hair.

Preferably, composition A is obtained by mixing, just before use, the powder of indigofere plant (s) i) and optionally henna ii) with an aqueous composition to obtain a ready-to-use coloring composition A, preferably in the form of a poultice.

Preferably, composition A is an aqueous composition. / ') powder and / or extract of specific plant (s))

The coloring composition A according to the invention comprises powder and / or an extract of indigofere plant (s). (By “indigofere plant extract” is understood within the meaning of the present invention a “indigofere plant dye extract”)

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

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

One can use all or part (in particular the leaves in particular for Indigofera tinctoria) of the indigofere plant.

The indigofere plant powder can be sieved to obtain particles of upper limit sizes corresponding to the orifices or mesh sizes of the sieve particularly between 35 and 80 mesh (US).

According to a particular embodiment of the invention, the particle size of the indigofere plant powder is fine. According to the invention, more particularly means a particle size less than or equal to 500 μm. Preferably, the powder consists of fine particles of size inclusive between 50 and 300 μm and more particularly between 10 and 200 μm.

It is understood that said particles of indigofere plant (s) preferably have a moisture content of between 0 to 10% by weight, relative to the total weight of the powders. The indigofere plant extract according to the invention is a maceration product in generally organic solvents of all or part (in particular the leaves, in particular for Indigofera tinctoria) of the indigofere plant.

The indigofere plant powder according to the invention is a natural product from indigofere plants, reduced by grinding or other mechanical means, to fine particles.

Preferably, a powder of indigofere plant (s) is used.

According to a particular embodiment of the invention, composition A is in the form of a solid composition, preferably pulverulent, preferably anhydrous. According to this embodiment, the powder of indigofere plant (s) is preferably present in composition A in a content varying from 10 to 99% by weight, relative to the total weight of composition A, more particularly varying from 20 to 90% by weight, preferably varying from 20 to 80% by weight.

According to another particular embodiment of the invention, composition A is obtained by mixing just before use (that is to say extemporaneously) the powder and / or extract of indigofere plant (s) i) and optionally henna ii) with water or with an aqueous composition to obtain a ready-to-use coloring composition A, preferably in the form of a poultice.

According to this embodiment, the powder and / or extract of indigofere plant (s) is present in composition A preferably in a content varying from 0.5 to 50% by weight, relative to the total weight of the composition A, when composition A is aqueous, more particularly varying from 1 to 40% by weight, preferably varying from 5 to 90% by weight.

According to a particularly preferred embodiment, composition A when it is ready for use comprises water.

It is therefore preferably aqueous. By "ready to use" is meant a composition ready to be applied directly to the keranitic fibers.

According to a particular embodiment of the invention, composition A of the invention may also contain one or more surfactant (s), preferably anionic (s) or nonionic (s).

The composition A ready for use applied to the keratin fibers according to the process of the invention is preferably obtained from the mixture between powder and / or extract of indigofere plant (s) i) in compact form or not , optionally henna ii), and an aqueous composition, preferably water.

Preferably composition A ready for use applied to the keratin fibers according to the process of the invention is in the form of a poultice.

Preferably, the ready-to-use coloring composition A comprises a water content ranging from 10% to 99% by weight, more particularly from 20% to 98% by weight, better still from 40% to 95% by weight relative to the weight of composition A ready for use.

To do this i) the powder and / or extract of indigofere plant (s), optionally henna ii) and optionally the additional compounds as described above, are mixed with an aqueous composition comprising water , to obtain a poultice of a smooth and pleasant consistency corresponding to composition A ready for use. When the powder of indigofere plant (s) is compact, it is crumbled into the aqueous composition, and preferably the compact composition is crumbled into water.

Henna ii)

The coloring composition A) according to the invention preferably comprises henna ii).

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

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

It is understood that "henna powder" (and "indigofere plant powder" is different from an extract). Indeed, an extract is a maceration product in generally organic solvents, while the powder according to the invention is a natural product originating from henna plants or indigoferes, reduced by grinding or other mechanical means, into fine particles.

Preferably the henna used in the invention is red henna (Lawsonia inermis, alba). Lawone [83-72-7] (Cl Natural Orange 6; Cl 75420) also known as isojuglone, can be found in Henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably the henna is in powder form. The henna powder can be sieved to obtain particles of upper limit sizes corresponding to the orifices or mesh sizes of the sieve particularly between 35 and 80 mesh (US). According to a particular embodiment of the invention, the particle size of the henna powder is fine. According to the invention, more particularly means a particle size less than or equal to 500 μm. Preferably, the powder consists of fine particles of size inclusive between 10 and 300 μm and more particularly between 50 and 250 μm. It is understood that said henna particles preferably have a moisture content of between 0 to 10% by weight, relative to the total weight of the powders.

Preferably, said henna particles come from henna leaves.

As indicated above, according to a particular embodiment of the invention, composition A is in the form of a solid composition, preferably pulverulent, preferably anhydrous. According to this embodiment, henna is preferably present in composition A in a content varying from 5 to 99% by weight, relative to the total weight of composition A, more particularly varying from 10 to 60% by weight, preferably varying from 15 to 40% by weight, in particular when composition A is anhydrous.

As indicated above, according to another particular embodiment of the invention, composition A is obtained by mixing just before use (that is to say extemporaneously) the powder of indigofere plant (s) i) and henna ii) (when present) with water or with an aqueous composition to obtain a ready-to-use coloring composition A, preferably in the form of a poultice.

According to this embodiment, the henna is present in the composition A preferably in a content varying from 0.1 to 30% by weight, relative to the total weight of the composition A, when the composition A is aqueous, more particularly varying from 0.15 to 20% by weight, preferably varying from 0.2 to 10% by weight.

Preferably, when the coloring process according to the invention uses henna, then the powder and / or the extract of indigofere plant i) and henna ii) are present in composition A in a weight ratio i) / ii) varying from 0.1 to 95 preferably from 0.5 to 50, better still from 1 to 10.

Composition B:

Composition B used according to the invention is an aqueous composition, the pH of which is less than 7. Preferably, the pH of composition B is less than 6, preferably less than 5.0.

Preferably the pH of composition B used according to the invention has a pH inclusive between 0.5 and 5; more particularly between 0.5 and 4.5; preferably between 2 and 4.

Composition B according to the invention comprises iv) one or more acidifying agents, preferably chosen from mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, alpha hydroxy carboxylic acids (AHA) such as citric acid, lactic acid; and their mixtures.

In particular, the pH of composition B can be adjusted to the desired value by means of acidifying agents as described above or even using conventional buffer systems.

According to a particular embodiment of the invention, the composition (A) comprises at least one acid, preferably chosen from mineral acids which are preferably chosen from hydrochloric, phosphoric and sulfuric acids and their conjugated salts, in particular l phosphoric acid and its salts.

Preferably, composition (B) comprises an inorganic buffer system comprising a mixture of at least one mineral (inorganic) acid and its conjugate base, namely the inorganic salt of said inorganic acid. Preferably, composition (B) comprises an inorganic buffer system comprising a mixture of at least phosphoric acid (H3PO4) and at least one inorganic phosphate salt, in particular chosen from potassium dihydrogen phosphate KH2PO4, sodium dihydrogen phosphate NaH2PO4 , dipotassium hydrogen phosphate K2HPO4, disodium hydrogen phosphate Na2HPO4, potassium hydrogen phosphate K3PO4, sodium phosphate Na3PO4 and mixtures thereof.

The acidifying agent (s) iv) as defined above preferably represent from 0.001% to 15% by weight of the weight of composition B. More particularly from 0.005% to 10% by weight, relative to the weight of composition B better from 0.5 to 5%.

Preferably, the acidifying agent (s) iii) are present in the aqueous composition B, in a concentration inclusive between 0.1 M and 1 M, such as 0.5 M.

Natural dyes iii) present in composition B:

Composition B used according to the invention comprises one or more natural dye (s) iii) chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, lacaic acid, and / or kermesic acid, iii-ii) betalains, preferably betanin iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) preferably of formula (Vg) which contain at least three hydroxy groups, preferably chosen from cyanidine, delphinidine, pelargonin, malvidine, peonidine, petunidine, and mixtures thereof; iii-iv) carthamine iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxy groups, preferably chosen from alkanine (also called Orcanette) and / or shikokine; and their mixtures.

According to an advantageous embodiment of the invention, the natural dye (s) iii) are chosen from anthraquinones comprising at least two hydroxyl groups, preferably chosen from alizarin, xanthopurpurin, rubiadin, lucidine, munjistin, anthragallol, purpurin, pseudopurpurine, morindone, and their mixtures, preferably at least three hydroxyl groups, preferably chosen from anthracallol, purpurine, pseudopurpurine, morindone, munjistin, and their mixtures.

Preferably, the anthraquinone (s) are dyes which absorb in the red.

According to an advantageous embodiment of the invention 1e or your natural dyes iii) are compounds comprising at least one carboxylic acid function.

Preferably, according to this embodiment, your natural dyes iii) are preferably chosen from: iii-i) your anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, the acid laccaic A, laccaic acid B, laccaic acid C, laccaic acid D, pseudopurpurin, munjistin and / or kermesic acid, iii-ii) betalains, preferably betanine; and their mixtures.

According to another advantageous embodiment of the invention, the natural dye (s) iii) are chosen from: - iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) preferably of formula (Vg) which comprise at least three hydroxy groups, preferably chosen from cyanidine, delphinidine, pelargonin, malvidine, peonidine, petunidine, and mixtures thereof;

Among your natural dyes used according to the invention, we include your compounds which can be present in nature and which are reproduced by (hemi) chemical synthesis.

The natural dye (s) according to the invention can be salified (s) or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.

By "glycosylated" radical is meant a radical derived from a mono or polysaccharide.

The natural dyes according to the invention can be in the form of powders or liquids. Preferably, your natural dyes of the invention are in the form of powders.

Preferably, the natural dyes used according to the invention in composition B have an absorption wavelength Xmax of between 625 and 750 nm or between 300 and 470 nm, better still between 625 and 750 nm.

Preferably the dyes of the invention are dyes which absorb in the red ie at an absorption wavelength which is included in the range particularly between 300 and 470 nm, or the violet between 625 and 750 nm of the reds - orange, preferably red.

In particular, according to a first preferred embodiment of the invention, the natural dye (s) iii) are anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from those of formula (A1) below, comprising at least less a carboxylic acid function: R8 O R1 R5 O R4 (A1) as well as their tautomeric and / or mesomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, and their solvates such as hydrates; formulas (A1) in which: • R1 and R8, identical or different, represent a hydrogen atom, a hydroxy group, or alkyl such as methyl; • R2 represents a hydrogen atom, a hydroxyl group, carboxy -C (O) OH or carboxylate -C (O) O ', Q + with Q + representing an alkali or alkaline earth metal such as potassium or calcium; • R3 represents an i) hydrogen atom, ii) a hydroxy group, or a group iii) aryl optionally substituted, preferably a phenyl group optionally substituted by one or more groups chosen from a) hydroxy, b) amino, c) (Ci-Ce) alkyl optionally substituted by one or more groups chosen from hydroxy, carboxy and (Ci-C4) alkylcarbonylamino; • R4 represents a hydrogen atom, or a hydroxy group; • R5 represents a hydrogen atom, or a hydroxy, carboxy or carboxylate group -C (O) O ', CTwith as defined above; • R6 represents a hydrogen atom, a hydroxy group, -O ', Q + with Q + as defined above, carboxy or carboxylate -C (O) O', Q + with Q + as defined above; • R7 represents a hydrogen atom, a hydroxy group or a glycosylated radical, preferably glucose. •

Preferably, the dyes of the invention are of formula (A1) and in particular, taken together or separately in which: R1 represents a hydroxy group, or (Ci-C4) alkyl; R2, R4 and R8, identical or different, represent a hydrogen atom or a hydroxy group; R3 represents a hydrogen atom, a hydroxy group, or a substituted phenyl group optionally substituted by one or more groups chosen from hydroxy, carboxy and (Ci-C4) alkylcarbonylamino such that: with Y representing a group chosen from: -CH ( NH2) -C (O) OH, -CH2-OH, -NH-C (O) -CH3; and the point of attachment to the rest of the molecule. • R5 and R6, identical or different, represent a hydrogen atom, or a hydroxy group, carboxy -C (O) OH or carboxylate-C (O) O ', Q + with Q + representing an alkali or alkaline earth metal such as potassium or calcium; and • R7 represents a hydrogen atom or a hydroxy group.

According to one embodiment, the dye (s) of the invention are of formula (A1): and in particular, taken together or separately in which, R1 represents a (Ci-C4) alkyl group; R2 represents a carboxy or carboxylate group -C (O) O ', Q + with Q + representing an alkali or alkaline earth metal such as potassium or calcium; R3 and R8 represent a hydroxy group; R4 represents a hydrogen atom or a hydroxy group, preferably hydrogen; R6 represents a hydroxy group, -O ', Q + with Q + as defined above; and • R7 represents a hydrogen atom or a glycosyl radical such as glucose.

In a particularly preferred manner, the natural dyes iii) are chosen from anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, acid

lacca C, lacca acid D (also known as Flavokermesic acid), pseudopurpurin, munjistin, and mixtures thereof; preferably from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, preferably from lacaic acid D and / or kermesic acid.

The structures of these compounds are as follows:

Preferably, the natural dyes iii) are chosen from carminic acid, laccaic acid D or kermesic acid, pseudopurpurin and munjistin and their mixtures. According to a second advantageous embodiment of the invention, the natural dye (s) iii) are chosen from betalains, preferably betanine. Betalains are dyes from red beet.

According to a third advantageous embodiment of the invention the natural dye (s) iii) are chosen from anthocyanidins (also called anthocyanides, or anthocyanidols) preferably of formula (Vg) which contain at least three hydroxy groups, preferably chosen from cyanidol, cyanidine, delphinidine, pelargonine, malvidine, peonidine, petunidine, aurantinidine, luteolinidine, and their mixtures, their heterosides such as dihydroxyanthocyanes (or dihydroxyanthocyanosides, or anthocyanins on the English model), their oligomers and polymers such as proanthocyanins; preferably anthocyanidols and in particular extracts of blackcurrant, blueberry, raids, grapes, red cabbage, elderberry, black carrot, black rice .; preferably chosen from cyanidine, delphinidine, pelargonin, malvidine, peonidine, petunidine, and their mixtures.

According to an advantageous embodiment of the invention, the natural dye (s) iii) are chosen from anthocyanidins (also called anthocyanides, or anthocyanidols) of formula (Vg) which preferably contain at least three hydroxy groups:

formula (Vg) in which: • R1, R2, R3, R4, R10, R11, R12, R13 and R14, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from i) hydroxy, ii) (Ci-C6) alkyl, iii) (Ci-Cs) alkoxy, iv) (Ci-Cejalkylthio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vii) optionally substituted amino, viii) linear or branched alkenyl possibly substituted, ix)

optionally substituted cycloalkyl, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di) ((hydroxy) (Ci-C6) alkyl) amino, xiii) glucosyl, xiv) RZC (X) -Y- with R representing a hydrogen atom, a (Ci-C6) alkyl or aryl group optionally substituted in particular by at least one hydroxy group such as 3,4,5-trihydroxyphenyl; Y and Z, which may be identical or different, represent a bond, or an oxygen or sulfur atom or a group --N (R ') - with R' representing a hydrogen atom or a (Ci-Ce) alkyl group, Y also being able to represent a group (Ci-C6) alkylene; X representing an oxygen or sulfur atom, or N-R "with R" representing a hydrogen atom or a (Ci-Ce) alkyl group; • R6 and R8, identical or different, represent a hydrogen atom, or a group chosen from a hydroxy group, a (Ο-Οβ) alkyl group, or an RZC (X) -Y- group as defined above, • or then the motif (V) constitutes the polymeric unit of a polyphenol which will be linked to the other units of said polyphenol by positions 4, 6 or 8 of the chroman ring in which case R1, or R3 and R6 form a covalent bond with the others units of said polyphenol; it being understood that at least three radicals of the compounds of formula (Vg) chosen from R1, R2, R3, R4, R8, R10, R11, R12, R13 and R14, represent a hydroxy group; the compounds of formula (Vg) being cationic and there is associated therewith an anionic, organic or inorganic ion, such as halide. preferably, the radicals R1, R6, R14 and R10 representing a hydrogen atom.

Preferably the group R-Z-C (X) -Y- of the compounds of formula (V) represents a 3,4,5-trihydroxyphenyl-1-carbonyloxy (-O-gallate). Preferably, the radicals Ri, R2, R3, R4, R10, Ru, R12, R13 and Ri4 are chosen from the hydrogen atom, and the hydroxy, glycosyloxy, and alkoxy groups.

According to a particularly preferred embodiment of the invention, the natural dyes iii) are anthocyanidins of formula Vg, in which the radicals R1, R6, R14 and R10 represent a hydrogen atom .:

The other radicals R2, R3, R4, R8, R13, R12 and R11 comprising at least 4 at least 4 hydroxys and / or alkoxy functions (preferably methoxy), better at least 5 hydroxys and / or methoxy functions

According to a preferred embodiment of the invention, the natural dyes iii) are anthocyanidins of formula Vg chosen from the compounds listed in the table below and their mixtures.

According to a preferred embodiment of the invention, the natural dyes iii) are anthocyanidins chosen from cyanidine, delphinidine, malvidine, peonidine, petunidine, and mixtures thereof.

According to a preferred embodiment of the invention, the natural dyes iii) are chosen from anthocyanidins chosen from delphinidine, malvidine, petunidine, and their mixtures.

According to a fourth advantageous embodiment of the invention, the natural dye (s) iii) are chosen from carthamine.

According to a fifth advantageous embodiment of the invention, the natural dye (s) iii) are chosen from naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxy groups, preferably chosen from alkanine (also called Orcanette ) and / or shikokine.

According to a preferred embodiment, the natural dyes iii) used in the present invention are polyphenols (and / or extracts rich in polyphenols).

By “polyphenol” is meant a compound comprising in its structure several hydroxyl functions carried on one or more 6-membered carbon aromatic rings.

According to this embodiment, the natural dye (s) iii) used according to the

present invention are polyphenols chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, iaccaide acid B, laccaic acid C, laccaic acid D, and / or kermesic acid, iii-ii) betalains, preferably betanine; iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) of formula (Vg) which comprise at least three hydroxy groups, preferably chosen from cyanidine, delphinidine, malvidine, peonidine, petunidine, and their mixtures; iii-iv) carthamine; and their mixtures;

According to another advantageous embodiment of the invention the natural colorant (s) iii) are compounds comprising at least one carboxylic acid function.

Preferably, according to this embodiment, the natural dyes iii) are chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A , laccaic acid B, laccaic acid C, laccaic acid D,, 1a pseudopurpurine and munjistine and / or kermesic acid; iii-ii) betalains, preferably betanine; and their mixtures.

Preferably, the natural dye (s) iii) chosen from: - anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, l acid Iaccaide B, laccaic acid C, laccaic acid D, and / or kermesic acid, pseudopurpurin and munjistine betanin

Preferably, the natural dye (s) iii) chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, Iaccaide acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistine and / or kermesic acid iii-ii) betanin; and their mixtures.

Even more preferably, the natural dye (s) iii) chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaide acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistine and / or kermesic acid ^

In the context of the present invention, the natural dye (s) iii) “pure” are present in composition B in a total amount ranging from 0.05 to 25% by weight of the total weight of the dye composition, in particular ranging from 0 , 1 to 10% by weight of the total weight of the coloring composition, preferably 0.5 to 5% by weight relative to the total weight of composition B.

As regards extracts iii), the content in composition B containing the extract (s) as such is preferably between 0.1 and 20% by weight, relative to the weight of composition B, more preferably from 0.5 to 5% by weight.

Organic solvents:

The compositions A and / or B as defined above can comprise one or more organic solvent (s). As organic solvent, lower C1-C4 alkanols such as ethanol and isopropanol are preferred; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol.

The organic solvents are present in proportions preferably of between 0.1 and 20% by weight approximately relative to the total weight of the composition considered, and even more preferably between 0.5 and 10% by weight approximately.

Oils

The compositions A and / or B as defined above can comprise one or more oils, identical or different.

By "oil" is meant a "fatty substance" which is liquid at room temperature (25 ° 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 range of shear stress from 0.1 Pa to 100 Pa)

By “fatty substance” is meant an organic compound insoluble in water at ordinary temperature (25 ° C) and at atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably 1% even more preferably 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as, for example, chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THF), petrolatum oil or decamethylcyclopentasiloxane.

The term "non-silicone oil" means an oil containing no silicon atom (Si) and a "silicone oil" means an oil containing at least one silicon atom.

More particularly, the oils are chosen from non-silicone oils and in particular hydrocarbons and C 6 -C 16 or with more than 16 carbon atoms and in particular alkanes; oils of animal origin; vegetable triglyceride oils; essential oils ; glycerides or fluorinated oils of synthetic origin, fatty alcohols; fatty acid and / or fatty alcohol esters other than triglycerides, fatty acid amides and silicone oils.

Preferably, the oils are not oxyalkylenated or glycerol ethers.

Preferably, the oils do not comprise a C2-C3 oxyalkylene unit or a glycerol unit.

Preferably, the oils are not fatty acids which, in salified form, give water-soluble soaps.

The oils which can be used as second ingredient b) in composition A or B in accordance with the invention can be silicones.

The silicones can be volatile or not, cyclic, linear or branched, modified or not by organic groups, having a viscosity of 5.10-6 to 2.5 m2 / s at 25 ° C and preferably 1.10-5 to 1 m2 / s.

Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organo-modified polysiloxanes comprising at least one functional group chosen from poly (oxyalkylene) groups, amino groups and alkoxy groups.

Organopolysiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly still from: (i) cyclic polydialkylsiloxanes comprising from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name of VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name of VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE ® 70045 V5 by RHODIA, as well as their mixtures.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as SILICONE VOLATILE® FZ 3109 sold by the company UNION CARBIDE, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1, r ~ (hexa- 2,2,2 / 2 ^ 3,3- ^ 01011 ^ 1-silyloxy) bis-neopentane; (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to l 10 10 m / s at 25 ° C. These are, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by TORAY SILICONE. Silicones included in this class are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32 -TODD & BYERS "Volatile Silicone fluids for cosmetics".

Preference is given to using non-volatile polydialkylsiloxanes, gums and resins of polydialkylsifoxanes, polyorganosiloxanes modified by the above organofunctional groups and their mixtures.

These silicones are more particularly chosen from polydialkylsiloxanes among which mention may mainly be made of polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to standard ASTM 445 Appendix C.

Among these polydialkylsiloxanes, non-limiting examples that may be mentioned are the following commercial products: - SILBIONE® oils of series 47 and 70,047 or MIRASIL® oils sold by RHODIA such as, for example, oil 70,047 V 500,000; - the oils of the MIRASIL® series sold by the company RHODIA; - oils of the 200 series from the company DOW CORNING such as DC200 having a viscosity of 60,000 mm2 / s; - VISCASIL® oils from GENERAL ELECTRIC and certain oils from the SF series (SF 96, SF 18) from GENERAL ELECTRIC.

Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as oils of the 48 series from the company RHODIA.

The compositions A and / or B as defined above can comprise one or more oils, chosen from fatty alcohols, fatty acid amides and fatty acid esters in the form of oils.

It is recalled that within the meaning of the invention, 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 unsaturated, these compounds can have one to three carbon-carbon double bonds, conjugated or not.

More specifically, the latter may represent an ester of C1-C10 alcohol and C6-C3o fatty acid such as RC (O) -O-R 'with R representing a C6-C30 alkyl group, linear or branched , C6-C30 alkenyl, linear or branched, comprising one or two unsaturations, and R representing a C1-C10 alkyl group, linear or branched.

Preferably R represents a linear alkyl group in JSiO-C2o and R ’represents a preferably branched C1-C6 alkyl group such as isopropyl myristate.

According to another advantageous variant, the ingredient ii) represents one or more amides of C6-C3o fatty acid and of primary or secondary C1-C10 amine, preferably of primary amine, such as those of formula R ”- C (O) -N (Ra) -R ”'with R” representing a linear or branched C6-C3o alkyl group, linear or branched C6-C3o alkenyl, comprising one or two unsaturations, which may be substituted by a or more hydroxy, or (di) (Ci-C6Xalkyl) amino groups, and R '”representing a C1-C10 alkyl group, linear or branched, Ra representing a hydrogen atom or an alkyl group as defined for R' ". Preferably R ”represents a C14-C20 alkenyl group, Ra represents a hydrogen atom and R '” represents a C1-C6 alkyl group optionally substituted by (di) (Ci-C4) (alkyl) amino such that l oleyl amidopropyl dimethyl amine.

As regards the C6-C16 alkanes, the latter are linear, branched, possibly cyclic. By way of example, mention may be made of hexane, dodecane, isoparaffins such as isohexadecane, isodecane. Linear or branched hydrocarbons of more than 16 carbon atoms can be chosen from paraffin oils, petrolatum, petrolatum oil, polydecenes, hydrogenated polyisobutene such as Parléam®, squalane, squalene and their mixtures ,

Among the hydrocarbons, there may be mentioned the refined vegetable perhydrosqualene marketed under the name fitoderm by the company Cognis; vegetable squalane sold for example under the name Squalive by the company Biosynthis.

The following compounds may also be mentioned: - a mixture of C15-C16 branched alkanes, for example that which is marketed by the company SEPPIC under the name EMOGREEN L15; - A mixture of linear and / or branched C13-C15 alkanes, for example that which is marketed by the company SEPPIC under the name EMOSMART L15.

Among animal oils include perhydrosqualene.

Among the triglycerides of vegetable 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 also, for example, sunflower, corn, soy, squash, grapeseed, sesame, hazelnut, apricot, macadamia, macaw, sunflower, castor, avocado, caprylic / capric acid triglycerides like those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil.

Among the fluorinated oils, mention may be made of perfluoromethylcyclopentane and perfluoro-1,3 dimethylcyclohexane, sold under the names of "FLUTEC® PC1" and "FLUTEC® PC3" by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names of "PF 5050®" and "PF 5060®" by the company 3M, or alternatively bromoperfluorooctyle sold under the name "FORALKYL®" by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by the company 3M.

Among the essential oils contained in the composition of the invention, or may mention 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).

Preferably, the oil or oils of the invention are non-silicone. The term "non-silicone oil" means an oil containing no silicon atom (Si) and a "silicone oil" means an oil containing at least one silicon atom.

According to a variant of the invention, the oil or oils are chosen from C6-C16 alkanes, hydrocarbons with more than 16 carbon atoms, polydecenes, liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or their mixtures.

Better still, the oils are chosen from petrolatum oil and Ο6-Ο16ι alkanes, polydecenes, hydrocarbons with more than 16 carbon atoms.

In this variant preferably, the oil or oils are chosen from mineral oils such as petrolatum oil, squalane, squalene.

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 chosen from jojoba, babassu, sunflower, olive and nut oils. coconut, brazil nut, marula, corn, argan, soy, squash, grapeseed, flax, sesame, hazelnut, apricot, macadamia, arara, coriander, almond, castor, avocado, shea butter oil as well as rapeseed oil, borage, evening primrose, pomegranate, mango, palm, cottonseed and coconut oil, and their mixtures.

More particularly, compositions A, and / or B may contain one or more oils of vegetable origin preferably chosen from avocado oil, olive oil, coconut oil, coconut oil, argan oil and sunflower oil; more preferably the oil or oils of the invention are chosen from coconut oils, and their mixtures.

According to a preferred embodiment, the compositions A, and / or B can contain one or more oils chosen from hydrocarbons in Ce-Cwou with more than 16 carbon atoms and in particular alkanes; preferably from: - C6-Ci6 hydrocarbons, these are linear, branched, optionally cyclic, preferably chosen from hexane, dodecane, isoparaffins such as isohexadecane, isodecane, and mixtures thereof; linear or branched hydrocarbons of more than 16 carbon atoms, preferably chosen from paraffin oils, petrolatum, petrolatum oil, polydecenes, hydrogenated polyisobutene such as Parléam®, hemisqualane, squalane, squalene and their mixtures; and their mixtures.

The compositions A and / or B used in the process of the invention preferably comprise one or more oils in an amount inclusive between 1 and 80% by weight, more particularly between 2 and 50% by weight, preferably between 3 and 40% by weight, and more preferably between 2 and 25% by weight relative to the total weight of said compositions.

The additives :

The compositions A and / or B used in the process of the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, amphoteric or nonionic surfactants, mineral thickening agents or organic, and in particular associative anionic, eationic, nonionic and amphoteric polymeric thickeners, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example ceramides, film-forming agents, preserving agents, opacifying agents and mineral or organic thickening agents such as clays.

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

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 useful in the coloring process according to the invention are not, or not substantially, altered by the planned addition (s).

Additional dyes:

The compositions A and / or B used in the dyeing process of the invention may also contain one or more additional direct dyes, in particular synthetic or of natural origin, different from the powder and / or plant extract (s) indigofere (s) i) and henna ii) and natural dyes iii as described above.

The synthetic direct dyes are preferably chosen from those conventionally used in direct dyeing, and among which mention may be made of all the aromatic and / or non-aromatic dyes of common use such as neutral, benzene, acid or cationic direct dyes, dyes direct azo neutral, acid or cationic, natural direct dyes, direct dye quinones and in particular neutral anthraquinone, acid or cationic, direct dyes azine, triarylmethanic, indoamine, methines, styriles, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes.

Preferably, the natural direct dyes different from indigo i) and henna ii) are chosen from condensed, gallic or ellagic tannins, naphthoquinones (juglone, lawsone) and anthraquinones (emodin, alizarin, ...), l 'isatin, curcumin, spinulosin, flavonoid polyphenols, isoflavonoids, pterocarpanes, neoflavones, orceins ,.

These natural colors can be added as defined compounds, extracts, or parts of plants. Said defined compounds of extracts, or part of plants are preferably in the form of powders, in particular fine powders whose particles have sizes identical to that of the powder of indigofere plant (s) as defined above.

When (s) are (are) present, the direct, natural or synthetic dye (s) different from the powder of indigofere plant (s) i) and henna ii) used in the process of the invention, represents in particular, from 0.001% to 10% by weight of the total weight of the ready-to-use composition and even more preferably from 0.05% to 5% by weight, relative to the total weight of the composition considered.

Preferably, the compositions of the invention do not contain synthetic direct dyes, i.e. which have no natural occurrence.

Advantageously, composition B can comprise one or more additional natural dyes are chosen from the compounds of formulas (a) or (b) below, or their mixtures:

Such compounds are for example extracted from molds of the species Monascus purpureus (synonyms: M. albidus, M. anka, M. araneosus, M. major, M. rubiginosus, and M. vinty

Composition A used in the process of the invention can also comprise one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

Among the oxidation bases that may be mentioned are para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts

Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

When (s) is (are) present, The oxidation base (s) present in the composition (s) are generally present each in an amount between 0.001 to 10% by weight of the total weight of the coloring compositions.

Preferably, the coloring process of the invention does not use an oxidation dye. pH of composition A ready to use

According to a particular embodiment of the invention, the pH of composition A ready for re-use after mixing with the aqueous composition, preferably with water, containing the ingredients i) and optionally ii), varies from 2 to 9, preferably from 3 to 7, better from 4 to 6.5

The pH of the ready-to-use composition A can be adjusted to the desired value by means of acidic or alkaline agent (s) usually used in dyeing keratin fibers or even by using conventional buffer systems,

Among the acid agents used in the compositions of the invention, there may be mentioned mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid , citric acid, lactic acid, sulfonic acids, preferably the acid is an organic acid such as citric acid.

Surfactants)

According to a particular embodiment, the coloring process implements one or more surfactant (s). Preferably the surfactant (s) is (are) chosen from anionic and nonionic surfactants

Staining method according to the invention

The dyeing process according to the invention uses two separate compositions A and B implemented in two distinct steps E1) and E2), via their application to keratin fibers.

According to a preferred embodiment of the method according to the invention, composition A is applied first to the keratin fibers; and composition B is applied to the keratin fibers after application of composition A; the method preferably using at least one rinsing step, and / or one washing step between the coloring step using composition A and the treatment step using application of composition B.

Preferably, the coloring process according to the invention implements the following steps: - the first step consists in the preparation of composition A as defined above, in particular in the form of a poultice as defined above comprising water , from powder and / or extract of indigofere plant (s) i) and possibly henna ii); - then composition A ready for use as defined above is applied to the keratin fibers and is left on said fibers preferably a minimum time of 10 minutes, preferably a time ranging from 10 minutes to 12 hours, better ranging from 15 at 75 minutes, better from 15 to 60 minutes; - Then is applied to said fibers the aqueous composition B whose pH is less than 7 and comprising one or more natural dye (s) iii) chosen from: iii-i) anthraquinones preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistine and / or kermesic acid iii ii) betalains, preferably betanine; iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) preferably of formula (Vg) as described above which comprise at least three hydroxy groups preferably chosen from cyanidine, delphinidin, pelargonin, malvidin, peonidin, petunidine, and mixtures thereof; iii-iv) carthamine iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxy groups, preferably chosen from alkanine (also called Orcanette) and / or shikokine; and their mixtures; and iv) one or more acidifying agents

Preferably, between the step of applying composition A ready for use and the step of applying composition B, the keratin fibers are rinsed with water until the poultice disappears, and / or washed, in the presence of a shampoo, preferably according to this third step, the fibers are rinsed with water without shampooing; preferably after this rinsing and / or washing step, if it is carried out, the keratin fibers can then be either dried or left wet, preferably left wet.

According to another embodiment of the method according to the invention, composition B as defined above is applied first to the keratin fibers, then composition A ready for use as defined above is applied to the keratin fibers and is left to lay on said fibers preferably as defined above. According to this embodiment, the fibers are preferably also rinsed as described above.

Preferably, at the end of the coloring process according to the invention, the keratin fibers are washed and / or rinsed.

The composition A ready for use preferably comprises water and is in the form of a poultice, it can also comprise one or more oils, and / or one or more organic solvents and cosmetic additives, mixed with the plant powder. (s) indigofere (s) i) and possibly with henna ii).

According to another embodiment of the invention, the powder of indigofere plant (s) i) and optionally the henna and is mixed or crumbled with or in an aqueous composition and preferably water at a temperature below 100 ° C, in particular between 25 ° C and 70 ° C, better between 25 ° C and 50 ° C.

Preferably, the application temperature of composition A varies from room temperature (15 to 25 ° C) to 50 ° C and more particularly from 25 to 40 ° C.

It is advantageously possible, after application of the poultice according to the invention, to subject the hair to a heat treatment by heating at a temperature varying from 30 to 150 ° C. better still 30 ° C to 60 ° C. In practice, this operation can be carried out using a hairdressing helmet, a hair dryer, an infrared ray dispenser and other conventional heating devices.

A particular embodiment of the invention relates to a coloring process which is carried out at room temperature (25 ° C). The evaluation of the coloration obtained from keratin fibers can be carried out visually or with a spectrocolorimeter in the CIE L * a * b * system, for example by means of a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10 °, specular component included).

In this system L * a * b *; L * represents the clarity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the value of L *, the darker, more powerful the coloration.

The lower the value of a * and the greener the color, the higher the value of a * the more the color is red.

The lower the value of b * and the more blue the color, the higher the value of b * the more yellow the color.

The rise in color corresponds to the variation in coloring between the locks of hair, before and after treatment or coloring is defined by (ΔΕ *) according to the following equation:

In this equation, L *, a * and b * represent the values measured on locks of hair after coloring and Lo *, a0 * and bo * represent the values measured on locks of uncolored hair. The larger the value of ΔΕ *, the better the rise in color. The stability of the coloration of the keratin fibers is also evaluated over time, in particular after 9 days by measuring the colon coordinates of the keratin fibers and by comparing them to the colon coordinates immediately after implementation of the coloring process according to the invention. The color difference ΔΕ * between the color at TO and the color after 9 days represents the stability of the hair color and is calculated by the following equation:

In this equation, Lo *. ao * and bo * represent the colorimetric coordinates measured on locks of hair at TO immediately after the implementation of the process and L3S *, a3s * and b * 3S represent the colorimetric coordinates 9 days after the implementation of the process. The lower the value of AE * stab, the more stable the coloration.

In particular, in the context of the invention, a coloration is considered to be stable over time for which the ΔΕ * 9 days after coloration is less than 2.

In the context of the present invention, it is therefore sought to obtain immediately after the coloring process a value of b * as low as possible and / or a value of a * as high as possible. We seek to obtain these results while having an effective color rise (large color rise value) and stable coloring over time.

EXAMPLES OF COLORING EXAMPLE 1:

The following compositions were prepared:

The percentages are given by weight relative to 100 g of composition. 1. Coloring step

The following coloring composition is prepared by mixing the natural dye powder with water at 50 ° C. at the time of re-use in order to produce the following poultice:

The ingredients described i) and ii) are dissolved or dispersed in the relative amounts described in the table above in water at 50 ° C in a bowl. The whole is homogenized with a spoon or spatula.

The poultice obtained is very smooth, and is applied to locks of natural hair 90% white hair at the rate of 10 grams of composition per 1g of locks. The locks are left to stand for 60 min at 33 ° C. under cellophane. At the end of the pause time, the locks are rinsed and washed with Ultra Soft Chamomile Shampoo and then wrung out. 2. Neutralizing Post-Processing Stage

The following post-treatment compositions were prepared: _

At the end of the coloring step, the compositions are then applied at a rate of 5 g per gram of hair and left to stand for 15 min at 40 ° C. under cellophane compared to reference locks which have not undergone post-treatment. At the end of the pause time, all the locks are then rinsed and washed with Ultra Soft Chamomile Shampoo and then dried. Color results

The color of the locks was evaluated in the CIE L * a * b * system, using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10 °, specular component included).

In this system L * a * b *, L * represents the intensity of the color, a * indicates the axis of color green / red and b * the axis of color blue / yellow.

The rise in color corresponds to the variation in coloring between the locks of hair, before and immediately after implementation of the method are defined by (ΔΕ *) according to the following equation: ΔΕ * = * -4 *) 2 + ( a * -a0 *) 2 + (b * -bo *) 2

In this equation, L *, a * and b * represent the values measured on locks of hair after coloring and Lo *, a0 * and b0 * represent the values measured on locks of

uncolored hair. The larger the value of ΔΕ *, the better the rise in color. Colorimetric measurements were carried out immediately after the implementation of the process (TO), then after 9 days (T 9J). The color difference delta E between the color at TO and the color after 3 weeks represents the stability of the hair color and is calculated by the following watering:

In this equation, Lo *, ao * and bo * represent the colorimetric coordinates measured on locks of hair at TO immediately after the implementation of the method and Lgj, agj * and b * 9j represent the colorimetric coordinates 9 days after the implementation implementing the process.

Delta b represents the variation between bo and b3s.

We have observed that the colorings obtained with the methods according to the invention, implementing a post treatment with compositions B2 and B3, do not have yellow / green reflections.

Indeed, the coloring method according to the invention implementing a post treatment with

compositions B2 and B3 make it possible to neutralize the unsightly yellow / green color on the day of coloring, unlike the comparative treatments of the invention without post treatment or else with post treatment compositions B1 (comparatives 1 and 2).

This results in: significantly higher values of a * (less green and therefore more red) for the hair treated in post-treatment with compositions B2 and B3 (methods of the invention) compared to colored hair without post-treatment. or with post-treatment B1 (comparatives 1 and 2).

In addition, the methods according to the invention using a post-treatment composition according to the invention (compositions B2 and B3) make it possible to obtain colorations having a better rise in color (higher DE).

In addition, for the colorings obtained with the post-treatment compositions B2, and B3 (methods of the invention), we also obtain b * values significantly lower (less yellow) compared to colored hair without post-treatment or else with post processing B1 (comparative 1 to 2).

Furthermore, the colors obtained with the process of the invention are stable over time (value DE TO / T 9J low,), unlike the colors without post-treatment (comparison 1) which require a certain time before obtaining an aesthetic color. (Brown).

In conclusion, the post-treatments of the invention (compositions B2 and B3) make it possible to obtain colorations having a better rise in color (higher DE) and more esthetic brown (components of higher red or lower yellow ) at the end of the coloring process. These colors are moreover stable over time (AETgjours-Tofaible). -> The process of the invention therefore makes it possible to accelerate the revelation of the coloring from henna and indigo to obtain the final coloring result from the day of application and to avoid intermediate unsightly reflections, while obtaining a better rise in color. EXAMPLE 2 1. Coloring step: The following coloring composition was prepared by mixing, at the time of use, the powders of natural dyes with water at 50 ° C. in order to produce the following poultice:

This mixture is applied to locks of permed Caucasian hair (BP) containing 90% white hair at a bath ratio of 10 grams per 1g of lock. The locks are left to stand for 60 min at 33 ° C. under cellophane. At the end of the pause time, the locks are rinsed and washed with Ultra Soft Chamomile Shampoo and then wrung out. • 2. Neutralizing dye post-treatment

The following post-treatment compositions were prepared:

At the end of the coloring step time, each of the post-treatment compositions is then applied at the rate of 5 g per gram of hair on locks previously colored with composition C2 and left to stand for 15 min at 33 ° C. under cellophane comparatively to reference locks colored with composition C2 to which no post-treatment composition has been applied. At the end of the pause time, all the locks are then rinsed and washed with Ultra Soft Chamomile Shampoo and then dried.

Results:

The locks were evaluated visually and in the CIEIab system as described previously.

We observed that:

Without post treatment applied, the poultice colors the hair in unsightly golden green. Over time, the color changes and the green reflection disappears, but the color retains an unsightly shade.

The basic post-treatment with dye (comparative composition B4) partially neutralizes the green of the coloring but the shade remains unsightly. - The post treatment of the acid invention with the carminic acid dye according to the invention (composition B5) allows and intensifies the color in terms of increase in

color and power and to neutralize the unsightly green / golden reflection, unlike comparative coloring processes (without post treatment or with an alkaline post treatment with dye).

These observations are confirmed by the values of the colorimetric measurements, in particular by significantly lower b * values (less yellow) for the hair treated with composition C2 followed by a post treatment with composition B5 (process of the invention) compared to colored hair without post-treatment or with alkaline post-treatment C (comparatives 1 and 2).

In addition, the measured colorimetric values demonstrate, in the case of post-treatment with composition B5 according to the invention, significantly higher DE * values (better rise in color), and lower L * values (more coloration intense). > Color evolution over time:

Visual evaluation: After 3 weeks, in the case of comparative methods 1 and 2, we observed that the color changes over time, in particular that the green component of the color disappears. On the other hand, in the case of coloring with the method according to the invention, the color is more stable than with the comparative methods.

Colorimetric evaluation of the color revolution:

The values of DE T3semaines / TO and Db * T3semaines / T0 were calculated from the same equation as that described above, but from the colorimetric values measured 3 weeks after the implementation of the coloring process.

This is confirmed by the colorimetric measurements with lower values of variation of the yellow / blue component (Db *) in the case of treatments with the compositions of the invention and also lower color variations (DE *). -> Consequently, the coloring process according to the invention makes it possible to stabilize the coloring from the day of the application and aesthetically (less yellow / green) and more effectively than with the comparative processes.

Claims (31)

1. A process for dyeing keratin fibers, in particular human keratin fibers, such as the hair, in which said fibers are treated in several stages, comprising: - at least one dyeing step E1) of said fibers using a cosmetic composition dye A comprising powder of plant (s) tndigofère (s) and / or dye extract of plant (s) indigofère (s) i) and optionally henna ii); - at least one step of treatment E2) of said fibers using an aqueous cosmetic composition B whose pH is less than 7, comprising one or more natural dye (s) iii), chosen from: o iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, and / or l kermesic acid; o iii-ii) betalains, preferably betanine, o iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) preferably comprising at least three hydroxy groups, preferably chosen from cyanidine, delphinidine, pelargonine, malvidine, peonidine, petunidine, and mixtures thereof; o iii-iv) carthamine o iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxy groups, preferably chosen from alkanine (also called Orcanette) and / or shikokine; o and their mixtures; iv) one or more acidifying agents, it being understood that composition A is preferably applied first to the keratin fibers; and that composition B is applied to the keratin fibers after application of composition A; the method preferably using at least one rinsing step, and / or one washing step between the coloring step using composition A and the treatment step using application of composition B. 2. Method according to any one of the preceding claims, in which the indigofere plant (s) is (are) chosen from the species of the genera: - Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata Indigofera arrecta , Indigofera gerardiana, Indigofera argenta, Indigofera indica, or Indigofera longiracemosa; - / saiis such as Isatis tinctoria; - Polygonum or Persicaria such as Polygonum tinctorium or Persicaria tinctoria; - Wrightia such as Wrightia tinctoria; - Calanthe such as Calanthe veratrifolia; and - Baphicacanthus such as Baphicacanthus cusia. 3. Method according to any one of the preceding claims wherein the indigofere plant (s) is (are) of the genus Indigofera and more particularly is Indigofera tinctoria. 4. Method according to any one of the preceding claims, in which the composition A comprises a powder content of indigofere plant (s) varying from 10 to 99% by weight, relative to the total weight of the composition A, more particularly varying from 20 to 90% by weight, preferably varying from 40 to 80% by weight, relative to the total weight of said composition A, when composition A is anhydrous. 5. Method according to any one of the preceding claims, characterized in that composition A comprises henna ii). 6. Method according to the preceding claim, characterized in that the henna is red henna. 7. Method according to any one of claims 5 and 6, characterized in that composition A used in the coloring process comprises a henna content varying from 5 to 99% by weight, relative to the total weight of composition A, more particularly varying from 10 to 6% by weight, preferably varying from 15 to 40% by weight, relative to the total weight of said composition A, when composition A is anhydrous. 8. Method according to any one of claims 1 to 3 and 5 to 6 wherein the composition A comprises water, preferably comprises a water content ranging from 10% to 99% by weight, more particularly from 20% at 98% by weight, better from 40% to 95% by weight relative to the weight of composition A. 9. Method according to the preceding claim, in which the composition A comprises a powder and / or extract content of indigofere plant (s) varying from 0.5 to 50% by weight, more particularly varying from 1 to 40%. by weight, preferably varying from 5 to 30% by weight, composition A comprising water. 10. Method according to any one of claims 5, 6, 8 and 9 characterized in that composition A used in the coloring process comprises a henna content varying from 0.1 to 30% by weight, more particularly varying from 0.15 to 20% by weight, preferably varying from 0.2 to 10% by weight relative to the total weight of composition A, composition A comprising water. 11. Method according to any one of claims 5 to 10, characterized in that the ingredients i) and ii) are present in composition A in a weight ratio i) / ii) varying from 0.1 to 95, preferably from 0, 5 to 50, better from 1 to 10. 12. A coloring method according to any one of the preceding claims, characterized in that composition A comprises one or more organic solvent (s) preferably in a total content ranging from 0.2 to 35% by weight, preferably from 0.5 to 20% by weight, better still from 0.5 to 10% by weight relative to the total weight of composition A, preferably chosen from lower C1-C4 alkanols, such as ethanol and isopropanol ; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof . 13. Method according to any one of the preceding claims, in which the pH of composition A varies from 2 to 9, preferably from 3 to 7. Better from 4 to 6.5 14. Method according to any one of the preceding claims, characterized in that composition B has a pH of less than 6; preferably less than 5. 15. Method according to any one of the preceding claims, characterized in that composition B has a pH inclusive between 0.5 and 5; more particularly between 0.5 and 4.5; preferably between 1 and 4. 16. Method according to any one of the preceding claims, characterized in that composition B comprises at least one acidifying agent chosen from organic or inorganic acids. 17. Method according to any one of the preceding claims, characterized in that the acidifying agent is chosen from hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids chosen from acetic acid, acid citric; and their mixtures. 18. Method according to any one of the preceding claims, characterized in that the acidifying agent (s) from 0.001% to 10% by weight of the weight of composition B, more particularly from 0.005% to 8% by weight , relative to the weight of composition B. 19. Method according to any one of the preceding claims, characterized in that the natural dye (s) of composition B have an absorption wavelength λ max between 625 and 750 nm or between 300 and 470 nm, better between 625 and 750 nm 20. Method according to any one of the preceding claims, characterized in that the natural dye (s) of composition B are present in a content of between 0.05 and 25% by weight of the total weight of the dye composition , in particular ranging from 0.1 to 10% by weight of the total weight of the coloring composition, preferably from 0.5 to 5% by weight relative to the total weight of composition B 21. Method according to any one of the preceding claims, characterized in that the natural dye (s) iii) of composition B is (are) polyphenols chosen from: - iii-i) anthraquinones comprising ao less a carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistin and / or acid kermesic, iii-ii) betalains, preferably betanine; iii-iii) anthocyanidins (also called anthocyanides, or anthocyanidols) preferably of formula (Vg) which comprise at least three hydroxy groups, preferably chosen from cyanidine, delphinidine, pelargonine, malvidine, peonidine, petunidine , and mixtures thereof; iii-iv) carthamine and mixtures thereof; 22. Method according to any one of the preceding claims, characterized in that the natural dye (s) iii) of composition B comprise at least one carboxylic acid function, and are chosen from: iii-i) anthraquinones, preferably comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistin and / or kermesic acid, iii-ii) betalains, preferably betanine; iii-iv) carthamine 23. Method according to any one of the preceding claims, characterized in that the natural dye (s) iii) of composition B is (are) chosen from anthraquinones, comprising at least one acid function carboxylic, chosen from those of formula (A1) below: (A1) as well as their tautomeric and / or mesomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, and their solvates such as hydrates; formula (A1) in which: • R1 and R8, identical or different, represent a hydrogen atom, a hydroxy group, or alkyl such as methyl; • R2 represents a hydrogen atom, a hydroxyl group, carboxy -C (O) OH or carboxylate -C (O) O ', Q + with Q + representing an alkali or alkaline earth metal such as potassium or calcium; • R3 represents an i) hydrogen atom, ii) a hydroxy group, or a group iii) aryl optionally substituted, preferably a phenyl group optionally substituted by one or more groups chosen from a) hydroxy, b) amino, c) (Ci-C6) alkyl optionally substituted by one or more groups chosen from hydroxy, carboxy and (Ci-C4) alkylcarbonylamino; • R4 represents a hydrogen atom, or a hydroxy group; • R5 represents a hydrogen atom, or a hydroxy, carboxy or carboxylate group -C (O) O ', Q + with as defined previously; • R6 represents a hydrogen atom, a hydroxy group, -O; Q + with Q + as defined above, carboxy or carboxylate -C (O) O ', Q + with Q + as defined above; • R7 represents a hydrogen atom, a hydroxy group or a glycosylated radical, preferably glucose; • With the provision that at least one of R2, R5, and / or R6 represents a carboxy group -C (O) OH or carboxylate -C (O) O ', Q + with Q + representing an alkali or alkaline-earth metal such as potassium or calcium; 24. Method according to any one of the preceding claims, characterized in that the natural dye (s) iii) of composition B is (are) chosen from anthraquinones comprising at least one carboxylic acid function, preferably chosen from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, and / or kermesic acid. 25. Method according to any one of claims 1 to 22, characterized in that the natural dye (s) of composition B is (are) chosen (s) from betalains, preferably betanine. 26. Method according to any one of claims 1 to 21, characterized in that the natural dye (s) of composition B is (are) chosen (s) from anthocyanidins (also called anthocyanides, or anthocyanidols) of the following formula (Vg) which contain at least three hydroxy groups: formula (Vg) in which: • R1, R2, R3, R4, R10, R11, R12, R13 and R14, identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from i) hydroxy, ii) (Ci-Ce) alkyl, iii) (Ci-Ce) alkoxy, iv) (Ci-C6) alkylthio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vii) optionally substituted amino, viii) linear alkenyl or optionally substituted branched, ix) optionally substituted cycloalkyl, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di) ((hydroxy) (Ci-C6) alkyl) amino, xiii) glucosyl , xiv) RZC (X) -Y- with R representing a hydrogen atom, a (Ci-Ce) alkyl or aryl group optionally substituted in particular by at least one hydroxy group such as 3,4,5-trihydroxyphenyl; Y and Z, which may be identical or different, represent a bond, or an oxygen, sulfur atom or a group --N (R ') - with R' representing a hydrogen atom or a (Ci-Cs) alkyl group, Y can also represent a (Ci-Ce) alkylene group; X representing an oxygen or sulfur atom, or N-R "with R" representing a hydrogen atom or a (Ci-C6) alkyl group; • R6, R8, identical or different, represent a hydrogen atom, or a group chosen from a hydroxy group, a (Ci-Ce) alkyl group, or an RZC (X) -Y- group as defined above, • or then the motif (V) constitutes the polymeric unit of a polyphenol which will be linked to the other units of said polyphenol by positions 4, 6 or 8 of the chroman ring in which case R1, or R3 and R6 form a covalent bond with the other units said polyphenol; it being understood that at least three radicals of the compounds of formula (V) chosen from R1, R2, R3, R4, R8, R10, R11, R12, R13 and R14 represent a hydroxy group; the compounds of formula (Vg) being cationic and there is associated therewith an Anionic counter ion, organic or mineral, such as halide. preferably, the radicals R1, R6, R14 and R10 representing a hydrogen atom. 27. A method according to any one of claims 1 to 21 and 26, in which the said natural dye (s) iii) is chosen from anthocyanidins chosen from cyanidine, delphinidine, pelargonin, malvidine, peonidine, petunidine, and their mixtures. 28. A coloring method according to any one of claims T to 22, characterized in that the said natural dye (s) iii) is chosen from carthamine. 29. A coloring method according to any one of the preceding claims, characterized in that composition A is applied first to the keratin fibers; and composition B is applied to the keratin fibers after application of composition A. 30. A coloring method according to any one of the preceding claims, characterized in that it implements at least one rinsing step, and / or a washing step between the coloring step using composition A and the treatment step using composition B, preferably a rinsing step. 31. Use of an aqueous composition B, the pH of which is less than 7, comprising one or more acidifying agent (s) iv) as defined in any one of the preceding claims and one or more natural dyes iii ) as defined according to any one of the preceding claims to accelerate the stabilization of the color of the colored fibers from powder and / or dye extract of indigofere plant (s) and possibly of henna over time and to improve the intensity and / or the rise of the color and / or the color fastness.