FR3075643B1 - 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 dyeing 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 MULTI-STAGE KERATIN FIBERS FROM INDIGOFERE (S) PLANT POWDER AND ACID PROCESSING COMPRISING A PARTICULATE COLOR

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 i) indigestible plant powder (s) and / or a dye extract of indigo plant (s) and possibly henna ii); at least one post-treatment step E2) of said fibers employing an aqueous cosmetic composition B whose pH is less than 7, comprising one or more natural dye (s) iii) particular, different (s) from henna and indiqoids and iv) one or more acidifying agents; the composition A preferably being applied first to the keratinous fibers; and the composition B being applied to the keratinous fibers after application of the composition A and (II) the use of an aqueous acid composition B, comprising one or more particular natural dyes, to accelerate the stabilization of the color of the colored fibers to from indigo and possibly henna in time (the day of the implementation of the coloring process) and improve the intensity, the rise of the color and / or the behavior of the color.

Indeed, the colorings from indigo and possibly henna are generally evolutive in time in terms of color, they have a yellow / green color characteristic on the day of application (that is to say, the day of coloring). This color "raw" unattractive, little appreciated by color cutisers) that evolve to the desired color after a few hours (48H to 1 week) and can turn color over time (appearance of purplish red highlights after generally 2 to Three weeks). There is therefore a need to stabilize this coloration to obtain an aesthetic coloration on the day of application (brown example free of yellow / green reflections) which evolves little in time (without color change) and while respecting the integrity of the keratinous fibers.

Two major modes of staining human keratinous fibers, and in particular the hair, are known.

The first, called oxidation or permanent staining, consists in implementing 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, combined with oxidizing products, make it possible to access, by a process of oxidative condensation, 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 indolic compounds.

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

The second mode of staining, called direct or semi-permanent staining, comprises the application of direct dyes which are colored and coloring molecules having an affinity for the fibers. Given the nature of the molecules used, these remain rather on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of precursors of oxidation dyes. The main advantages of this type of staining is that it does not require an oxidizing agent which limits the degradation of the fibers and does not use dyes with a certain reactivity, thus 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", section 5.2.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002 / 14356007.a 571, pub2). Indigo continues to be used to beautify women by coloring hair, nails, or to color leather, silk and wool fabrics, etc. Indigo [482-89-3] is a blue natural dye and its indirect isubere is red. Their crude formulas are: C16H10N2O2; and their chemical structures are as follows:

Depending on the oxidation and oxidation, isatin may give indogotin or indirubin. (Maugard et al, 2001). The presence of these two isomers explains the purple color of the indigo more or less marked depending on the respective proportion in the hair of the two isomers formed in the hair (especially purple to purple if the amount of indirubin increases).

Indigo is derived from indican can be prepared from different plants called indigo-like Indigofera tinctoria, suffruticosa indigo, Polygonum tinctorium etc (see Kirk-Othmer Encyclopedia of Chemical Technology, updated 17/04 / 2009, DOI 10.1002 / 0471238961.0425051903150618.a01.pub2). Indigestible plants are usually cut and soaked in hot, heated, fermented and air-oxidized water to release the purple-blue indigo (see Rev. Chem., 2011, 111, 25372561, p. 2537-2561). Indigo is the result of the hydrolysis and oxidation of the indican (glycosylated precursor).

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

The colorings resulting from mixtures of indigo and henna are therefore generally generally progressive in time in terms of color, they have a yellow / green color characteristic on the day of coloring (color "raw" unsightly, unappreciated by female consumers. staining) that evolve towards the desired colorations after a few hours (48H to 1 week) and can turn color over time (appearance of purplish red glints after generally 2 to 3 weeks). There is therefore a need to stabilize this coloration to obtain aesthetic coloration on the day of application (brown example without yellow / green reflections) which evolves little in time (without color change).

In order to remedy this problem of unattractive coloration on the day of coloring and color evolution, it is known to "dope" the coloring by adding direct dyes to mask the undesirable reflections, these dyes being generally 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). This option has the disadvantage for users of natural products, or supporters of "natural / organic", that the color is partly made from synthetic dyes. However the reflection made on the day of the application does not prevent the bend of color in time (evolution of the yellow reflection always present in the fiber, although masked, towards red).

Moreover, the colorations 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, pp. 236-241 (2005)).

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

There is therefore a real need to develop coloring processes which make it possible to obtain powerful, aesthetic and natural colorations as soon as the application is finished, while respecting the cosmetic properties of the keratin fibers and which make it possible in particular to obtain colorations as soon as possible. fast, whose coloring obtained does not show yellow / green reflections which are judged unsightly by the user, having an increase in color improved and less aggressive for the hair and at the same time resistant to external agents (light, bad weather) , shampoos), which are stubborn and / or homogeneous while remaining powerful and / or chromatic, which does not change over time (especially towards red highlights).

This object is achieved by the present invention which relates to a method for dyeing keratinous fibers, in particular human keratinous fibers, such as the hair, wherein said fibers are treated in several steps, comprising:

at least one staining step E1) of said fibers employing a coloring cosmetic composition A 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, andcomprising 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, laccalic acid C, laccal acid D and / or kermesic acid;

iii-ii) betalaines, preferably betanine;

iii-Hi) the anthocyan id i born (also called anthocyanides or anthocyanidols), preferably of formula (Vg) having at least three hydroxy groups _v preferably chosen from lacyanidine, delphinidin, the pelargonine, malvidin, peonidin petunidine and their mixtures;

iii-iv) carthamine;

- iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxyl 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 composition A is preferably applied first to the keratinous fibers; and that the composition B is applied to the keratinous fibers after application of the composition A;

the method preferably implementing at least one rinsing step, and / or a washing step between the dyeing step employing composition A and the treatment step implementing the application of composition B .

Thus, according to a preferred embodiment, the dyeing method according to the invention implements a first step of dyeing the keratinous fibers via the application of a coloring composition A to the fibers comprising powder and / or extracted from plant (s) indigestible (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, in post-processing.

According to another embodiment, the dyeing method 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 staining the keratinous fibers via the application of a coloring composition A to the fibers comprising powder and / or extract of indigestible plant (s) and possibly 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 color stabilization of 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.

The method for dyeing keratin fibers according to the invention has the advantage of coloring said fibers, in particular human keratinous fibers, in particular the hair, with results of natural colorings without yellow / green reflections, and / or powerful chromatic colorations. resistant to washes, perspiration, sebum and light and more durable without altering the fiber. In addition, the colorations obtained from the process are homogeneous from the root to the tip of a fiber (low color selectivity). The treated keratinous 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. they are cosmetically acceptable therefore suitable for use for application to keratinous fibers, especially for application to human keratinous fibers, such as the hair.

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

Preferably, the composition A is an aqueous composition.

(') powder and / or extract of indigestible plant (s)

The dye composition A according to the invention comprises powder and / or an indigestible plant extract (s). (For the purposes of the present invention, the expression "indigo-plant extract" is understood to mean an "indigo-plant dye extract")

As indigo plant we can cite many species from the genera:

- Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata Indigofera arrecta, Indigofera gerardiana, Indigofera argenta, Indigofera indica, Indigofera longiracemosa;

- / satis such as Isatis tinctoria;

- Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria);

Wrightia such as Wrightia tinctoria;

- Calanthus such as Calanthe veratrifolia; and

- Baphicacanthus such as Baphicacanthus cusia.

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

All or part (especially leaves especially for Indigofera tinctoria) of the indigo plant can be used.

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

It is understood that said indigestible plant particles (s) preferably have a moisture content of between 0 and 10% by weight, relative to the total weight of the powders.

The indigo-producing 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 indigo plant.

The indigo-producing plant powder according to the invention is a natural product derived from indigestible plants, reduced by grinding or other mechanical means, into fine particles.

Preferably, an indigestible plant powder (s) is used.

According to a particular embodiment of the invention, the composition A is in the form of a solid, preferably pulverulent, preferably anhydrous composition. According to this embodiment, the indigestible plant powder (s) is preferably present in the composition A in a content ranging 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 ranging from 20 to 80% by weight.

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

According to this embodiment, the powder and / or indole plant extract (s) is present in the composition A preferably in a content ranging from 0.5 to 50% by weight, relative to the total weight of the composition A, when the composition A is aqueous, more particularly ranging from 1 to 40% by weight, preferably ranging from 5 to 100% by weight.

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

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

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

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

Preferably the ready-to-use composition A 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 weight of the composition A ready to use.

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

Henna ii)

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

According to the present invention, "henna" means a henna plant powder and / or a henna plant coloring extract, preferably a henna plant such as Lawsonia alba or Lawsonia inermis. The powder and / or the henna plant dye extract especially comprises lawsone and / or one of its glucosyl precursors.

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

It is understood that "henna powder" (and "indigestible 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 from henna plants or indigesters, reduced by grinding or other mechanical means, into fine particles.

Preferably the henna used in the invention is red henna (Lawsonia inermis, alba). The lawsone [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 one particular embodiment of the invention, the particle size of the henna powder is fine. According to the invention, more particularly is meant a particle size of less than or equal to 500 μm. Preferably, the powder consists of fine particles of size included between 10 and 300 μm and more particularly between 50 and 250 μm. It is understood that said henna particles preferentially have a moisture content of between 0 and 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, the composition A is in the form of a solid, preferably pulverulent, preferably anhydrous composition. According to this embodiment, the henna is preferably present in the composition A in a content ranging from 5 to 99% by weight, relative to the total weight of the composition A, more particularly ranging from 10 to 60% by weight, preferably varying from 15 to 40% by weight, in particular when the composition A is anhydrous.

As indicated above, according to another particular embodiment of the invention, the composition A is obtained by mixing just before use (that is to say extemporaneously) the indigestible plant powder (s) i) and henna ii) (when present) with water or an aqueous composition to obtain a ready-to-use dye 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 ranging 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 ranging from 0.2 to 10% by weight.

Preferably, when the dyeing process according to the invention uses henna, then the powder and / or the indigo plant extract i) and the henna ii) are present in the composition A in a weight ratio i) / ii) ranging from 0.1 to 95, preferably from 0.5 to 50, more preferably from 1 to 10.

Composition B:

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

Preferably, the pH of the composition B used according to the invention has a pH of between 0.5 and 5 inclusive; 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 inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, alpha hydroxy carboxylic acids (AHAs) such as citric acid, lactic acid; and their mixtures.

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

According to one 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 phosphoric acid and its salts.

Preferably the composition (B) comprises an inorganic buffer system comprising a mixture of at least one inorganic (inorganic) acid and its conjugate base, namely the inorganic salt of said inorganic acid. Preferably the 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 NaH ₂ PO ₄ , dipotassium hydrogen phosphate K ₂ HPO ₄ , disodium hydrogen phosphate Na ₂ HPO ₄ , potassium hydrogen phosphate K ₃ PO ₄ , sodium phosphate Na ₃ PO ₄ and mixtures thereof.

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

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

Natural dyes iii) present in composition B:

The 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, laccaic acid and / or kermesic acid,

ii) betalaines, preferably bethanol iii-iii) anthocyanidins (also called anthocyanidins, or anthocyanidols) preferably of formula (Vg) which comprise at least three hydroxyl groups, preferably chosen from cyanidine, delphinidin pelargonin, malvidin, peonidin, petunidin, and mixtures thereof;

iii-iv) carthamine

- iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxyl 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, xanthopurpurine, rubiadine, lucidine, munjistin, anthragallol, purpurin, pseudopurpurine, morindone, and mixtures thereof, preferably at least three hydroxyl groups, preferably selected from anthragallol, purpurine, pseudopurpurine, morindone, munjistin, and mixtures thereof.

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

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

Preferably, according to this embodiment, the natural dyes iii) are preferably 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, munjistin and / or kermesic acid; iii-ii) betalaines, 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 anthocyanidins, or anthocyanidols), preferably of formula (Vg), which comprise at least three hydroxyl groups, preferably chosen from cyanidin, delphinidin, pelargonin, malvidine, peonidine, petunidine, and mixtures thereof;

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

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, the 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 λ _max 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 that absorb in the red

i.e. at an absorption wavelength which is in the range particularly between 300 and 470 nm, or the violet between 625 and 750 nm of red-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 the following formula (A1), comprising at least one less a carboxylic acid function:

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:

• R ¹ and R ⁸ , identical or different, represent a hydrogen atom, a hydroxy group, or alkyl such as methyl;

R ² represents a hydrogen atom, a hydroxy group, carboxy -C (O) OH or carboxylate -C (O) O ', Q ⁺ with Q ⁺ representing an alkali metal or alkaline earth metal such as potassium or calcium;

R ³ represents a hydrogen atom, a hydroxy group, or an optionally substituted (iii) aryl group, preferably a phenyl group optionally substituted with one or more groups chosen from a) hydroxy, b) amino, c ) (Ci-Ce) alkyl optionally substituted with one or more groups selected from hydroxy, carboxy and _(Ci-C4) alkylcarbonylamino;

• R ⁴ represents a hydrogen atom, or a hydroxyl group;

R ⁵ represents a hydrogen atom, or a hydroxy, carboxyl or carboxylate group -C (O) O ', CT with as defined above;

R ⁶ represents a hydrogen atom, a hydroxyl group, -O ', Q ⁺ with Q ⁺ as defined above, carboxy or carboxylate -C (O) O', Q ⁺ with Q ⁺ as defined above;

R ⁷ represents a hydrogen atom, a hydroxyl 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:

R ¹ is hydroxy, or (C ₁ -C ₄ ) alkyl;

R ² , R ⁴ and R ⁸ , which may be identical or different, represent a hydrogen atom or a hydroxyl group;

R ³ represents a hydrogen atom, a hydroxy group, or a substituted phenyl group optionally substituted by one or more groups selected from hydroxy, carboxy and (C ₁ -C ₄ ) alkylcarbonylamino such as:

OH

with Y representing a group selected from: -CH (NH ₂ ) -C (O) OH, -CH ₂ -OH, -NH-C (O) -CH ₃ ; and the point of attachment to the rest of the molecule.

R ⁵ and R ⁶ , which are identical or different, represent a hydrogen atom, or a hydroxyl, carboxy -C (O) OH or carboxylate-C (O) O 'group, Q ⁺ with Q ⁺ representing an alkali metal or alkaline earth such as potassium or calcium; and • R ⁷ 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,

R ¹ represents a group (C ¹ -C 9) alkyl;

R ² represents a carboxyl or carboxylate group -C (O) O ', Q ⁺ with Q ⁺ representing an alkali metal or alkaline earth metal such as potassium or calcium;

R ³ and R ⁸ are hydroxy;

R ⁴ represents a hydrogen atom or a hydroxy group, preferably hydrogen;

R ⁶ represents a hydroxy group, -O ', Q ⁺ with Q ⁺ as defined previously; and • R ⁷ represents a hydrogen atom or a glycosyl radical such as glucose.

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

The structures of these compounds are as follows:

Laccaic Acid AR = CH ₂ CH ₂ NHCO CH ₃

Laccaic Acid BR = CH ₂ CH ₂ OH

Laccaic Acid CR - CH ₂ CH (NH ^C 0 0 H)

CO OH

OH

Laccaic Acid D

Laccaic acid

Preferably, the natural dyes iii) are selected from carminic acid, laccaic acid D or kermesic acid, pseudopurpurine and munjistin and mixtures thereof.

According to a second advantageous embodiment of the invention, the natural dye (s) iii) are chosen from betalaines, preferably betaine. Betalaines are dyes from red beets.

bétanine

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

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

formula (Vg) in which:

R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from i) hydroxy, ii) (C ₁ -C ₆ ) alkyl, iii) (C ₁ -C ₆ ) alkoxy, iv) (C ₁ -C ₆ ) alkylthio, v) carboxyl, vi) alkyl carboxylate or alkoxycarbonyl, vii) optionally substituted amino, viii ) linear or branched optionally substituted alkenyl, ix) cycloalkyl optionally substituted, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di) ((hydroxy) (Ci-C ₆₎ alkyl) amino , xiii) glucosyl, xiv) RZC (X) -Y- with R representing a hydrogen atom, a (CiC ₆ ) alkyl or aryl group optionally substituted in particular by at least one hydroxyl group such as 3,4,5-trihydroxyphenyl; ; Y and Z, which may be identical or different, represent a bond, or an oxygen atom, sulfur atom or a group -N (R ') - with R' representing a hydrogen atom or a (Ci-C ₆ ) alkyl group Y may also represent a (C 1 -C 6) alkylene group; X represents an oxygen atom, sulfur, or NR "with R" representing a hydrogen atom or a group (C ₁ -C ₆ ) alkyl;

R ⁶ and R ⁸ , which may be identical or different, represent a hydrogen atom, or a group chosen from a hydroxyl group, a (C 1 -C 6) alkyl group or an R-ZC (X) -Y- group such as defined above, or • the unit (V) constitutes the polymeric unit of a polyphenol which will be connected to the other units of said polyphenol by positions 4, 6 or 8 of the chromane ring in which case R ¹ , or R ³ and R ⁶ form a covalent bond with the other units of said polyphenol;

it being understood that at least three radicals of the compounds of formula (Vg) chosen from R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent a group hydroxy;

the compound of formula (Vg) being cationic and it is associated with it an anionic counterion, organic or inorganic, such as halide.

preferably, the radicals R1, R6, R14 and R10 representing a hydrogen atom.

Preferably the group R-Z-C (X) -Y- compounds of formula (V) represents a

3,4,5-trihydroxyphenyl-1-carbonyloxy (-O-gallate). Preferably, the radicals R 1, R ₂ , R ₃ , R ₄ , R ₁₀ , R ₁₁ , R ₁₂ , R 13 and R 14 are chosen from hydrogen, and 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 R 2, R 3, R 4, R 8, R 13, R 12 and R 11 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.

R2 R3 R4 R8 R13 R12 R11 R1, R6, R14 and R10 cyanidin -OH -H -OH -OH -OH -OH -H -H delphinidin -OH -H -OH -OH -OH -OH -OH -H malvidine -OH -H -OH -OH -OCH3 -OH -OCH3 -H peonidin -OH -H -OH -OH -OCH3 -OH -H -H petunidin -OH -H -OH -OH -OCH3 -OH -OH -H Rosinidin -OCH3 -H -OH -OH -OCH3 -OH -H -H Pulchellinidin -OH -H -OCH3 -OH -OH -OH -OH -H Europinidin -OH -H -OCH3 -OH -OCH3 -OH -OH -H Hirsutidin -OCH3 -H -OH -OH -OCH3 -OH -OCH3 -H Capensinidin -OH -H -OCH3 -OH -OCH3 -OH -OCH3 -H Carajurin -OH -OH -OCH3 -H -H -OCH3 -H -H Arrabidin -OH -OH -OCH3 -H -H -OH -H -H 3-hydiOxyarrabidin -OH -OH -OCH3 -H -OH -OH -H -H 6 hydiOxydelphinidin -OH -OH -OH -OH -OH -OH -OH -H

According to a preferred embodiment of the invention, the natural dyes iii) are anthocyanidins chosen from cyanidin, delphinidin, malvidin, peonidin, petunidin, and mixtures thereof.

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

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 hydroxyl groups, preferably chosen from alkanine (also called Orcanette). ) and / or the shikokine.

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

By "polyphenol" is meant a compound comprising in its structure several hydroxyl functional groups carried on one or more six-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 selected from carminic acid, laccaic acid A, laccaide acid B, laccaic acid C, laccaic acid D, and / or kermesic acid, iii-ii) betalaines, preferably betanine;

iii-iii) anthocyanidins (also called anthocyanidins, or anthocyanidins) of formula (Vg) which comprise at least three hydroxyl groups, preferably chosen from cyanidin, delphinidin, malvidin, peonidin, petunidin, and mixtures thereof;

iii-iv) carthamine;

and their mixtures;

According to another advantageous embodiment of the invention, the natural dye (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, pseudopurpurin and munjistin and / or keretic acid; ii) betalaines, preferably betanin;

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, laccaid acid B, laccaic acid C, laccaic acid D, and / or kermesic acid, pseudopurpurin and munjistin betaine

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, laccaid acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistin 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 munjistin and / or kermesic acid

In the context of the present invention, the natural dye (s) iii) "pure" are present in the 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 , 1 to 10% by weight of the total weight of the dye composition, preferably from 0.5 to 5% by weight relative to the total weight of composition B.

With regard to extracts iii), the content in composition B containing the extract (s) such (s) which (s) which (s) is (s) 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:

Compositions A and / or B as defined above may comprise one or more organic solvent (s). As the 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, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and 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 in question, and still more preferably between 0.5 and 10% by weight approximately.

Oils

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

By "oil" is meant a "fat" 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 less than 500 cps (defined for example from the Newtonian plateau determined using a TA Instruments ARG2 rheometer equipped with a mobile geometry cone plane d a diameter of 60 mm and an angle of 2 degrees over a range of shear stress ranging from 0.1 Pa to 100 Pa)

By "fatty substance" is meant an organic compound which is insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg) (solubility of less than 5% and preferably of 1%, even more preferentially at 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, the fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, 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" 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 more than 16 carbon atoms and in particular alkanes; oils of animal origin; triglyceride oils of vegetable origin; essential oils ; glycerides or fluorinated oils of synthetic origin, fatty alcohols; esters of fatty acids and / or fatty alcohol different from triglycerides, fatty acid amides and silicone oils.

Preferably, the oils are not oxyalkylenated or glycerolated ethers.

Preferably, the oils do not comprise an oxyalkylenated C2-C3 unit or a glycerolated unit.

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

The oils that can be used as the second ingredient b) in the composition A or B according to the invention can be silicones.

The silicones may be volatile or non-volatile, cyclic, linear or branched, modified or otherwise with organic groups, having a viscosity of 5.10 ⁶ to 2.5 m ² / s at 25 ° C. and preferably 1.10 ⁵ to 1 m ² / s.

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

Organopolysiloxanes are further defined in the work of Walter Noll Chemistry and Technology of Silicones (1968), Academie Press. They can be volatile or nonvolatile.

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 between:

(i) cyclic polydialkylsiloxanes having from 3 to 7, preferably from 4 to 5, silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name 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 the VOLATILE® SILICONE FZ 3109 marketed by UNION CARBIDE, of formula:

i- D - D --- --- D -D'- | CH, CrL 1 with : - Si-O - with' : | -Si-O - ch ₃ c ₈ h ₁₇

Cyclic polydialkylsiloxane mixtures can also be mentioned with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '- (hexa) -2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane;

(ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10 ^ m ² / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name SH 200 by the company 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.

Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used.

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

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products:

the SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil;

the oils of the MIRASIL® series marketed by RHODIA;

the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm ² / s;

- VISCASIL® oils from GENERAL ELECTRIC and some oils from 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 the oils of the 48 series from the company RHODIA.

Compositions A and / or B as defined above may 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 for the purposes of the invention, the alcohols, esters and fatty acids more particularly have at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising 6 to 30 carbon atoms, which is optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise.

More specifically, the latter may represent a C ₁ -C ₁₀ alcohol and C ₆ -C ₃ fatty acid ester such as RC (O) -O-R 'with R representing a linear C ₆ -C ₃₀ alkyl group. or branched, linear or branched C ₃ -C ₃ alkenyl, comprising one or two unsaturations, and R representing a linear or branched C ₁ -C ₁₀ alkyl group.

Preferentially, R represents a linear alkyl group C ₁ -C ₂₀ and R 'represents a C ₁ -C ₆ alkyl group, preferably branched, such as isopropyl myristate.

According to another advantageous variant, ingredient ii) represents one or more C ₆ -C ₃₀ fatty acid amides and C ₁ -C ₁₀ primary or secondary amine, preferably primary amine, such as those of formula R "-C (O) -N (R _a) -R '" wherein R "is alkyl, C6-C ₃ o linear or branched alkenyl, C6-C ₃ o linear or branched, with one or two unsaturated, which may be substituted by one or more hydroxyl groups, or (di) (CiC ₆ Xalkyl) amino, and R '"represents a linear or branched Ci-Ci ₀ alkyl group, R _a representing a hydrogen atom or an alkyl group as defined for R '". Preferably R represents a C ₄₄ -C _{2 6} alkenyl group, R _a represents a hydrogen atom and R '"represents a C ₁ -C ₆ alkyl group optionally substituted with (di) (C ₁ -C ₄ ) (alkyl) ) amino such as oleylamidopropyl dimethylamine.

As regards the C 6 -C alkanes, the latter are linear, branched, and possibly cyclic. By way of example, mention may be made of hexane, dodecane and isoparaffins, such as isohexadecane and isodecane. The linear or branched hydrocarbons having more than 16 carbon atoms may be chosen from paraffin oils, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and squalene, and mixtures thereof. ,

Among the hydrocarbons, mention may be made of the refined plant perhydrosqualene sold under the name Fitoderm by Cognis; vegetable squalane marketed for example under the name Squaueve by Biosynthis.

The following compounds may also be mentioned:

a mixture of branched C15-C16 alkanes, for example that marketed by the company SEPPIC under the name EMOGREEN L15;

a mixture of linear and / or branched C 13 -C 15 alkanes, for example that marketed by the company SEPPIC under the name EMOSMART L15.

Among the animal oils there may be mentioned perhydrosqualene.

Among triglycerides of plant or synthetic origin, mention may be made of liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or else, for example, sunflower, corn, soya, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, caprylic / capric acid triglycerides as 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 perfluoromethyl

1,3-dimethylcyclohexane, sold under the names FLUTEC® PC1 and FLUTEC® PC3 by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or the bromoperfluorooctyl 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 include those mentioned in Ullmann's Encyclopedia of Industrial Chemistry ("Flavors and Fragrances", Karl-Georg Fahlbusch et al., Published Online: JAN 15, 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" an oil containing at least one silicon atom.

According to a variant of the invention, the oil or oils are chosen from C ₆ -C 16 alkanes, hydrocarbons containing more than 16 carbon atoms, polydecenes, liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or mixtures thereof.

More preferably, the oils are chosen from liquid petroleum jelly and alkanes from Οβ-Οι ₆₁ polydecenes, hydrocarbons with more than 16 carbon atoms.

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

According to another particularly preferred embodiment of the invention, the oils are chosen from oils of natural origin, more particularly oils of vegetable origin preferentially chosen from jojoba, babassu, sunflower, olive and nut oils. coconut, brazil nuts, marula, maize, argan, soya, squash, grape seed, 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, the compositions A and / or B may contain one or more oils of vegetable origin, preferably chosen from avocado oil, olive oil, coconut oil and coconut oil. argan oil and sunflower oil; more preferably, the oil or oils of the invention are chosen from coconut oils, and mixtures thereof.

According to a preferred embodiment, the compositions A and / or B can contain one or more oils chosen from C 6 -C 6 hydrocarbons and more than 16 carbon atoms and in particular alkanes; preferably from:

hydrocarbons C ₆ -C _6, the latter are linear, branched, optionally cyclic, preferably selected 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, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, hemisqualane, squalane, squalene and mixtures thereof;

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 of between 1 and 80% by weight, more particularly between 2 and 50% by weight, and preferably between 3 and 40% by weight. by weight, and more preferably between 2 and 25% by weight relative to the total weight of said compositions.

The additives :

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

The adjuvants above are generally present in an amount for each of them 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, one 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 substantially not, altered by the addition or additions envisaged.

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) indigo (s) i) and henna ii) and natural dyes iii as previously described.

The synthetic direct dyes are preferably chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of common use such as neutral, benzene neutral, acid or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azinigues, triarylmethaniques, indoaminiques, methines, styriles, porphyrins, metalloporphyrines, phthalocyanines, methine cyanines, and fluorescent dyes.

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

These natural dyes 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, especially fine whose particles have sizes identical to that of the indigo plant powder (s) as defined above.

When they are present, the direct, natural or synthetic dye (s) different from the indigenous plant powder (s) and henna ii) used in the process of the invention, particularly represents 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, the composition B can comprise one or more natural additional 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. vinip

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

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

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

When they are present, the oxidation base (s) present in the composition (s) are in general present each in an amount of between 0.001% and 10% by weight relative to the total weight of the substance (s). coloring compositions.

Preferably, the dyeing method of the invention does not use oxidation dye.

pH of the composition A ready to use

According to a particular embodiment of the invention the pH of the composition A ready to 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, more preferably from 4 to 6.5

The pH of the ready-to-use composition A can be adjusted to the desired value by means of acid or alkaline agent (s) usually used for dyeing keratinous fibers or else at the same time. using conventional buffer systems,

Among the acidic agents used in the compositions of the invention, mention may be made of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid and 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 dyeing process uses one or more surfactants. Preferably, the surfactant (s) is (are) chosen from anionic and nonionic surfactants.

Coloring process according to the invention

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

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

Preferably, the dyeing method according to the invention implements the following steps:

the first step consists in the preparation of the composition A as defined above, in particular in the form of a poultice as defined above comprising water, from powder and / or extract of indigestible plant (s) i) and possibly henna ii);

- Then the ready-to-use composition A as defined above is applied to the keratinous 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 from 15 minutes. 75 minutes, better 15 to 60 minutes;

and then, on said fibers, the aqueous composition B having a pH of less than 7 and comprising one or more natural dye (s) iii) chosen from:

iii) i) the 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) betalaines, preferably betanin;

iii-iii) anthocyanidins (also called anthocyanidins, or anthocyanidols) preferably of formula (Vg) as described above which comprise at least three hydroxy groups preferably chosen from cyanidine, delphinidine _T pelargonine, malvidine, peonidine petunidine and their mixtures;

- iii-iv) carthamine

- iii-v) naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxyl 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 to use and the step of applying composition B, the keratinous 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 at the end of this rinsing and / or washing step, if this is carried out, the keratin fibers may then be either dried or left wet, preferably left wet.

According to another embodiment of the process according to the invention, the composition B as defined above is applied first to the keratinous fibers, then the ready-to-use composition A as defined above is applied to the keratinous fibers and is left to be laid 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 dyeing process according to the invention, the keratinous fibers are washed and / or rinsed.

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

According to another embodiment of the invention, the indigenous plant powder (s) i) and optionally 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, more preferably between 25 ° C and 50 ° C.

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

Advantageously, after application of the poultice according to the invention, the hair is subjected to a heat treatment by heating at a temperature ranging from 30 to 150 ° C, more preferably 30 ° C to 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices.

A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C).

The evaluation of the coloration obtained of the keratinous 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 the color, powerful.

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

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

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

ΔΕ * = 7 (Z * -Z _o *) ² + (a * -a0 *) ² + (b * -b0 *) ²

In this equation, L *, a * and b * represent the values measured on locks of hair after staining and L _o *, ao * and bo * represent the values measured on locks of unstained hair. The higher the value of ΔΕ *, the better the rise of the color. The staining stability of the keratinous fibers is also evaluated over time, in particular after 9 days by measuring the colon coordinates of the keratinous fibers and comparing them with the colon coordinates immediately after implementation of the dyeing method according to the invention. The color difference ΔΕ * between the color at T0 and the color after 9 days represents the stability of the hair color and is calculated by the following equation:

^ΔΕ "* = + (a3, * - a" *) ² + (b3, "- b ₀ *) ²

In this equation, Lo *, ao * and bo * represent the colorimetric coordinates measured on strands of hair at T0 immediately after the implementation of the method and Las *, a ₃ s * and b * _3s represent the colorimetric coordinates 9 days after the implementation of the method. The lower the value of AE * stab, the more staining is stable.

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

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

EXAMPLES OF COLORING

EXAMPLE 1

The following compositions have been prepared:

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

1. Coloring step

The following coloring composition is prepared by mixing, at the time of refilling, the natural dyestuff powder with water at 50 ° C. in order to produce the following poultice:

Composition Cl i) Indigo leaf powder (Indigofera tinctoria) (marketed by Nomade Palize under the reference Black Henna of Persia - Henno) 20 ii) LAWSONIA INERMIS SHEET POWDER (marketed by Intermarket Trading Exporter under the reference Henne) 5 Water 75

The ingredients described in (i) and (ii) are solubilized 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 unctuous, and is applied on strands of natural hair 90% of white hair at a rate of 10 grams of composition for 1g of locks. The wicks are left for 60min at 33 ° C under cellophane.

After the break time, the locks are rinsed and washed with Ultra Gentle Chamomile Shampoo and wrung out.

2. Neutralizing post-treatment step

We prepared the

Composition B1 (Comparative) Composition B2 according to the invention Composition B3 according to the invention CITRIC ACID 4 4 4 BENZYL ALCOHOL 1 1 1 HAEMATOXYLON CAMPECHIANUM (WOOD) PURIFIED EXTRACT 1 MA - - BEETROOT EXTRACT (20% BETANIN) - 1 MA - CARMINIC ACID - 1 MA WATER QSP 100 QSP 100 QSP 100 PH 2.2 ± 0.3 2.8 ± 0.3 2.4 ± 0.3

At the end of the staining step, the compositions are then applied at the rate of 5 g per gram of hair and left to rest for 15 min at 40 ° C. under cellophane compared with reference locks that have not undergone post-treatment.

At the end of the break time, all the locks are then rinsed and washed with Ultra Gentle Chamomile Shampoo and dried.

Colorimetric results

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

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

The rise of the color corresponds to the variation of coloration between the locks of hair, before and immediately after implementation of the process are defined by (ΔΕ *) according to the following equation:

ΔΕ "= ^ (Z * -Z" *) ² + (a * -a, *) ² + (b * -b ₀ *) ²

In this equation, L *, a * and b * represent the values measured on locks of hair after staining and L _o *, a ₀ * and b ₀ * represent the values measured on unstained locks of hair. The higher the value of ΔΕ *, the better the rise of the color. Colorimetric measurements were carried out immediately after the implementation of the process (T0), then after 9 days (T 9J).

The delta color difference E between the color at T0 and the color after 3 weeks represents the stability of the hair color and is calculated by the following equation:

Δ E * = *) ² + (a ,, * -a0 *) ² + (bw * -b ₀ *) ²

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

Delta b represents the variation between bo and b _3s .

L * at* b * OF* Color to OF* Enter TO and T9J db * Enter T0 and T9J Color T9J Reference natural hair dyed 67.25 0.73 15.27 - - - Dyed hair without post treatment (comparative 1) 40.65 1.33 14.48 26.62 Green 5.39 -3.16 Beige Hair dyed with post treatment B1 (comparative 2) 40.61 5.73 19.69 27.46 Yellow green 2.15 -1.17 Yellow green Hair dyed with post treatment B2 (invention) 31,05 13.85 3.47 40.27 Warm brown 1.27 0.25 Warm brown Hair dyed with post B3 treatment (invention) 36.45 10.95 10.84 32.75 Brown 1.25 -1.03 Brown

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

Indeed, the dyeing method according to the invention implementing a post-treatment with the compositions B2 and B3 make it possible to neutralize the yellow / green unsightly color on the day of the coloration in contrast to the comparative treatments of the invention without post-treatment or else with post-treatment compositions B1 (comparative 1 and 2).

This translates:

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

In addition, the processes 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, the colorations obtained with the post-treatment compositions B2 and B3 (processes of the invention) also have significantly lower b * values (less yellow) with respect to the colored hair without post-treatment or with post-treatment B1 (comparative 1 to 2).

Furthermore, the colorations obtained with the process of the invention are stable over time (DE TO value / T 9 low), unlike stainings without post-treatment (Comparative 1) which require a certain time before obtaining a color. aesthetic (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 attractive brown (components of higher red or lower yellow). ) at the end of the coloring process. These colorations are also stable over time (AE _T 9j _O ursTofaible).

The method of the invention thus makes it possible to accelerate the revelation of the coloration from henna and indigo to obtain the final coloring result from the day of application and to avoid unsightly intermediate reflections, while obtaining better results. rise of color.

EXAMPLE 2

1. Staining step. The following coloring composition was prepared by mixing the powders of natural dyes with water at 50 ° C. at the time of use in order to produce the following poultice:

Composition C2 LAWSONIA INERMIS SHEET POWDER (marketed by Intermarket Trading Exporter under the reference Henne) 7 INDIGOFERA TINCTORIA POWDER (marketed by Nomade Palize under the reference Henné noir from Perse - Henno) 18 Water 75

This mixture is applied to strands of Caucasian hair permed (BP) to 90 white hair at a bath ratio of 10 grams per 1g of lock. The locks are left for 60 min at 33 ° C under cellophane.

After the break time, the locks are rinsed and washed with Ultra Gentle Chamomile Shampoo and wrung out.

• 2. Post-treatment neutralizing dye

We have

B4 (compare 2) B5 according to the invention Carminic acid 2 2 L-Arginine Qsp pH 8.7 Citric acid PH 3.5 SCLEROGLUCAN GUM (DGLUCOPYRANOSE) PURIFIED 2.7% 2.7% DESIONIZED WATER MICROBIOLOGICALLY CLEAN Qs 100 Qs 100

AI from the time of the staining step, each of the post-treatment compositions is then applied at a rate of 5 g per gram of hair on strands previously stained with the composition C2 and left to pose 15 min at 33 ° C under cellophane compared to reference locks stained with composition C2 on which no post-treatment composition has been applied.

After the break time, all the locks are then rinsed and washed with Ultra Gentle Chamomile Shampoo and dried.

Results:

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

hair L * at* b * DE * ascent Color to Color T 3weeks Hair reference BP undyed BP 70.2 0.67 16.36 - Dyed hair without post treatment (comparative 1) BP 44,01 6.64 20.4 24.52 Golden green Brown Golden Hair dyed with post treatment basic dye + dye composition B4 (comparative 2) BP 45.45 7.27 14.71 22.77 Golden green Brown Golden Dyed hair with post treatment acid with selected dye (composition B5 (invention)) BP 38.79 6.68 11.96 29.27 Brown Brown

We observed that:

Without post treatment applied, the poultice colors the hair in unsightly green gold. With time, the color evolves and the green glow disappears but the coloring 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 acidic invention with the carminic acid dye according to the invention (composition B5) makes it possible and intensifies the color in terms of the rise of the color and of the power and of neutralizing the unsightly green / golden reflection, unlike comparative staining procedures (without post-treatment or with an alkaline post-dye treatment).

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 the composition C2 followed by a post-treatment with the composition B5 (process of the invention) compared to the colored hair without post-treatment or with the alkaline post-treatment C (comparative 1 and 2).

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

> Evolution of the color in 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 coloration disappears. On the other hand, in the case of staining with the method according to the invention, the color is more stable than with the comparative methods.

Colorimetric evaluation of color revolution:

The values of DE T3weeps / T0 and Db * T3weeves / T0 were calculated from the same equation as that described previously, but from the colorimetric values measured 3 weeks after the implementation of the staining process.

hair OF* T3semaines / T0 db * T3semaines / T0 Hair dyed without post treatment (comparative 1) BP 4.5 -2.26 Hair dyed with post-treatment B4 (comparative 2) BP 2.3 1.97 Hair dyed with post treatment B5 (invention) BP 0.9 -0.05

This is confirmed by colorimetric measurements with lower yellow / blue (Db *) component variation values in the case of treatments with the compositions of the invention and also lower color variations (DE *).

Therefore, the dyeing method according to the invention makes it possible to stabilize the coloration as of the day of the application and in an aesthetic manner (less yellow / green) and more efficiently than with the comparative methods.

Claims (31)

1. A process for dyeing 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 employing a coloring cosmetic composition A comprising indigestible plant powder (s) and / or indigo plant (s) colorant extract and optionally henna ii); at least one treatment step E2) of said fibers employing an aqueous cosmetic composition B whose pH is less than 7, 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; o iii-ii) betalaines, preferably betanine, o iii-iii) anthocyanidins (also called anthocyanidins, or anthocyanidols), preferably comprising at least three hydroxyl groups, preferably chosen from cyanidin, delphinidin, pelargonin, malvidine, peonidine, petunidine, and mixtures thereof; o iii-iv) the carthamine o iii-v) the naphthoquinones comprising at least 2 hydroxy groups, preferably at least three hydroxyl 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 preferably the composition A is applied first to the keratinous fibers; and that the composition B is applied to the keratinous fibers after application of the composition A; the method preferably implementing at least one rinsing step, and / or a washing step between the dyeing step implementing composition A and the treatment step implementing the application of composition B. 2. Method according to any one of the preceding claims, in which the indigestible plant (s) is (are) chosen from among 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; - Isatis such as Isatis tinctoria; - Polygonum or Persicaria such as Polygonum tinctorium or Persicaria tinctoria; Wrightia such as Wrightia tinctoria; - Calanthus such as Calanthe veratrifolia; and - Baphicacanthus such as Baphicacanthus cusia. 3. Method according to any one of the preceding claims wherein the indigestible plant (s) is (are) of the genus Indigofera and more particularly is Indigofera tinctoria. 4. Process according to any one of the preceding claims, in which the composition A, comprises a content of indigestible plant powder (s) ranging 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 ranging from 40 to 80% by weight, relative to the total weight of said composition A, when the 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 the composition A used in the dyeing process comprises a henna content ranging from 5 to 99% by weight, relative to the total weight of composition A, plus particularly varying from 10 to 60% by weight, preferably ranging from 15 to 40% by weight, relative to the total weight of said composition A, when the composition A is anhydrous. 8. A process 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 20% at 98% by weight, better still from 40% to 95% by weight relative to the weight of composition A. 9. Process according to the preceding claim, in which the composition A comprises a content of powder and / or extract of indeterminate plant (s) varying from 0.5 to 50% by weight, more particularly ranging from 1 to 40%. by weight, preferably ranging 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 the composition A used in the dyeing process comprises a henna content ranging from 0.1 to 30% by weight, more particularly ranging from 0.15 to 20% by weight, preferably ranging from 0.2 to 10% by weight relative to the total weight of composition A, composition A comprising water. 11. Process according to any one of claims 5 to 10, characterized in that the ingredients i) and ii) are present in the composition A in a weight ratio i) / ii) ranging from 0.1 to 95, preferably from 0, 5 to 50, better from 1 to 10. 12. Coloring method according to any one of the preceding claims, characterized in that the 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, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof . 13. The process as claimed in any one of the preceding claims, in which the pH of the composition A varies from 2 to 9, preferably from 3 to 7, more preferably from 4 to 6.5. 14. Process 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. Process according to any one of the preceding claims, characterized in that composition B has a pH of between 0.5 and 5 inclusive; more particularly between 0.5 and 4.5; preferably between 1 and 4. 16. Process 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. Process 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, and acid. citric; and their mixtures. 18. Process 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 the 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 the composition B have an absorption wavelength λ _max of between 625 and 750 nm or between 300 and 300 nm. and 470 nm, better between 625 and 750 nm 20. Process according to any one of the preceding claims, characterized in that the natural dye (s) of the 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 dye 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 the composition B is (are) polyphenols chosen from: iii) i) 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, pseudopurpurine and munjistin and / or kermesic acid, iii-ii) betalaines, preferably betanine; iii-iii) the anthocyanidins (also called anthocyanidins, or anthocyanidols) preferably of formula (Vg) which comprise at least three hydroxyl groups, preferably chosen from cyanidine, delphinidin, pelargonine, malvidine, peonidine, petunidine , and mixtures thereof; iii-iv) carthamine and mixtures thereof; 22. Process according to any one of the preceding claims, characterized in that the natural dye (s) iii) of the 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 selected from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, pseudopurpurin and munjistin and / or kermesic acid, ii) betalaines, preferably betaine; iii-iv) carthamine 23. Process according to any one of the preceding claims, characterized in that the natural dye (s) iii) of the composition B is (are) chosen from anthraquinones, comprising at least one acid function. carboxylic acid, chosen from those of formula (A1) below: R ⁸ OR ¹ (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: • R ¹ and R ⁸ , identical or different, represent a hydrogen atom, a hydroxy group, or alkyl such as methyl; R ² represents a hydrogen atom, a hydroxy group, carboxy -C (O) OH or carboxylate -C (O) O ', Q ⁺ with Q ⁺ representing an alkali metal or alkaline earth metal such as potassium or calcium; R ³ represents a hydrogen atom, a hydroxy group, or an optionally substituted (iii) aryl group, preferably a phenyl group optionally substituted with one or more groups chosen from a) hydroxy, b) amino, c ) (Ci-C ₆₎ alkyl optionally substituted with one or more groups selected from hydroxy, carboxy and (Ci-C-Oalkylcarbonylamino; • R ⁴ represents a hydrogen atom, or a hydroxyl group; R ⁵ represents a hydrogen atom, or a hydroxyl, carboxyl or carboxylate group -C (O) O ', Q ⁺ with as defined above; R ⁶ represents a hydrogen atom, a hydroxyl group, -O ', Q ⁺ with Q ⁺ as defined above, carboxy or carboxylate -C (O) O', Q ⁺ with Q ⁺ as defined above; R ⁷ represents a hydrogen atom, a hydroxyl group or a glycosylated radical, preferably glucose; With the proviso 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 metal or alkaline -terrous such as potassium or calcium; 24. Process according to any one of the preceding claims, characterized in that the natural dye (s) iii) of the composition B is (are) chosen from anthraquinones comprising at least one carboxylic acid function, preferably selected from carminic acid, laccaic acid A, laccaic acid B, laccaic acid C, laccaic acid D, and / or kermetic acid. 25. Method according to any one of claims 1 to 22, characterized in that the natural dye (s) (s) of the composition B is (are) chosen from betalaines, preferably betaine. 26. Process according to any one of claims 1 to 21, characterized in that the natural dye (s) of the composition B is (are) chosen from anthocyanidins (also called anthocyanins, or anthocyanidols) of the following formula (Vg) which contain at least three hydroxyl groups: formula (Vg) in which: R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from i) hydroxy, ii) (Ci-Ce) alkyl, iii) (Cr Ce) alkoxy, iv) (Ci-Ce) alkylthio, v) carboxyl, vi) alkyl carboxylate or alkoxycarbonyl, vii) optionally substituted amino, viii) alkenyl linear or branched optionally substituted, ix) optionally substituted cycloalkyl, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di) ((hydroxy) (C1-C6) alkyl) amino, xiii) glucosyl, xiv) RZC (X) -Y- with R representing a hydrogen atom, a (CiCe) alkyl or aryl group optionally substituted in particular by at least one hydroxyl group such as 3,4,5-trihydroxyphenyl; Y and Z, which may be identical or different, represent a bond, or an oxygen atom, sulfur atom or a group -N (R ') - with R' representing a hydrogen atom or a (Ci-Cs) alkyl group, Y may also represent a (Ci-Ce) alkylene group; X represents an oxygen atom, sulfur, or NR "with R" representing a hydrogen atom or a group (C ₁ -C ₆ ) alkyl; R ⁶ , R ^{8, which are} identical or different, represent a hydrogen atom, or a group chosen from a hydroxyl group, a (C 1 -C 6) alkyl group or an R-ZC (X) -Y- group as defined above, Or else the unit (V) constitutes the polymeric unit of a polyphenol which will be connected to the other units of said polyphenol by positions 4, 6 or 8 of the chromane ring in which case R ¹ , or R ³ and R ⁶ form a bond covalent with other units of said polyphenol; it being understood that at least three radicals of the compounds of formula (V) chosen from R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , represent a hydroxy group; the compound of formula (Vg) being cationic and it is associated with it a counterion An anionic, organic or inorganic, such as halide. preferably, the radicals R1, R6, R14 and R10 representing a hydrogen atom. 27. Method according to any one of claims 1 to 21 and 26, wherein said natural dye (s) iii) is selected from anthocyanidins selected from cyanidine, delphinidin, pelargonine, malvidine, peonidine, petunidine, and their mixtures. 28. The method of dyeing according to any one of claims T to 22, characterized in that the said natural dye (s) iii) is chosen from carthamine. 29. A method of dyeing according to any one of the preceding claims, characterized in that the composition A is applied first to the keratinous fibers; and the composition B is applied to the keratinous fibers after application of the composition A. 30. Staining process 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 staining step using the composition A and the treatment step using the composition B, preferably a rinsing step. 31. Use of an aqueous composition B, whose pH 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 in any one of the preceding claims for accelerating the color stabilization of the colored fibers from powder and / or extracting indigo plant (s) dye and possibly henna over time and improving the intensity and / or the rise of the color and / or the holding of the color.