WO2018229297A1

WO2018229297A1 - Process for dyeing keratin fibres employing at least one fluorescent direct dye and at least one blue-purple-green benzoindolinium direct dye

Info

Publication number: WO2018229297A1
Application number: PCT/EP2018/066118
Authority: WO
Inventors: Abel Messavussu; Christian Blaise
Original assignee: L'oreal
Priority date: 2017-06-16
Filing date: 2018-06-18
Publication date: 2018-12-20
Also published as: FR3067600A1; FR3067600B1

Abstract

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, employing at least one blue-purple-green benzoindolinium direct dye and at least one fluorescent direct dye. The present invention also relates to a cosmetic composition comprising the dyes defined above, and also to a multi-compartment device containing said dyes. The present invention also relates to the use of said dyes for dyeing light keratin fibres, especially human keratin fibres such as the hair, chestnut brown, dark chestnut brown, dark brown, multi-tonal dark brown, or even black, without using an additional dye other than those defined above.

Description

The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, and in particular a process for dyeing keratinous fibers using at least one fluorescent direct dye and at least one direct dye. employing at least one direct blue-violet-green benzoindolinium dye, and at least one fluorescent direct dye.

The present invention further relates to a cosmetic composition comprising the dyes defined above, as well as a multi-compartment device containing said dyes.

The present invention also relates to the use of said dyes for dyeing clear keratinous fibers, especially human keratin fibers such as hair, in chestnut, dark chestnut, brown, brown with a reflection, or even black, without using an additional dye other than those defined above.

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

It is in particular known to dye keratinous fibers, in particular human keratinous fibers, with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

The shades obtained with these oxidation bases can be modified by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

Another well-known method consists in obtaining so-called semi-permanent stains by applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for said fibers.

The direct dyes conventionally employed are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species can be nonionic, anionic (acidic dyes) or cationic (basic dyes). Direct dyes can also be natural dyes.

Conventional direct dyeing methods consist in applying to the keratin fibers, dye compositions comprising direct dyes. After application, a pause time is observed in order to allow the coloring molecules to penetrate by diffusion inside the fibers. At the end of the process, the fibers are rinsed.

In contrast to oxidative stains, these direct staining methods have tend to better protect the integrity of the fibers. The resulting colorations are generally chromatic but are however only semi-temporary. The nature of the interactions that bind direct dyes to keratin fibers, as well as their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power.

Although a wide range of colors is currently available, it is generally necessary to combine three complementary color dyes - trichromic principle - to obtain a natural shade (see eg WO 95/15144, and WO 95/01772). This tripartite association, however, does not have a good remanence to repeated shampoos. In general, it induces, in a systematic way, an unattractive color shift, which is unacceptable for the consumer.

These colors are not sufficiently stubborn against external agents such as light or perspiration.

Thus, there is a real need to implement direct dyeing processes for keratinous fibers, in particular human keratinous fibers such as the hair, which do not have the disadvantages mentioned above, ie which make it possible in particular to lead to natural colors having good properties, especially in terms of chromaticity, power, intensity, gloss and selectivity, and which are remanent to shampoos.

Another object of the invention is therefore to be able to effectively color the keratinous fibers effectively in chestnut, dark chestnut, brown, brown with a reflection or even black, by mixing the direct dyes, and preferably only two types of direct dye. .

The Applicant has surprisingly discovered that a method for staining keratin fibers using one or more direct blue-violet benzoindolinium dyes, and one or more fluorescent direct dyes, made it possible to achieve the objectives set out above; in particular to lead to natural colorings, chestnut, dark chestnut, brown, brown with reflection or black, which are not only powerful and brilliant, but also resistant to shampoos.

The subject of the present invention is in particular a process for dyeing keratinous fibers, in particular human keratinous fibers, such as the hair, comprising the application to said keratinous fibers of the following ingredients:

a) one or more blue-violet-green direct dyes benzoindoliniums of formula (I):

As well as their acid or base salts, organic or inorganic, their optical isomers, geometric, tautomers and solvates such as hydrates

formula (I) in which,

R ¹ represents a radical:

alkyl, linear or branched, C 1 -C 10,

Optionally interrupted by one or more heteroatoms or groups chosen from oxygen, sulfur, N (R), N ⁺ (R) (R ') An ^" , C (X), S (O), S (O) ₂ or combinations thereof such as -N (R) -C (0) - or -C (0) -N (R) - and -S-S-, with X representing an oxygen, sulfur or a group N (R), and R and R ', which may be identical or different, representing a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, and / or

Optionally substituted by one or more hydroxyl groups, (di) (C 1 -C ₄ ) (alkyl) amino, or of formula (Γ), preferably said alkyl group being optionally substituted by one or more hydroxyl groups, or of formula ( "'):

an optionally substituted aryl radical, such as phenyl, or

an aryl (C ₁ -C ₄ ) alkyl radical such as benzyl, the aryl group being optionally substituted;

R ² and R ' ² , which are identical or different, represent a group chosen from: i) (hetero) aryl- (T ¹ = T ² ) _n - and ii) ED- (T ¹ = T ² ) _n - with ( hetero) aryl representing an optionally substituted aryl or heteroaryl group, ΤΊ and T2 identical or different, representing a nitrogen atom or a group C (R) with R as defined above, and n is 0, 1, 2 or 3 and ED representing an electron donor group such as (di) (C ₁ -C ₄ ) (alkyl) amino or (di) hydroxy (C ₁ -C ₄ ) alkylamino; in particular R ² , R ' ² represent i) with n being 0 and optionally substituted hetero) aryl, preferably representing optionally substituted aryl such as phenyl optionally substituted with one or more (di) (Ci-C ₄ ) (alkyl) groups amino or (di) hydroxy (Ci-C ₄₎ alkylamino;

• R ³ , R ' ³ , R ⁴ , R' ⁴ , R ⁵ , R ' ⁵ , R ⁶ , R' ⁶ , R ⁷ , R ' ⁷ , R ⁸ , and R' ⁸ , which are identical or different, representing uu hydrogen, halogen, or a group selected from (C1- C6) alkyl, (Ci-Ce) alkoxy, (Ci-C6) alkylthio, (di) (Ci-C ₄₎ (alkyl) amino, hydroxy , mercapto, nitro (so), cyano, R "- (X) _p -C (X ') - (X") _q - and R "- (X) _p -S (O) _r - (X") _q X, X 'and X ", which may be identical or different, represent an oxygen or sulfur atom or a group ( C4) (alkyl) amino, in particular X 'represents an oxygen atom and X, X "represents an oxygen atom or amino, p and q, which are identical or different, are equal to 0 or 1, r is equal to 1 or 2, R "represents a hydrogen atom, or a (C 1 -C 4) alkyl group, preferably R ³ , R ' ³ , R ⁴ , R' ⁴ , R ⁵ , R ' ⁵ , R ⁶ , R' ⁶ , R ^7; , R ' ⁷ , R ⁸ , and R' ⁸ represent a halogen atom;

Represents the bond which links the group (Γ) to the rest of the molecule, and

• An ^" represents an anionic counterion ensuring the electroneutrality of the molecule, b) one or more fluorescent dyes;

it being understood that the direct dye (s) benzoindolinium a) and the fluorescent dye (s) b) are applied to said keratinous fibers jointly or sequentially.

Another subject of the invention is a cosmetic composition comprising:

a) one or more benzimidazolium dyes of formula (I) as defined above;

(b) one or more fluorescent dyes;

c) optionally one or more reducing agents, and

d) optionally the pH of said composition is between 6 and 11, preferably between 7 and 10, more preferably between 7.5 and 9.5, and more preferably between 9 and 9.5.

The combination of dyes a) and b) makes it possible in particular to obtain natural dyes having good coloring properties, especially in terms of power, intensity, gloss and selectivity.

In addition, the process and the composition according to the invention make it possible to be able to effectively color the keratin materials in chestnut, dark brown, brown, brown with a reflection, or even black, by mixing dyes a) with b) as defined above. without having to use an additional dye (or complementary) other than a) or b).

Furthermore, the colorations obtained by the process and the composition according to the invention are resistant to various attacks that may be experienced by the hair, such as light, bad weather, washing, perspiration. They are particularly persistent in shampoos, and especially after at least 3 shampoos.

The present invention also relates to a multi-compartment device comprising a first compartment containing one or more benzimidazolium dyes a) as defined above, and a second compartment containing one or more fluorescent dyes b), as defined above.

Another subject of the invention is the use of dye (s) b) as defined previously, associated with the dye (s) a) as defined (s). ) previously for the coloration of clear keratin fibers, especially preferably human keratin fibers, such as chestnut, dark chestnut, brown hair, brown with reflection, even black, without using an additional dye different from a) or b).

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

The present invention also relates to a multi-compartment device comprising a first compartment containing one or more dyes a) and a second compartment containing one or more fluorescent dyes b), as defined above.

Another subject of the invention is the use of fluorescent dye (s) b) as defined above, associated with or with the blue (s) violet dye (s) ( s) imidazolium (s) a) as previously defined for the coloring of light keratin fibers, in particular preferably human keratinous fibers, such as chestnut, dark chestnut, brown, brown hair with reflection or even black, without using an additional dye other than a) or b).

For the purposes of the present invention, and unless a different indication is given:

For the purposes of the present invention, the term "direct dye" means natural and / or synthetic dyes, soluble in the cosmetic medium, which absorb the color in the visible spectrum i.e. which appear visually colored; they are dyes that will diffuse superficially on the keratinous fibers; As visual color and absorption wavelength of the direct dyes of the invention associated with said color, mention may be made of the following colors "yellow"

= λ, τΐθχ> 400 nm up to 440 nm inclusive, "orange" = _max > 440 nm up to 490 nm inclusive, "red" = _max > 490 to up to 520 nm inclusive, "purple to purple "to _my = x> 520 nm and 560 nm terminal included," purple "= λ, τΐθχ> 560 nm to 580 nm included terminal," blue "= _max> 580 nm to 620 nm range terminal," blue- green "= at _my x> 620 nm up to 650 nm inclusive, and "Green"max> 650 nm up to and including 780 nm; preferably the fluorescent direct dyes b) are preferably of yellow, orange or red color;

a "fluorescent chromophore" is a radical derived from a fluorescent dye, that is to say a radical derived from a light-absorbing molecule in the visible range of the radiation visually perceptible by man and which appears at the colored eye ie absorbing light at an absorption wavelength _a b _S preferably between 300 and 700 nm inclusive; said chromophore is further that it is capable of re-emitting in the visible range at a transmission wavelength comprised e _m greater than the absorption wavelength ie preferably MEA including re-emits between 400 and 800 nm ; the difference of the absorption and emission wavelength also called Stoke or Stoke's shift is between 1 nm and 100 nm inclusive. More preferably, the fluorescent chromophores are capable of absorbing at a wavelength λ _a bs of between 420 nm and 550 nm inclusive and of reemitting in the visible at a wavelength λm included between 470 and 600 nm;

a "chromophore" is said to be "quaternized cationic" or "carrying a quaternized cationic group" if it comprises in its structure at least one permanent cationic charge consisting of at least one quaternized nitrogen atom (ammonium) or phosphorus quaternized (phosphonium), preferably nitrogen; a group is said to carry a quaternizable cationic group when it comprises at least one tertiary amine or a tertiary phosphine at the end of a hydrocarbon chain, preferably C1-C10 alkyl, such as - (CR ' R ") pN (R _a ) -Rb with R 'and R", which may be identical or different, representing a hydrogen atom or a (Ci-Ce) alkyl group; R _a and Rb, which may be identical or different, represent a (poly) (hydroxy) (C 1 -C 6) alkyl group or R _a and Rb together with the nitrogen atom which carry them form a heterocycloalkyl group such as morpholino, piperidino or piperazino; and p representing an integer inclusive of between 1 and 10; preferably R 'and R "represent a hydrogen atom, R _a and Rb represent a (d-C4) alkyl group and p is between 2 and 5;

the dyes according to the invention contain one or more colored and fluorescent chromophores as defined above, in particular they are capable of absorbing light at a wavelength λ _a b included between 300 and 700 nm and retransmitting in the visible at a longer wavelength than the absorption wavelength, in particular λem included between 400 and 800 nm: the difference of the absorption and emission wavelength also called Stoke shift or Stoke's shift is included between 1 nm and 100 nm. More preferably, Fluorescent dyes of the invention are dyes capable of absorbing at a wavelength λ _a bs of between 420 nm and 550 nm inclusive and reemitting in the visible at a wavelength λm included between 470 and 600 nm ;

chromophores are said to be "different" when they differ in their chemical structure and may be chromophores from different families or from the same family provided that they have different chemical structures: for example, chromophores may be chosen from family of azo dyes but differ by the chemical structure of the radicals constituting it or by the respective positions of these radicals;

an "alkylene chain" represents a divalent C1-C20 acyclic hydrocarbon chain; especially C1-C6, more particularly C1-C2 when the chain is linear; optionally substituted with one or more groups, identical or different, chosen from i) hydroxy, ii) (C ₁ -C ₂ ) alkoxy, iii) (poly) hydroxy (C ₂ -C ₄ ) alkoxy (di) (C ₁ -C ₂ ) ( alkyl) amino, iv) R ^a -Z ^a -C (Z ^b ) -Z ^c- , and v) R ^a -Z ^a -S (O) tZ ^c - with Z ^a , Z ^b , same or different, representing oxygen, sulfur, or NR ^a ', Z ^c is a bond, oxygen, sulfur, or NR ^a; R ^a , representing an alkali metal, a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and R ^a 'representing a hydrogen atom or an alkyl group and t is 1 or 2; more particularly the grouping iv) are chosen from carboxylate -C (O) 0 ^" or -C (O) OMetal (Metal = alkali metal), carboxyl -C (O) -OH, guanidino H ₂ HC (NH ₂ ) -NH -, amidino H ₂ HC (NH ₂ ) -, (thio) ureo H ₂ NC (O) -NH- and H ₂ NC (S) -NH-, aminocarbonyl -C (O) -NRa ' ₂ or aminothiocarbonyl -C (S) -NRa '₂; carbamoyl Ra'-C (O) -NRa'- or thiocarbamoyl Ra'-C (S) -NRa'- with Ra', identical or different, representing a hydrogen atom or a group (Ci -C4) alkyl;

a "divalent C1-C30 hydrocarbon-based chain, saturated or unsaturated, optionally substituted", represents a hydrocarbon chain, especially C 1 -C 8, optionally comprising one or more double bonds p, conjugated or not, particularly the hydrocarbon chain is saturated; said chain is optionally substituted with one or more groups, identical or different, chosen from i) hydroxy, ii) (Ci-C ₂ ) alkoxy, iii) (poly) hydroxy (C ₂ -C ₄ ) alkoxy (di) ( C ₁ -C ₂ ) (alkyl) amino, iv) R ^a -Z ^a -C (Z ^b ) -Z ^c -, and v) R ^a -Z ^a -S (O) tZ ^c - with Z ^a , Z ^b , identical or different, representing an oxygen atom, sulfur, or a group NR ^a ', Z ^c , representing a bond, an oxygen atom, sulfur, or a group NR ^a ; R ^a , representing an alkali metal, a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and R ^a 'representing a hydrogen atom or an alkyl group and t is 1 or 2; more particularly groupings iv) are selected from carboxylate -C (O) 0 ^" or -C (O) OMetal (Metal = alkali metal), carboxyl -C (O) -OH, guanidino H ₂ HC (NH ₂ ) -NH-, amidino H ₂ HC ( NH ₂ ) -, (thio) ureo H ₂ NC (O) -NH- and H ₂ NC (S) -NH-, aminocarbonyl -C (O) -NR _a ' ₂ or aminothiocarbonyl -C (S) -NR _a _'2; carbamoyl R _a' -C (0) -NR _a '- thiocarbamoyl or R _a' -C (S) -NR _a '- with R _a \ identical or different, representing a hydrogen atom or a (Cl- C4) alkyl;

the "fluorescent dyes" according to the present invention are to be distinguished from optical brighteners. Optical lightening agents generally called "optical brighteners", or "brighteners", or "fluorescent brighteners" or "fluorescent brightening agents", or "fluorescent whitening agents" or "whiteners" or "fluorescent whiteners" in English terminology , are colorless compounds to the eye, which do not stain and are therefore not dyes since they do not absorb in visible light, but only absorb in the Ultra-Violets (wavelength ranging from 200 at 400 nanometers) and transform the absorbed energy into fluorescent light of longer wavelength emitted in the visible part of the spectrum in blue. The color impression is then only generated by the purely fluorescent light predominantly blue,

coloring "blue-violet-green" according to the invention are dyes that absorb light in the visible spectrum, which appear violet, blue, green or visually, ie which absorb light to an absorption length To _my x greater than 520 nm and less than or equal to 700 nm, in particular _max included between 560 nm and 700 nm, preferably in the blue, ie to _M x between 580 and 620 nm;

"(hetero) aryl" generally means aryl and heteroaryl; the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom chosen from:

a C ₁ -C ₆ , preferably C ₁ -C ₄ , alkyl radical optionally substituted by one or more radicals chosen from hydroxyl, C ₁ -C ₂ alkoxy, (C ₂ -C ₄ ) poly (C ₂ -C ₄ ) -hydroxyalkyl, acylamino, amino radicals; substituted with two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7; 5-membered, preferably 5-membered, optionally substituted saturated or unsaturated linkages optionally comprising another heteroatom identical to or different from nitrogen;

a halogen atom such as chlorine;

a hydroxyl or thiol group;

a C1-C6 alkoxy or C1-C6 alkylthio radical; a C2-C6 (poly) -hydroxyalkoxy radical;

an amino radical;

a heterocycloalkyl radical of 5 or 6 membered ring, preferably morpholino, piperazino, piperidino, or pyrrolidino optionally substituted by (C1- _C4) alkyl, preferably methyl;

a 5- or 6-membered heteroaryl radical preferably imidazolyl, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl;

an amino radical substituted with one or two identical or different C1-C6 alkyl radicals optionally carrying at least:

i) a hydroxy group,

ii) an amino group optionally substituted by one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, optionally saturated or unsaturated; substituted optionally comprising at least one other heteroatom different or different from nitrogen,

iii) a quaternary ammonium group -N ⁺ R'R "R"', Y ^" for which R', R", R "', which may be identical or different, represent a C1-C4 alkyl group; and Y ^" represents a counter-group; anionic ion,

iv) or an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl;

an acylamino radical (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl radical;

a carbamoyl radical ((R) 2 N-C (O) -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group;

an alkylsulphonylamino radical (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical or a phenyl radical;

an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; ,

a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); > a cyano group;

> a nitro or nitroso group;

a polyhaloalkyl group, preferentially trifluoromethyl;

the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent chosen from the groups:

- hydroxy;

- C1-C4 alkoxy, (poly) hydroxyalkoxy C2-C4;

C1-C4 alkyl;

alkylcarbonylamino (RC (O) -N (R ') -) in which the radical R' is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a C 1 -C 2 alkyl radical, amino optionally substituted with one or two identical or different C 1 -C 4 alkyl groups, themselves optionally carrying at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle optionally comprising at least one other non-nitrogen heteroatom;

alkylcarbonyloxy (RC (O) -O-) in which the radical R is a C 1 -C 4 alkyl radical, an amino group optionally substituted by one or two identical or different C 1 -C 4 alkyl groups, themselves optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which may or may not be different from nitrogen; ;

- alkoxycarbonyl (R-Xi-C (O) -) in which the radical R is a C1-C4 alkoxy radical, Xi is an oxygen atom, or an amino group optionally substituted with a C1-C4 alkyl group; they may also carry at least one hydroxyl group, said alkyl radical being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered saturated or unsaturated heterocycle optionally comprising at least one other heteroatom different or different from nitrogen; a cyclic, heterocyclic, or non-aromatic portion of an aryl or heteroaryl radical may also be substituted by one or more oxo groups;

an "aryl" radical represents, in general, a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; A "cationic heteroaryl radical" is a heteroaryl group as defined previously which comprises an endocyclic or exocyclic cationic group;

when the charge is endocyclic, it is taken in the electronic delocalization by mesomeric effect, for example it is a pyridinium, imidazolium or indolinium group:

with R and R 'being a heteroraryl substituent as defined previously and particularly a (hydroxy) (C 1 -C 8) alkyl group such as methyl;

when the charge is exocyclic, it is not taken up in the electronic delocalization by mesomeric effect, for example it is a substituent R ⁺ ammonium, phosphonium such as trimethylammonium, being outside the heteroaryl such that pyridinyl, indolyl, imidazolyl, or naphthalimidyl in question:

with R a heteroaryl substituent as defined below and R ⁺ an ammonium group R _a RbR _c N ⁺ -, phosphonium R _a RbR _c P ⁺ - or ammonium R _a RbR _c N ⁺ - (Ci- C ₆ ) alkylamino, R _a RbRcN ⁺ - (C ₁ -C ₆ ) alkyl or R _a R _b RcN ⁺ - (C ₁ -C ₆ ) alkoxy with R _a , R _b and R _{c the} same or different represent a group (Ci-Cs) alkyl such as methyl;

^■ a "heteroaryl radical" represents a monocyclic or polycyclic group, condensed or not, comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from nitrogen, oxygen, and sulfur, and which at at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyryl, triazolyl, xanthylyl and its ammonium salt;

a "heterocyclic radical" is a radical which may contain one or two unsaturated but non-aromatic, mono or polycyclic, condensed or non-fused, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from the nitrogen atom, from oxygen, and sulfur;

a "heterocycloalkyl radical" is a heterocyclic radical comprising at least one saturated ring;

"alkyl radical" is a hydrocarbon radical -C 20 linear or branched, preferably Ci-C10, more preferably Ci-Cs, more preferably Ci to C6, more preferably Ci to C _4;

the expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals chosen from the radicals i) hydroxy, ii) alkoxy Ci-C ₄ , iii) RZC (X) - Y- with X, Y and Z representing an oxygen atom, sulfur or N (R '), or X and / or Z represents (nt) a bond, R and R', identical or different, represent an atom of hydrogen or a (C 1 -C 6) alkyl group, preferably X represents an oxygen atom, iv) amino optionally substituted by one or two identical or different C ₁ -C ₄ alkyl radicals, said alkyl radicals being able to form with the nitrogen atom carrying them a 5- to 7-membered heterocyclic ring, optionally comprising another heteroatom other than nitrogen; v) a quaternary ammonium group N ⁺ R'R "R"', M ^" for which R', R", R '", which may be identical or different, represent a Ci-C ₄ alkyl group, or else -N ⁺ R 'R "R'" form a 5- or 6-membered ring such as imidazolium optionally substituted with a Ci-C ₄ alkyl group, and M ^"represents the anionic against ion, vi) carboxy C (0) OH, vii) carboxylate C (O) O ^" , M ⁺ with M ⁺ representing a cationic counterion such alkali or alkaline earth metal, viii) sulfonic acid -SO3H, ix) -SO3 ^" sulfonate, M ⁺ with M ⁺ as defined above, x) cyano, and xi) a carbamoyl radical ((R) 2 N-C (O) -) in which R, which may be identical or different, represent a hydrogen atom or a C ₁ -C ₄ alkyl radical optionally carrying at least one hydroxy group;

an "alkoxy radical" is, in general, an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, Ci to Cs, preferably C1 to C6;

when the alkoxy group is optionally substituted, it implies that the alkyl group is optionally substituted as defined above;

the term "organic or inorganic acid salt" is intended to mean, more particularly, the salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid hbSC, iv) acids alkylsulfonic: Alk-S (O) 20H such as methylsulfonic acid and ethylsulfonic acid; v) acids arylsulfonic: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulphinic acids: Alk-O-S (O) -OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C (O) -OH; xiv) of triflic acid CF3SO3H and xv) of tetrafluoroboric acid by "anionic counterion or anion" means an anionic or anionic group cosmetically acceptable, organic or inorganic, derived from organic or inorganic acid salt associated with the cationic charge of the dye; more particularly the anion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulphonates, including C1-C6 alkylsulphonates: Alk-S (O) 20 ^" such as methylsulphonate or mesylate and ethylsulphonate; iv) arylsulphonates: Ar-S (O) 20 ^" such as benzenesulphonate and toluenesulfonate or tosylate; v) Alk-C (O) -OH carboxylates with Alk representing a (C 1 -C 6) alkyl group optionally substituted by one or more hydroxyl or carboxylate groups such as citrate; vi) succinate; (vii) tartrate; viii) lactate; (ix) Alkyl sulphates: Alk-O-S (O) 0 ^- such as methylsulfate and ethylsulphate; x) arylsulfates: Ar-O-S (O) 0 ^- such as benzenesulphate and toluenesulphate; (xi) alkylsulphates: Alk-O-S (O) 20 ^" such as methyl sulfate and ethylsulphate; xii) arylsulphates: Ar-O-S (O) 20 ^" , xiii) 0 = P (OH) phosphates ) ₂ -0-, 0 = P (0> OH 0 = Ρ (0 ^" ) ₃ , HO- [P (0) (0 ^" )] wP (0) (0-) 2 with w being an integer; xiv ) acetate; xv) triflate; (xvi) borates such as tetrafluoroborate; xvii) sulphate S (0) 2C> 2 ^" or SO4 ^2" ; xviii) hydrogensulfate HSO 4 ^"; xix) carbonate; xx) hydrogencarbonate; xxi) perchlorate (ClO ^4") and xxii) dianionic inorganic salts such as zinc tetrachloride;

the anionic counterion, derived from organic or inorganic acid salt, ensures the electroneutrality of the molecule: thus it is understood that when the anion comprises several anionic charges then the same anion can be used for the electroneutrality of several cationic groups in the same molecule or else can be used for the electroneutrality of several molecules; for example, a dye which contains two cationic groups may contain either two "monocharged" anionic counterions or contains a "bicharged" anionic counterion such that (0 =) ₂ S (O-) 2 or 0 = P (0 ^" ) 2-OH;

In particular, the anionic counterions are chosen from halides such as chloride, bromide, fluoride, iodide; a hydroxide; sulphate; a hydrogen sulfate; a linear or branched C1-C6 alkyl sulphate, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; linear or branched C1-C6 alkylsulfonates such as the methylsulfonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted with one or more C1-C4 alkyl radicals such as, for example, 4-tolylsulphonate; alkylsulfonyls such as mesylate;

• "Chemical oxidizing agent" means any oxidizing agent other than the oxygen of the air conventionally used in the field. Thus, mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, as well as enzymes, among which mention may be made of peroxidases, oxido-reductases, 2 electrons such as uricases and 4-electron oxygenases such as laccases. Preferably, the chemical oxidizing agent is hydrogen peroxide.

Moreover, the addition salts which can be used in the context of the invention are chosen especially from the addition salts with a cosmetically acceptable base, such as alkalinizing agents as defined below, such as alkali metal hydroxides, such as soda, potash, ammonia, amines or alkanolamines.

• the expression "at least one" is equivalent to "one or more";

• the boundaries of a domain of values are included in this domain, in particular in the expressions "between" and "ranging from ... to ..."; and

• the expression "inclusively" means that the limits of the range are part of the defined interval. a) Blue, purple and green benzoindolinium dyes

According to one particular embodiment, the blue, violet and green dyes a) of the invention are chosen from benzimidazolium dyes of formula (I) as defined above. Preferably, the benzimidazolium dye (s) of formula (I) of the invention are blue-violet dyes.

The benzoindolinium dyes of the invention are prepared according to the synthesis scheme below:

a process which consists in a first step i) of reacting phthalic anhydride (a) in an alkaline medium, in particular the presence of a base such as, for example, pyridine, preferably at reflux of solvent for 1 to 3 hours, at a compound Ra-SC H with Ra representing a halogen atom or a (hetero) aryl group, in particular a sulphonic acid halide such as sulphonic acid chloride or a paratoluenesulphonic acid, preferably at reflux for 1 to 3 hours to yield the compound compound (b); the latter in a second step ii) is reacted in a water / (C 1 -C 6) alkanol mixture such as, for example, ethanol and in the presence of an alkaline agent, preferably a mineral agent such as, for example, sodium hydroxide. sodium, the medium is refluxed with solvent for 2 to 4 hours and then maintained at reflux by removing the water preferably using a Dean Stark, the medium is then cooled and acidified with a strong acid especially mineral such that hydrochloric acid optionally followed by purification by filtration, for example to give compound (c),

the compound (c) can then follow the synthetic route A, step iii) by reacting it in a sulfur-containing solvent such as sulfolane in the presence of R2-H, in particular an aromatic amine, preferably at reflux of solvent for 1 to 3 hours; followed by halogenation, in particular with phosphorus oxyhalide such as phosphorus oxychloride, at reflux of solvent for 1 to 3 hours, The medium is then cooled to room temperature and then poured into water, the medium is then neutralized with the aid of a mineral base such as, for example, sodium hydroxide to precipitate the product, optionally followed by purification by filtration which is brought into contact with a halogenated reagent in a polar solvent such as refluxing acetonitrile to yield compound (d); the latter during step iv) is reacted in a polar solvent such as acetonitrile in the presence of the alkylating agent Ri-An with R1 and An as defined above, to lead optionally after purification to the compound (I) according to the invention;

the compound (c) can also follow the synthetic route B, step v) the compound (c) is brought into contact with an alkaline agent preferably mineral such as potassium carbonate, preferably at reflux of solvents for 1 to 6 hours, to lead to the compound (e), the latter is brought into the presence of R2-H such as an aromatic amine and a mixture of phosphorus oxyhalide and phosphoric anhydride preferably at reflux of solvent for 2 to 5 hours; the reaction medium is then poured into water and then neutralized with an alkaline agent, preferably mineral, such as sodium hydroxide, to conduct, optionally after acidification and purification, by precipitation and separation with the compound (I) of the invention;

According to a particular embodiment, the benzoindolinium dye (s) b) are chosen from the dyes of formula (Ia):

formula (la) in which;

R ¹ represents a radical:

C6 alkyl, linear or branched, preferably linear;

an optionally substituted aryl radical, such as phenyl, or

an aryl (C 1 -C 4) alkyl radical such as benzyl, the aryl group being optionally substituted

preferably, R ¹ represents a linear or branched C 1 to C 10 alkyl group, optionally substituted, more preferably a linear C 1 to C 6 alkyl group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above in formula (I) preferably R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ , represent a hydrogen atom;

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ , which may be identical or different, represent a hydrogen atom or a group chosen from hydroxyl, mercapto, (Ci-C4) alkyl, (hydroxyl) (Ci-C4) alkoxy, (C 1 -C 4) alkylthio, (di) (C 1 -C 4) (alkyl) amino or (di) hydroxy (C 1 -C 4) alkylamino; preferably R ¹⁰ and R ¹² represent a hydrogen atom, and more particularly R ⁹ , R ¹⁰ , R ¹² and R ¹³ represent a hydrogen atom, and R ¹¹ represents a group (C 1 -Coxy, (di) ( C 1 -C 4) (alkyl) amino or (di) hydroxy (C 1 -C 4) alkylamino;

represents the bond that connects the group (Γ) to the rest of the molecule, and

An ^" represents an anionic counterion ensuring the electroneutrality of the molecule.

More particularly, the indolinium dyes blue, violet, green of formula "a) below:

as well as their acid salts, organic or inorganic, their solvates such as hydrates,

formula (I "a) in which:

R ¹ represents a linear or branched, preferably linear, C6 alkyl group; R ⁹ , R ¹¹ and R ¹³ represent a hydrogen atom or a (di) (C 1 -C 4) (alkyl) amino, (di) hydroxy (C 1 -C 4) alkylamino group, it being understood that all the radicals R ⁹ , R ¹¹ and R ¹³ can not represent a hydrogen atom, in particular (l "a) represents:

With An ^" as defined previously.

According to another particular embodiment, the blue, violet, green indolinium dye (s) of formula (I "'a) below:

formula (I "a) in which:

linear or branched, C 1 to C 10, preferably C 1 to C 6, linear or branched, preferably linear, alkyl substituted with one or more hydroxy, (di) (C 1 -C 4) (alkyl) amino groups, such as amino or dimethylamino:

R ⁹ , R ¹¹ and R ¹³ represent a hydrogen atom or a (di) (C 1 -C 4) (alkyl) amino, (di) hydroxy (C 1 -C 4) alkylamino group, it being understood that all the radicals R ⁹ , R ¹¹ and R ¹³ can not represent a hydrogen atom, in particular (1 "a) represents:

Dye (a2)

An = against anionic ion such as Cl ^" , or Br

Dye (a3)

An = against anionic ion such as Cl ^" , or Br, whose amino group can be salified, eg with HBr, or non-salified

Coloring (a4)

According to another particular embodiment of the invention, the indolinium dye (s) are di-indolinium dyes of formula (Ib):

formula (Ib) in which

L represents a divalent alkylene radical, linear or branched, C 1 -C 10, optionally substituted and / or optionally interrupted by one or more heteroatoms or groups selected from oxygen, sulfur, N (R), N ⁺ (R) (R ') An ^" , C (O), S (O), S (O) ₂ or combinations thereof such as -N (R) -C (O) - or -C (O) -N (R) - and -SS-, with R and R ', identical or different, representing a hydrogen atom or a (C 1 -C 4) alkyl group;

preferably L represents a C1-C10 alkylene group, linear or branched, particularly linear, optionally interrupted by one or more heteroatoms or groups selected from oxygen, sulfur, N (R), N ⁺ (R) (R ') An ^" , C (O), or combinations thereof such as -N (R) -C (O) - or -C (O) -N (R) - and -SS-;

• R ² , R ' ² , R ³ , R' ³ , R ⁴ , R ' ⁴ , R ⁵ , R' ⁵ , R ⁶ , R ' ⁶ , R ⁷ , R' ⁷ , R ⁸ , and R ' ⁸ , being as defined previously in formula (I), preferably R ³ , R ' ³ , R ⁴ , R' ⁴ , R ⁵ , R ' ⁵ , R ⁶ , R' ⁶ , R ⁷ , R ' ⁷ , R ⁸ and R ' ⁸ represent a hydrogen atom and R ² and R' ² represent a phenyl group optionally substituted with (di) (C 1 -C 4) (alkyl) amino or (di) hydroxy (C 1 -C 4) alkylamino preferably substituted ortho or para, more preferably para;

Represents the bond which links the group (Γ) to the rest of the molecule, and

• An ^" represents anionic counterion ensuring the electroneutrality of the molecule.

According to a more particular embodiment of the invention, the di-indolinium or di-indolinium of formula (Ib) are chosen from those of formula (b):

formula (b) in which, An ^" , and L are as defined for (Ib), R ' ⁹ , R' ¹¹ , and R ^'13 have the same meaning as R ⁹ , R ¹¹ , and R ¹³ such defined in (Ia), preferably R ¹¹ and R ¹¹ are (di) (Ci-C ₄₎ (alkyl) amino or (di) hydroxy (Ci-C ₄₎ alkylamino, and R ^9, R ^13, R ' ⁹ , R' ¹¹ , and R ^'13 , represent a hydrogen atom.

Preferably, the dyes of formula (b) are symmetrical. b) Fluorescent dyes The method for dyeing keratinous fibers and the cosmetic composition according to the present invention implement, or comprise, in addition b) one or more fluorescent dyes.

Preferably, the fluorescent dye (s) of the invention are direct and do not comprise any identical contiguous heteroatom bond. As fluorescent dyes usable in the present invention, we may mention: acridine dyes, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro {2 - [(2H-pyrrol-2-ylidene) -kn) methyl] -1H-pyrrolato- kNJborons (BODIPY ^®), dipyrinones, diketopyrrolopyrrole, fluorindines, (poly) methine (cyanine and in particular styryl / hemicyanine), naphthalimides, naphtanilides, naphthylamine (such as dansylated) naphtholactams , oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squarans, stilbenes, xanthenes, thioxanthenes, thiazines and their mixtures.

We can also mention fluorescent dyes described in documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144, EP 714 954 and those listed in the encyclopedia The chemistry of synthetic dye by K. Venkataraman, 1952, Academy Press, volumes 1 to 7, in the encyclopaedia of K / ^' r / Othmer, Chemical Technology, chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in several chapters Ullman's Encyclopedia of Industrial Chemistry, th _ec | jtjon, Wiley and Sons, particularly in VUllman's Encyclopedia of Industrial Chemistry in chapter "Fluorescent Dyes", 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 143560007. a1 1_279; in The Handbook - A Guide to Fluorescent Probes and Labeling Technologies, io ^th edition Molecular Probes / Invitrogen - Oregon 2005 which circulates on the Internet or in previous print editions.

Preferably, the fluorescent dye (s) b) of the invention are chosen from coumarin dyes, (poly) methine dyes, in particular cyanine and styryl / hemicyanine dyes, and naphthalimide dyes.

More particularly, the fluorescent dye (s) of the invention are cationic. Preferably, the fluorescent dye (s) of the invention are direct dyes chosen from (poly) methine dyes, in particular cyanine and styryl / hemicyanine dyes, and naphthalimide dyes and their mixtures; more preferably, the fluorescent dyes are direct and cationic; and more preferably, the fluorescent dye (s) b) are selected from styryl or hemicyanin cationic dyes.

More preferably, the fluorescent dyes of the invention absorb light in the range of yellow, orange and red, preferably in the absorption wavelength λ _to bs inclusive between 400 nm and 500 nm.

According to one variant, the fluorescent dyes of the invention contain at least one cationic radical carried by, or included in, at least one of the fluorescent chromophores.

Preferably, the cationic radical is a quaternary ammonium; more preferably, the cationic charge is endocyclic.

These cationic radicals are, for example, a cationic radical:

- which carries an exocyclic (di / tri) (C 1 -C 8) alkylammonium charge, or - which carries an endocyclic charge, such as the following cationic heteroaryl groups: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium , naphthoxazolium, naphtopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phénoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

According to a preferred variant of the invention, the fluorescent dyes of the invention carry at least one cationic chromophore and comprise at least one quaternary ammonium radical such as polymethine chromophores chosen from formulas (VI) and (VII) below :

W ⁺ - [C (R ^c ) = C (R ^d )] _m -Ar '- (*) Q- (VI)

Ar- [C (R ^d ) = C (R ^c )] _m -W ^{, +} - ( ^* ) Q ^" (VII),

formulas (VI) and (VII), in which:

W ⁺ represents a cationic heteroaryl group, comprising in particular a quaternary ammonium optionally substituted with one or more (C 1 -C 8) alkyl group (s) optionally substituted (s) in particular with one or more hydroxyl group (s) (s);

• W ' ⁺ represents a divalent heteroaryl radical as defined for W ⁺ ;

Ar represents an aryl group such as phenyl or naphthyl, optionally substituted preferably by i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C 1 -C 8) alkyl group (s), preferably C 1 -C 4, such as methyl; iii) one or more hydroxyl group (s); iv) one or more (C 1 -C 5) alkoxy group (s) such as methoxy; v) one or more hydroxy (C 1 -C 8) alkyl group (s) such as hydroxyethyl, vi) one or more amino or (di) (C 1 -C 8) alkylamino group (s), preferably with the alkyl part C1- _C4 optionally substituted with one or more group (s) hydroxyl (s) as (s) (di) hydroxyethylamino, vii) one or more group (s) acylamino; viii) one or more heterocycloalkyl group (s), such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;

Ar 'is a divalent aryl radical as defined for Ar;

M 'represents an integer between 1 and 4 inclusive, in particular m is 1 or 2; better still 1;

• R ^c and R ^d , identical or different, represent a hydrogen atom or optionally a substituted (C 1 -C 8) alkyl group, preferably C 1 -C 4, or alternatively R ^c is contiguous with W or W and / or R ^d is contiguous with Ar or Ar 'and form, with the atoms which contain them, a (hetero) cycloalkyl, in particular R ^c is contiguous with W ⁺ or W ' ⁺ and forms a (hetero) cycloalkyl such as cyclohexyl;

• Q ^" is an organic or mineral anionic counterion;

• (*) represents the part of the fluorescent chromophore linked to the rest of the dye.

Preferably, W ⁺ or W ' ⁺ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium radical optionally substituted with one or more identical or different C1-C4 alkyl (s) alkyl (s).

According to a particularly preferred embodiment of the invention, the fluorescent chromophore (s) of the dyes (VI) or (VII) are those defined above with m '= 1, Ar representing a para-substituted phenyl group. to the styryl group -C (R ^d ) = C (R ^c ) - with a (di) (hydroxy) (C 1 -C 6) (alkyl) amino group such as dihydroxy (C 1 -C 4) alkylamino, and W ' ⁺ representing an imidazolium or pyridinium group, preferably ortho- or para-pyridinium.

According to another preferred variant of the invention, the fluorescent chromophore (s) of the dyes is (are) cationic and comprises at least one quaternary ammonium radical such as a naphthalimidyl carrying a charge. cationic exocyclic form (Via) or (Vlla):

(Via) (Vlla)

formulas (Via) and (Vlla), in which:

R ^e , R ^f , R ⁹ and R ^h , which may be the same or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group which is optionally substituted, preferably with a di (C 1 -C 6) group; ) alkylamino or tri (C 1 -C 6) alkylammonium such as trimethylammonium; and representing the bond that connects the naphthalimydyl radical to the rest of the molecule.

According to one particular embodiment, the fluorescent dye (s) of the invention (b) are chosen from those of formulas (VIII), (IX) or (X) below, as well as their acid or base salts, organic or mineral salts. , their optical isomers, geometrical, tautomers and their solvates such as hydrates:

formulas (VIII), (IX) and (X), wherein:

R 1 and R 2, which are identical or different, represent a hydrogen atom or a C 1 -C 6 alkyl group; preferentially a hydrogen atom atom;

D represents a hydrogen atom, or a group selected from NH 2 or OH;

• R _a , R ' _a , R " _a , R'" _a , Rb, R'b, R "b, and R"'b, which are identical or different, represent a) a hydrogen atom, b) a halogen, a group c) amino, d) (C 1 -C 4) alkylamino, e) (C 1 -C 4) dialkylamino, f) cyano, g) carboxy -C (O) OH or carboxylate -C (O) O ^" , Q ⁺ , h) hydroxy-OH or alkoxide -O ^" Q ⁺ , i) (poly) halo (C1-C6) alkyl such as trifluoromethyl, j) acylamino, k) (C1-C6) alkoxy, I) (C1-C6) ) alkylthio, m) (poly) hydroxyalkoxy C2-C4, n) (C1-C6) alkylcarbonyloxy, o) (C1-C6) alkoxycarbonyl, p) (C1-C6) alkylcarbonylamino, q) acylamino, r) carbamoyl, s ) (C1-C6) alkylsulfonylamino, t) amino-sulfonyl, u) -SO3H or sulfonate -SO3 ^" , Q ⁺ or v) (C1-C6) alkyl optionally substituted with a group selected from (C1-C6) alkoxy, hydroxy , cyano, carboxy, amino, (di) (C 1 -C 4) alkylamino, or the two alkyl radicals borne by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another identical heteroatom or different to that of the nitrogen atom; particularly R _a , R ' _a , R " _a , R'" _a , Rb, R'b, R "b, and R"'b, represent a hydrogen, halogen atom or a group (Ci-C4) ) alkyl, preferably a hydrogen atom;

or two groups R _a and R '_a; Rb, and R'b; carried by two adjacent carbon atoms together form a benzo, indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted by an atom halogen, amino, (C 1 -C 4) alkylamino, (C 1 -C 4) dialkylamino, nitro, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, (C 1 -C 4) alkoxy (poly) hydroxy (C 1 -C 4) ) alkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonylamino, acylamino, carbamoyl, alkoxyalkylsulfonylamino, amino-sulfonyl, (C1-C6) alkyl optionally substituted by: a chosen group from (C 1 -C 6) alkoxy, hydroxy, cyano, carboxy, amino, (C 1 -C 4) alkylamino, (C 1 -C 4) dialkylamino, or the two alkyl radicals carried by the nitrogen atom of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; preferentially R _a and R '_a; together form a benzo group;

or two groups R, and R _a ; and / or a group R ', and R' _a together form a (hetero) cycloalkyl preferably fused cycloalkyl such as cyclohexyl R _g represents a hydrogen atom, a (hetero) aryl (Ci-C4) alkyl group or a group ( C1-C10) optionally substituted alkyl; preferentially Rb represents a hydrogen atom or a (C 1 -C 5) alkyl or benzyl group;

R _e represents a covalent bond, an optionally substituted linear or branched (C 1 -C 8) alkylene or (C 2 -C 8) alkenylene hydrocarbon chain, preferably R _e represents an (C 1 -C 6) unsubstituted alkylene;

Rf represents a hydrogen atom or a (Ci-C4) alkoxy, amino R3R4N- group, quaternary ammonium, M ', R3R4RsN ⁺ - wherein R 3, R 4 and R _5, identical or different, represent a group (Ci-C4 ) alkyl or R3R4N- represents a heteroaryl group optionally substituted, preferably an optionally substituted imidazolyl group, or else M ', R3R4RsN ⁺ - represents a cationic heteroaryl group optionally substituted, preferably an imidazolinium group optionally substituted with a (C1-C3) alkyl group;

G represents i) a group -NR _c Rd, ii) -OR with R representing a) a hydrogen atom, b) an optionally substituted (C1-C6) alkyl group, preferentially unsubstituted c) a (hetero) aryl group optionally substituted, d) an optionally substituted (hetero) aryl (C1-C6) alkyl group such as benzyl, e) (hetero) cycloalkyl optionally substituted, f) (hetero) cycloalkyl (C1-C6) optionally substituted alkyl; according to a particular embodiment of réalsation G represents a group -NR _c Rd, according to another particular embodiment G represents a group (Ci-Ce) alkoxy;

or when G represents -NR _c Rd, two groups R _c and R ' _a and / or Rd and R _a ; together form a saturated heteroaryl or heterocycle, optionally substituted by one or more (C 1 -C 6) alkyl groups, preferentially a heterocycle containing one or two heteroatoms selected from nitrogen and oxygen and comprising between 5 and 7 members; more preferentially, the heterocycle is chosen from the morpholinyl, piperazinyl, piperidinyl and pyrrolidinyl groups; • R _c , and Rd, identical or different, represent a hydrogen atom, an optionally substituted a) (hetero) aryl group such as phenyl, b) (hetero) aryl (C 1 -C ₄ ) alkyl optionally substituted, c) (hetero) optionally substituted cycloalkyl, optionally substituted d) (hetero) cycloalkyl (C ₁ -C ₄ ) alkyl, optionally substituted (C ₂ -C 8) alkyl or g) (C 1 -C 5) alkyl, preferably optionally substituted with a group hydroxy, carboxy, carboxylate, sulphate or sulphonate;

or two adjacent radicals R _c and Rd, carried by the same nitrogen atom together form an optionally substituted heterocyclic group or optionally substituted heteroaryl;

Ri and R'i, which may be identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;

Represents a (hetero) aryl group fused to the phenyl ring; or else is absent from phenyl; preferentially when the ring is present the ring is a benzo;

M represents an integer inclusive between 1 and 18, particularly an integer inclusive of between 1 and 14; preferentially an integer inclusive of between 2 and 10; more preferably an integer between 3 and 8; more particularly an integer between 4 and 6;

M 'represents an anionic counterion, derived from organic or inorganic acid salt, or from an organic or inorganic base ensuring the electroneutrality of the dye;

• Q ⁺ represents a cationic counterion derived from organic or inorganic acid salt, or an organic or inorganic base ensuring the electroneutrality of the dye such as alkali metal, alkaline earth metal, or ammonium;

it being understood that when the dye comprises a carboxylate, sulphonate or alkoxide group or else M 'and Q ⁺ may be absent to ensure the electroneutrality of said dye.

According to one embodiment, the fluorescent dyes of the invention are of formula (VIII) as defined above.

According to a preferred embodiment, the fluorescent dye (s) of the invention are chosen from the following styryl dyes of formula (XI), as well as their acid or base salts, organic or mineral, their optical isomers, geometric, tautomers. and their solvates such as hydrates:

(XI)

formula (XI), wherein G, G 1, R _a , R _a , R " _a , Rb, R'b, R", R 1, R 1, R 1, R 2 and m are as defined above for (VIII).

In particular, the dye (s) of the invention are chosen from those of formula (XI) for which:

R 1 and R 2, which are identical or different, represent a hydrogen atom;

R 3 and R 4, which are identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group, preferably hydrogen;

• R _a , R'a, and R " _a , identical or different, represent a hydrogen atom, halogen such as fluorine, or a -OH group, -0 ^" Q ⁺ , (Ci-C6) alkoxy, nitro, or cyano, with Q ⁺ as defined previously;

Rb, R'b, and R "b, which are identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group;

or else 2 contiguous radicals Rb and R'b together with the carbon atoms which carry them a benzo group fused or fused to the pyridinium group form said benzo group which may be substituted, preferably said benzo group is not substituted;

G represents a group -NR _c Rd, or (Ci-Ce) optionally substituted alkoxy, preferably unsubstituted; according to a particular embodiment of réalsation G represents a group -NR _c Rd, according to another particular embodiment G represents a group (Ci-Ce) alkoxy;

• G1 represents a group selected from NH2 and OH;

R 1 and R ', which are identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group; · ^{"""^} Is aryl or heteroaryl fused to phenyl ring, or is absent then the phenyl ring; preferably when the ring is present the ring is a benzo;

M represents an integer inclusive of between 1 and 18; particularly an integer inclusive inclusive between 2 and 16; preferably an integer between 3 and 10; more preferably an integer between 4 and 6;

• R _c , and Rd, identical or different, represent a hydrogen atom, a group (C2-C4) alkyl, or a (C1-Cs) substituted alkyl group, preferably (C2- C4) alkyl substituted in particular with one or more groups selected from i) cyano, ii) (C1-C3) alkoxy, iii) hydroxy, and iv) (C1-C3) alkylcarbonyl, preferably with one or more hydroxy groups; and

M 'representing an anionic counterion, derived from organic or inorganic acid salt, or an organic or inorganic base ensuring the electroneutrality of the dye; it being understood that when the dye comprises an alcoholic group then M 'and Q ⁺ may be absent by ensuring the electroneutrality of said dye.

Preferably, the fluorescent dye (s) b) of the invention are chosen from the following styryl dyes of formula (XII), as well as their organic or inorganic acid or base salts, their optical, geometric and tautomeric isomers. their solvates such as hydrates:

(XII)

formula (XII), with G, d, R _a , R ' _a , Rb, R'b, and m as defined above.

According to a particular embodiment, the group G is in the para position of the group -CH = CH- i.e. at the 4 'position of the phenyl group. According to another particular embodiment of the invention, the group G is in the ortho position of the group - CH = CH- i.e. at the 2 'position of the phenyl group. According to one embodiment the group - CH = CH- is in the para position of the pyridinium group i.e. in position 4.

According to another advantageous variant the group -CH = CH- is in the ortho position of the pydinium group i.e. in position 2.

According to one preferred embodiment of the invention, the fluorescent dye (s) of the invention (b) are chosen from the following compounds of formula (XIII) and (XIV), as well as their acid or base salts, organic or mineral salts. , their optical isomers, geometrical, tautomers and their solvates such as hydrates:

(XIII) (XIV)

formulas (XIII) or (XIV), in which:

R ¹ , R ² , R ³ and R ⁴ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group; preferably R ² and R ³ represent a hydrogen atom and R ¹ and R ⁴ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group;

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , which are identical or different, represent i) a hydrogen atom, or ii) halogen such as Cl, Br, F iii) a group OR where R represents a hydrogen atom or Q ⁺ as previously described, a (C 1 -C 3) alkyl, iv) aryl group such as benzene, v) an aryl (C 1 -C 3) alkyl group such as benzyl, vi) cyano, vii ) nitro, viii) (C 1 -C 3) alkylthio, ix) amino NR ¹⁰ R ¹¹ with R ¹⁰ and R ¹¹ , identical or different, representing a) a hydrogen atom, b) a (C 2 -C 4) alkyl group, or c) a substituted (C 1 -C 8) alkyl group, preferably (C 2 -C 4) alkyl optionally substituted with one or more groups chosen from:

- cyano,

- (C1-C3) alkoxy,

- hydroxy, and

- (C 1 -C 3) alkylcarbonyl;

in particular, R ¹⁰ and R ¹¹ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group substituted with one or more hydroxyl, cyano or (C 1 -C 3) alkylcarbonyl groups, such as hydroxyethyl;

M 'represents an anionic counterion as defined above;

it being understood that when the dye comprises an alkoxide group or else M 'and Q ⁺ may be absent to ensure the electroneutrality of said dye.

According to a first embodiment of the invention, the fluorescent dye (s)

As well as their organic or inorganic acid or base salts, their optical isomers, geometric, tautomers and solvates such as hydrates,

According to a second embodiment, the fluorescent dye (s) b) are

As well as their acid or base salts, organic or inorganic, their geometric isomers, tautomers and solvates such as hydrates.

Preferably, the fluorescent dye (s) b) are chosen from those of the following formulas (ΧΙΙΙ ') and (XIV):

(ΧΙΙΙ ') (XIV) formulas (ΧΙΙΙ') and (XIV), in which R ⁵ , R ⁷ , R ⁸ and m are as defined above for (XIII) and (XIV), in particular:

R ⁵ and R ⁸ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkoxy group such as methoxy;

R ⁷ represents a (C 1 -C 4) alkoxy or NR ¹⁰ R ^{11 group} with R ¹⁰ representing a) a hydrogen atom, or b) a (C 1 -C 6) alkyl group optionally substituted by one or more groups selected from ) cyano, ii) (C 1 -C 3) alkoxy, iii) hydroxy, and iv) (C 1 -C ³ ) alkylcarbonyl and R ¹¹ represents a) a (C 2 -C 8) alkyl group substituted with one or more groups selected from i) cyano ii) (C 1 -C 3) alkoxy, iii) hydroxy, and iv) (C 1 -C 3) alkylcarbonyl;

in particular NR ¹⁰ R ¹¹ represents a (C 2 -C 4) alkyl group (di) hydroxy (C 2 -C 4) alkylamino or hydroxy (C 2 -C 4) alkyl ((C 1 -C 4) alkyl) amino;

M represents an integer inclusive of between 1 and 18; particularly an integer inclusive inclusive between 2 and 16; preferably an integer between 3 and 10; more preferably an integer between 4 and 6; and

• M 'represents an anionic counterion, derived from organic or inorganic acid salt, or an organic or inorganic base ensuring the electroneutrality of the dye.

According to this embodiment, the fluorescent dye (s) b) are preferably chosen from those of formula (ΧΙΙΙ ') or (XIV) with:

OCH ₃ OCH ₃ OCH ₃ 16

According to yet another preferred embodiment of the invention, the fluorescent dye (s) of the invention b) are chosen from the following compounds of formula (XV) and (XVI), as well as their acid or base salts, organic or mineral, their optical isomers, geometric, tautomers and their solvates such as hydrates:

(XV) (XVI) formulas (XV) or (XVI), in which:

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , which are identical or different, represent i) a hydrogen atom, or ii) halogen such as Cl, Br, F iii) a group OR where R represents a hydrogen atom or Q ⁺ as previously described, a (C 1 -C 3) alkyl, iv) aryl group such as benzene, v) an aryl (C 1 -C 3) alkyl group such as benzyl, vi) cyano, vii ) nitro, viii) (C 1 -C 3) alkylthio, ix) amino NR ¹⁰ R ¹¹ with R ¹⁰ and R ¹¹ , identical or different, representing a) a hydrogen atom, or b) a (C 1 -C 5) alkyl group optionally substituted with one or more groups selected from:

- cyano,

- (C1-C3) alkoxy,

- hydroxy, and

- (C 1 -C 3) alkylcarbonyl;

in particular, R ¹⁰ and R ¹¹ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group optionally substituted by one or more hydroxyl, cyano or (C 1 -C 3) alkylcarbonyl groups, such as methyl or ethyl groups; butyl, isobutyl, cyanoethyl, methylcarbonylethyl, or hydroxyethyl M represents an integer inclusive of between 1 and 18; particularly an integer inclusive inclusive between 2 and 16; preferably an integer between 3 and 10; more preferably an integer between 4 and 6;

M 'represents an anionic counterion derived from organic or inorganic acid salt, preferably from Y;

According to one embodiment of the invention, the fluorescent dye (s) (b) are of formula (XV) with:

According to another embodiment, the fluorescent dye (s) (b) are of formula (XVI) with:

More particularly, the fluorescent dyes of the invention (b) are chosen from the following ones:

(XV) (XVI ')

formulas (XV) and (XVI), in which R ⁵ , R ⁷ , R ⁸ and m are as defined previously for (XIII) and (XIV), in particular:

R ⁷ represents a (C 1 -C 4) alkoxy or NR ¹⁰ R ^{11 group} with R ¹⁰ and R ¹¹ , which may be identical or different, representing a) a hydrogen atom, or b) an optionally substituted (C 1 -C 6) alkyl group by one or more groups selected from i) cyano, ii) (C 1 -C 5) alkoxy, iii) hydroxy, and iv) (C 1 -C 5) alkylcarbonyl; in particular R ¹⁰ and R ¹¹ , which may be identical or different, represent a hydrogen atom, or a (C 1 -C 6) alkyl group optionally substituted for one or more hydroxyl, cyano or (C 1 -C 6) alkylcarbonyl groups such as methyl or ethyl butyl, isobutyl, cyanoethyl, methylcarbonylethyl, or hydroxyethyl; preferably R ¹⁰ and R ¹¹ , identical or different, represent a (C 1 -C 6) alkyl group optionally substituted by one or more hydroxyl groups such as hydroxyethyl;

M 'represents an anionic counterion, derived from organic or mineral acid salt, or from an organic or inorganic base ensuring the electroneutrality of the dye.

According to one embodiment, the fluorescent dye (s) of the invention (b) are of formula (XV) or (XVI ') with:

More particularly, the fluorescent dye (s) of the invention (b) are chosen from those of formula (VIII), (IX) or (XII) as defined above in which G represents a hydrogen atom.

More particularly, the fluorescent dye (s) of the invention (b) are chosen from those of the following formulas (XVII) and (XVIII):

(XVII) (XVIII) formulas (XVII) and (XVIII), wherein R ⁵ , R ⁷ , R ⁸ and m are as previously defined for (XIII) and (XIV), in particular:

R ⁵ and R ⁸ , which are identical or different, represent a hydrogen atom or a

(C 1 -C 4) alkoxy group such as methoxy, preferably R ⁵ and R ⁸ represent a hydrogen atom;

R ⁷ represents a (C 1 -C 4) alkoxy or NR ¹⁰ R ^{11 group} with R ¹⁰ and R ¹¹ , which may be identical or different, representing a) a hydrogen atom, or b) an optionally substituted (C 1 -C 6) alkyl group by one or more groups selected from i) hydroxy, ii) RZC (X) -Y- with X, Y and Z representing oxygen, sulfur or N (R '), or X and / or Z represents (nt) a bond, R and R ', which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group, preferably X represents an oxygen atom, iii) a sulfonic SO 3 H, iv) a sulfonate SO 3 ^" , Q ⁺ , v) carboxylate C (O) O ^" , Q ⁺ with Q ⁺ representing a cationic counter ion such as alkali metal or alkaline earth metal; in particular R ⁷ represents a group NR ¹⁰ R ¹¹ with R ¹⁰ and R ¹¹ , which are identical or different, representing a) a hydrogen atom, or b) a (C 1 -C 6) alkyl group optionally substituted with one or more groups chosen from i) hydroxy, ii) carboxy, iii) carboxylate, iv) sulphonic, and v) sulphonate, more particularly chosen from identical or different, representing a) a hydrogen atom, or b) a (Ci-Ce) alkyl group optionally substituted with a group selected from i) hydroxy, ii) carboxy, and iii) carboxylate;

M represents an integer inclusive of between 1 and 18; particularly an integer inclusive between 1 and 6; preferably an integer between 1 and 4; more preferably an integer between 1 and 2; and

M 'represents an anionic counterion, derived from organic or inorganic acid salt, or from an organic or inorganic base ensuring the electroneutrality of the dye; it being understood that when the dye comprises a sulfonate or carboxylate group then M 'and Q ⁺ may be absent to ensure the electroneutrality of said dye.

More preferably, the fluorescent dye (s) of the invention (b) are chosen from the following compounds, as well as their geometrical isomers, their tautomers, their solvates and their mixtures:

(I)

With M 'and Q ⁺ as defined above, preferably the fluorescent dyes of the invention are chosen from dyes (g) and (h).

The composition according to the invention contains, in a cosmetic medium, a quantity of fl uorescent dyes b) as defined above, which is particularly inclusive between 0.001% and 30% relative to the total weight of the composition. Preferably, the amount of fluorescent dyes b) is included between 0.01 and 5% by weight relative to the total weight of the composition. More preferably, the or the fluorescent dye (s) is (are) in an amount between 0.01% and 2% inclusive.

Reducing agents c)

The method for dyeing the keratinous fibers and the cosmetic composition according to the present invention may optionally implement, or comprise, in addition c) one or more reducing agents.

The reducing agent (s) c), useful for the present invention, are advantageously chosen from the compounds of formula (Ic) below, as well as their addition salts and their mixtures:

formula (the), in which,

X represents P, S or SO2,

q represents an integer number gi at 0 or 1 or 2, preferably 1 or 2 with X = S

- s represents an integer equal to 0 or 1

- 1 represents an integer equal to 1 or 2, and

R 10 represents a linear or branched, saturated or unsaturated C 1 -C 20 alkyl radical, optionally interrupted by one or more heteroatoms, and / or optionally substituted with one or more radicals chosen from hydroxyl, halogenated, aminated and carboxyl radicals; (C1-C3o) alkoxy) carbonyl, amido, ((C1-C3o) alkyl) aminocarbonyl, (C1-C3o) acyl) amino, mono or dialkylamino, and mono or dihydroxylamino.

Preferably, the reducing agent (s) of the invention are thiolated.

More particularly, the reducing agent (s) present in the activator agent (s) used according to the invention are chosen from organic compounds comprising one or more mercapto groups (-SH or -S-), or disulfide (-SS-), preferably -SH (thiol) and at least one other function selected from the carboxylic acid, amine, amide, ester and alcohol functional groups and mixtures thereof.

According to one particular embodiment of the invention, the reducing agent or agents used in the invention are chosen from those of formulas i-1 and i-2, as well as their salts of acids, or bases, organic or inorganic, their optical isomers, tautomers, and solvates such as hydrates:

R-SH R'-S-R "

i-1 i-2

Formulas i-1 and i-2 in which:

• R represents:

a (C 1 -C 8) alkyl group, preferably (C 1 -C 6) alkyl, linear or branched, optionally substituted, preferably substituted, with one or more groups chosen from C (O) OH carboxy (di) (C 1 -C 6); C4) (alkyl) amino, hydroxy-OH, thiol -SH; and / or optionally interrupted by one or more heteroatoms or groups selected from -O-, and -S-, -N (R "') -, C (O) or their associations such as -OC (O) -, -C (0) -O-, -N (R "') - C (O) -, or -C (O) -N (R"') -; with R '"representing a hydrogen atom or a group ( C 1 -C 6) alkyl; or

a (hetero) aryl group optionally substituted, in particular with one or more hydroxyl, thiol or carboxy groups;

• R 'and R ", identical or different, represent a (C 1 -C 8) alkyl group, preferably (C 1 -C 6) alkyl, preferably substituted with one or more groups selected from hydroxy, thiol, and carboxy;

or else R 'and R "form together with the sulfur atom which carry them a heterocyclic group, comprising from 5 to 7, preferably saturated, comprising from 1 to 3 heteroatoms, optionally substituted (in particular by one or more groups ( Ci-Ce) alkyl optionally substituted with one or more hydroxyl, thiol or carboxy groups), more preferably the heterocyclic group is a dithiolane group optionally substituted by a (C 1 -C 6) alkyl group optionally substituted by one or more carboxy groups.

According to one particular embodiment of the invention, the reducing agents are of formula I-1, in particular those for which R represents a linear or branched (C 1 -C 8) alkyl group, preferably (C 1 -C 6) alkyl,

- preferably substituted by one or more groups selected from carboxy C (O) OH, amino, hydroxy -OH, thiol -SH; and or

optionally interrupted by one or more heteroatoms or groups chosen from -O-, -N (R "') -, C (O) or their associations such as -OC (O) -, -C (O) -O-, -N (R "') - C (O) -, or -C (O) -N (R"') - Preferably R is (C 1 -C 6) alkyl, preferably (C 1 -C 6) alkyl linear or branched uninterrupted.

According to another particular embodiment of the invention, the reducing agents are of formula I-1 for which R represents:

a phenyl group optionally substituted with one or more hydroxyl, thiol or carboxy groups; or

- Heteroaryl comprising 5 to 10-membered, preferably bicyclic 9 or 10-membered, comprising 1 to 4 heteroatoms selected from O, S or N, preferably N, optionally substituted with one or more hydroxyl groups, or thiol.

According to another particular embodiment of the invention, the reducing agents are of formula I-2, in particular those for which R 'and R ", which are identical or different, represent a (C 1 -C 8) alkyl group, preferably (Ci -C6) alkyl, preferably substituted with one or more groups selected from hydroxy, thiol, and carboxy.

According to another particular embodiment of the invention, the reducing agents are of formula I-2, in particular those for which R 'and R "form together with the sulfur atom which carry them a heterocyclic group, comprising from 5 to 7 preferably saturated links, comprising from 1 to 3 heteroatoms, optionally substituted with one or more (C 1 -C 6) alkyl groups optionally substituted by one or more hydroxyl, thiol or carboxy groups, more preferably the heterocyclic group is an optionally substituted dithiolane group; by a (C 1 -C 6) alkyl group optionally substituted with one or more hydroxy, thiol or carboxy groups.

Preferably, the reducing agents comprising at least one mercapto or disulfide group of the invention are chosen from thioglycolic acid, thiolactic acid or 2-mercaptopropionic acid, cysteine, cysteamine, homocysteine and glutathione. thioglycerol, thiomalic acid, 3-mercaptopropionic acid, thiodiglycol, 2-mercaptoethanol, dithiothreitol, thioxanthine, thiosalicylic acid, thiodiglycolic acid, lipoic acid, V-acetyl cysteine, esters and amides of thioglycolic or thiolactic acids, in particular glycerol monothioglycolate, their salts and mixtures of these compounds.

More particularly, the reducing agents comprising at least one mercapto or disulfide group of the invention are chosen from thioglycolic acid, thiolactic acid or 2-mercaptopropionic acid, cysteine, cysteamine, homocysteine and glutathione. thioglycerol, thiomalic acid, 3-mercaptopropionic acid, thiodiglycol, 2-mercaptoethanol, dithiothreitol, thioxanthine, thiosalicylic acid, thiodiglycolic acid, lipoic acid, V-acetyl cysteine, esters and amides of thioglycolic or thiolactic acids, in particular glycerol monothioglycolate, their salts and mixtures of these compounds.

Preferably, the reducing agent (s) according to the invention are chosen from reducing agents comprising at least one -SH (thiol) group, also called thiolated reducing agents.

The at least one reducing agent (s) thiolated (s) can be used in particular in the form of salts, in particular the alkali metal salts such as sodium and potassium salts, alkaline earth metal salts, for example, magnesium and calcium salts, ammonium salts, amine salts and aminoalcohol salts. It is thus possible to use as the thiolated reducing agent ammonium thioglycolate.

In a particularly preferred manner, the reducing agent (s) c) of the invention are chosen from thioglycolic acid and its salts, thiolactic acid and its salts, cysteamine and its salts, and mixtures thereof. .

Even more preferably, the reducing agent (s) c) of the invention are chosen from thioglycolic acid and thiolactic acid and their salts.

The reducing agent or agents c) of the invention are chemical and are advantageously applied in the form of an aqueous solution whose content of chemical reducing agents is preferably between 0.01 and 10% by weight, and more preferably between 0.1 and 5% by weight, relative to the total weight of the aqueous solution. According to a particular embodiment of the invention, the dyeing method does not use a reducing agent.

According to this preferred embodiment of the invention, the cosmetic composition comprising ingredients a) and b) does not comprise a reducing agent.

Oxidizing agents d)

The method for dyeing keratinous fibers and the cosmetic composition according to the present invention may optionally implement, or comprise, in addition one or more oxidizing agents d).

Preferably, the oxidizing agent (s) d) are chosen from chemical oxidizing agents.

By "chemical oxidizing agent" is meant an oxidizing agent different from the oxygen of the air.

More particularly, the chemical oxidizing agent (s) d) are chosen from hydrogen peroxide, hydrogen peroxide generating systems, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors and alkali or alkaline earth metal percarbonates, and mixtures thereof.

Preferably, the chemical oxidizing agent (s) d) are chosen from hydrogen peroxide or systems generating hydrogen peroxide.

According to a preferred embodiment, the hydrogen peroxide generating system (s) are chosen from urea peroxide; polymeric complexes capable of releasing hydrogen peroxide, selected from polyvinylpyrrolidone / H 2 O 2; oxidases; perborates; and percarbonates.

Preferably, the chemical oxidizing agent (s) d) are hydrogen peroxide, and more preferably hydrogen peroxide in aqueous solution (hydrogen peroxide).

The chemical oxidizing agent (s) d) is advantageously applied in the form of an aqueous solution whose content of chemical oxidizing agents is preferably between 0.05 and 5% by weight, and more preferably between 0.1 and 2%. by weight, relative to the total weight of the aqueous solution.

According to a preferred embodiment of the invention, the dyeing method does not use a chemical oxidizing agent.

According to this preferred embodiment of the invention, the cosmetic composition comprising ingredients a) and b) does not comprise an oxidizing agent.

The cosmetic medium and solvents The green violet blue benzoindolinium dye (s) a) as defined above, and the fluorescent dye (s) b) as defined previously, and / or the reducing agent (s) c), may be previously dissolved before being applied. on keratinous fibers.

In other words, the ingredients used in the dyeing process of the present invention may be present in one or more compositions.

The composition or compositions comprising the ingredients according to the present invention are cosmetic compositions, that is to say they are preferably aqueous. In addition to water, they may include one or more organic solvents, or mixtures thereof.

Examples of organic solvents that may be mentioned include linear or branched C ₂ to C ₄ alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

DH The pH of the composition (s) used in the dyeing process of the invention and of the composition of the invention comprising the ingredients a) and b) as defined previously, is preferably between 2 and 12. and more preferably between 3 and 1 1. It can be adjusted to the desired value by means of acidifying or alkaline agents usually used for dyeing keratinous fibers or else using conventional buffer systems.

The pH of the composition which comprises the ingredients a) and / or b) and / or c) and that of the composition or compositions used in the dyeing process of the invention (in particular the composition which comprises the reducing agent (s) c) when present), is preferably included between 6 and 1 1, more preferably between 7 and 10, and more preferably between 7.5 and 9.5, such as between 9 and 9.5.

Among the acidifying agents the inorganic and organic acids as defined above, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

The alkaline agent (s) may in particular be chosen from inorganic, organic and hybrid alkaline agents and mixtures thereof. The inorganic alkaline agent (s) is (are) preferably chosen from ammonia, alkali carbonates or bicarbonates, such as ammonium, sodium or potassium carbonates or bicarbonates, ammonium, sodium or potassium hydroxides or their mixtures .

The organic alkaline agent (s) are preferably chosen from organic amines whose pKb at 25 ° C. is less than 12, and preferably less than 10, even more advantageously less than 6. It should be noted that this is pKb corresponding to the highest basicity function. In addition, the organic amines do not include a fatty chain, alkyl or alkenyl, comprising more than ten carbon atoms.

The organic alkaline agent (s) is (are) preferably chosen from alkanolamines, in particular mono-, di- or tri-hydroxy (C 1 -C 6) alkylamines such as triethanolamine, ethylenediamines which are oxyethylenated and / or oxypropylenated, amino acids and polyamines. of the following formula (Ie) and mixtures thereof:

N - W - NAR ^{y R} <(the)

formula (Ic), wherein, W is a divalent C 1 -C 6 alkylene radical optionally substituted by one or more hydroxyl groups or a C 1 -C 6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as O, or NR _U ; R _x , R _y , R _z , Rt, and R _{u, which are} identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl radical, or an aminoalkyl radical;

By way of example, amines of formula (Ic), 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine may be mentioned.

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

In particular, the organic amines chosen from alkanolamines, such as mono-, di- or tri-alkanolamines, comprising one to three identical or different C ₁ -C ₄ hydroxyalkyl radicals, are particularly suitable for carrying out the invention.

Among compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Ν, Ν-dimethylethanolamine, 2-amino-2-methyl-1-propanol and triisopropanol. amine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane.

More particularly, the usable amino acids are of natural origin or of synthesis, in their L, D, or racemic form and comprise at least one function acid chosen more particularly from carboxylic, sulfonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine and cysteine. , glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to the following formula (Ile) R-CH 2 -CH (NH 2) -C (O) -OH, and also their salts, formula (II), in which, R represents a group selected from imidazolyl, preferably imidazolyl-4-yl; aminopropyl; aminoethyl; - (CH ₂ ) ₂ N (H) -C (O) -NH ₂ ; and - (CH ₂ ) ₂ -N (H) -C (NH) -NH ₂ . The compounds corresponding to the formula (II) are histidine, lysine, arginine, ornithine, citrulline.

The organic amine may also be chosen from heterocyclic organic amines. In addition to the histidine already mentioned in the amino acids, mention may be made, in particular, of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides that can be used in the present invention, mention may be made in particular of carnosine, anserin and balenine

The organic amine may also be selected from compounds having a guanidine function. As amines of this type that may be used in the present invention, mention may in addition be made of arginine already mentioned as amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2 - ([amino (imino) methyl] amino) ethane-1 acid sulfonic.

As hybrid compounds, mention may be made of the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid.

In particular, guanidine carbonate or monoethanolamine hydrochloride can be used.

Preferably, the alkaline agent (s) useful for the invention are chosen from ammonia, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, and preferably corresponding to those of formula ( Isle). More preferably, the alkaline agent (s) are chosen from and mixtures thereof, and more preferably from ammonia, ammonium bicarbonate, ammonium hydroxide, mono-, di- or tri-hydroxy (C 1 -C 6) ) alkylamine, such as MEA, and mixtures thereof.

Forms of composition

The composition or compositions comprising the blue, violet, or green dye (s) a) as defined above, and the fluorescent dye (s) b) as defined above, may be in various galenic forms, such as in the form of liquids, lotions, creams, gels, or in any other form suitable for dyeing keratinous fibers.

They may also be packaged under pressure in an aerosol flask in the presence of a propellant or in a non-aerosol flask and form a foam.

additives

When the ingredients used in the dyeing process according to the present invention are present in one or more compositions, said one or more compositions may optionally further comprise one or more additives, different from the ingredients of the invention and from which mention may be made of fatty substances, cationic, anionic, nonionic, amphoteric or zwitterionic surfactants, cationic, anionic, nonionic or amphoteric polymers or mixtures thereof, anti-dandruff agents, antiseborrhoeic agents, agents for preventing hair loss and / or regrowth vitamins and pro-vitamins including panthenol, sunscreens, inorganic or organic pigments, sequestering agents, plasticizers, solubilizing agents, acidifying agents, mineral or organic thickeners, in particular polymeric thickeners, opacifiers or pearlescent agents, anti-ox agents ydants, hydroxyacids, perfumes, preservatives, pigments and ceramides.

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 (s) according to the invention are not, or not substantially, impaired by the one or more proposed additions.

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

The method for dyeing keratinous fibers according to the present invention comprises the application to said keratinous fibers of the following ingredients:

a) one or more green violet blue benzoindolinium dyes as defined above, and

b) one or more fluorescent dyes as defined above, it being understood that the blue green blue benzoindolinium dye (s) a) (ingredients a)) and the fluorescent dye (ingredients (b)) are applied to said keratinous fibers in a manner such that joint or sequential.

In other words, the staining method according to the present invention can be carried out in one or more steps.

According to a particularly preferred embodiment, the blue green blue benzoindolinium dye (s) a) and the fluorescent dye (s) b), as defined above, are applied jointly (or jointly), that is to say simultaneously , on keratinous fibers. According to this embodiment, the coloring process is carried out in one step.

According to this embodiment in one step, the method comprises a step of applying to said keratin fibers a cosmetic composition according to the invention which comprises one or more green purple blue indolinium dyes a) as defined previously, and one or more several fluorescent dyes b), as defined above, on keratinous fibers.

According to another particularly preferred embodiment, the green violet blue indolinium dye (s) a), as defined above, and the fluorescent dye (s) b), as defined above, are applied sequentially, that is to say say successively. According to this other embodiment, the dyeing process is carried out in at least two stages.

According to a first embodiment in at least two steps, the fluorescent dye (s) b), as defined above, are applied to the keratinous fibers after green violet blue indolinium dye (s) a), as defined previously. In other words, the fluorescent dye (s) b), as defined above, are applied after the green violet blue indolinium dye (s) as defined above.

According to this first embodiment, the method for dyeing keratinous fibers comprises at least the following two successive steps:

a first step of applying to said keratinous fibers a cosmetic composition comprising one or more green purple blue indolinium dyes a) as defined above, followed by a second step of applying to said keratin fibers a cosmetic composition which comprises one or more fluorescent dyes b), as defined above.

According to a preferred embodiment in at least two stages, the green violet blue indolinium dye (s) a), as defined above, are applied to the keratin fibers after the fluorescent dye (s) b), as defined previously. In other words, the one or more auto-oxidizable dyes and / or blue green violet oxidation dyes a), as defined previously, are applied after the fluorescent dye (s) b), as defined previously. According to this preferred embodiment, the method for dyeing keratinous fibers comprises at least the following two successive steps:

a first step of applying to said keratin fibers a cosmetic composition comprising one or more fluorescent dyes b), as defined above, followed by

a second step of applying to said keratinous fibers a cosmetic composition comprising one or more green purple blue indolinium dyes a) as defined above.

The keratinous fibers, in particular human fibers such as the hair, which are treated with the process of the invention, may be pretreated with one or more reducing agents c) as defined above, in particular if the process of the invention implements ingredient b) before ingredient a).

According to one particular embodiment of the process of the invention, the blue, violet or green indolinium dye (s) a), as defined above, and the fluorescent dye (s) b), as defined above, are applied together on the fibers. keratinic; preferably the method comprises a step of applying to the keratinous fibers of a cosmetic composition which comprises one or more fluorescent dyes b), as defined above.

Preferably, the ingredients a) and b) are applied to the keratinous fibers in a bath ratio ranging from 0.1 to 10, and more particularly from 0.2 to 8. By bath ratio, the meaning of the present invention the ratio between the total weight of ingredient a) or b) and the total weight of keratinous fibers to be treated.

When the dyeing process is carried out in one step, the ingredients a) and b) are advantageously left in place on the keratin fibers for a duration ranging from 1 to 90 minutes, and more preferably for a duration ranging from 5 to 60 minutes.

When the dyeing process is carried out in at least two stages, each of the ingredients a) and b) can advantageously be left in place on the fibers keratin for a duration ranging from 1 to 60 minutes, and more preferably for a duration ranging from 5 to 50 minutes.

At the end of the dyeing process according to the invention, in one or at least two stages, the keratinous fibers are advantageously rinsed with water. They can optionally be washed with a shampoo, followed by rinsing with water, before being dried or allowed to dry.

When the dyeing process is carried out in at least two stages, the keratinous fibers are advantageously rinsed with water between each step. In other words, the staining process may comprise an intermediate rinsing step between the application of the first ingredient and the application of the second ingredient. During this intermediate rinsing step, the keratinous fibers may optionally be washed with a shampoo, followed by rinsing with water, before being dried or allowed to dry.

The dyeing process according to the present invention can be carried out at room temperature (25 ° C) or under heating.

According to a particular embodiment, the method of the invention further comprises the application on said keratinous fibers of one or more reducing agents c) as defined above, the said reducing agent or agents c) being able to be applied before, at the same time time or after the application of the greenish blue indolinium dye (s) as defined above, and / or the application of the fluorescent dye (s) such as defined previously; preferably, said reducing agent (s) c) is (are) present with the fluorescent dye (s) as defined previously; preferably, said reducing agent (s) c) are chosen from reducing agents of formula (Ie) as defined previously, ii) thioglycolic acid, iii) thiolactic acid, iv) glycerol monothioglycolate, v ) cysteamine, vi) N-acetyl-cysteamine, vii) N-propionyl-cysteamine, viii) cysteine, ix) N-acetyl-cysteine, x) thiomalic acid, xi) panthe- tine, xii) 2,3-dimercaptosuccinic acid, xiii) N- (mercaptoalkyl) -ro-hydroxyalkylamides, xiv) N-mono- or N, N-dialkylmercapto-4-butyramides, xv) amino-mercaptoalkylamides, xvi) derivatives N- (mercaptoalkyl) -succinamic acids, xvii) derivatives of N- (mercaptoalkyl) succinimide acids, xviii) alkylamino mercaptoalkylamides, ix) the azeotropic mixture of 2-hydroxypropyl thioglyconate and (2-hydroxy-1-thioglycolate) - methyl) ethyl, x) mercaptoalkylaminoamides, xi) N-mercaptoalkylalkanediamides, xii) formamidine acid derivatives, finally, their addition salts and mixtures thereof; preferably the reducing agent (s) c) is (are) in the presence of the dye (s) blue (s), violet (s) or green (s) a) such as defined (s) pécédemment and the fluorescent dye (s) as defined previously or the reducing agent (s) c) are applied at the same time the dye (s) a) as defined above, and the fluorescent dye (s) as defined previously.

When present, the reducing agent (s) c) can therefore be applied separately or in combination with one of the ingredients a) or b). Preferably, when present, the reducing agent (s) c) are applied together with ingredient b).

According to a particular embodiment, the method for dyeing keratinous fibers according to the present invention comprises the following successive steps:

a first step of applying to said keratin fibers a cosmetic composition comprising one or more dyes a) as defined above, followed by

a second step of applying to said keratin fibers a cosmetic composition comprising one or more fluorescent dyes b), as defined above, and one or more reducing agents c), as defined above.

According to a particular embodiment of the dyeing method of the invention, no step of said method uses an oxidizing agent.

According to another advantageous embodiment of the dyeing method of the invention, no step of said method uses a reducing agent.

The dyeing process according to the present invention may be applied to dry or moist keratinous fibers, and preferably dry.

The present invention also relates to a multi-compartment device comprising a first compartment containing one or more dyes a) as defined above, and a second compartment containing one or more fluorescent dyes b), as defined above, optionally a third compartment comprising one or more reducing agents c) as defined above, and optionally another compartment comprising one or more oxidizing agents d) as defined above.

The subject of the present invention is also the use of one or more fluorescent dye (s) b) as defined previously, associated with one or more dyes indolinium (s) a) as defined above, for the coloration of light keratin fibers, especially human keratinous fibers, such as hair, in chestnut, dark chestnut, brown, brown with reflection, even black, without using an additional dye different from a) or b).

According to one particular embodiment, the "keratinous fibers" are human keratinous fibers, and more particularly the hair.

The following examples serve to illustrate the invention without being limiting in nature.

EXE M P LES

I) Synthesis of benzoindolinium dyes:

The dye synthesis of the invention is carried out according to the following general reaction scheme:

Phthalic anhydride (1) is reacted with hydroxylamine hydrochloride in the presence of a base such as, for example, refluxing pyridine for 1 to 3 hours. A sulphonic acid chloride is then added, such as, for example, paratoluene sulphonic acid under reflux for 1 to 3 hours. The middle is then poured in water to recover the compound (2). This compound is then reacted in a water + alcohol mixture such as, for example, ethanol and in the presence of a base such as, for example, sodium hydroxide. The medium is then refluxed for 2 to 4 hours and then maintained at reflux by removing water with a stark dean. The medium is then cooled and acidified with a strong acid such as, for example, hydrochloric acid to yield the compound (3) which precipitates. It is then recovered by filtration.

Way A:

The compound (3) is reacted in a solvent such as sulfolane in the presence of the aromatic amine under reflux for 1 to 3 hours.

The halogenating agent such as, for example, phosphorus oxychloride is then added to the reaction medium and kept under reflux for 1 to 3 hours. The medium is then cooled to room temperature and then poured into water. The medium is then neutralized with the aid of a mineral base such as, for example, sodium hydroxide to precipitate the compound (5) thus obtained by filtration.

Compound (5) is then reacted in the presence of the halogenated reagent in a solvent such as refluxing acetonitrile to yield compound (6). Path B:

Compound (3) is reacted in a solvent such as acetonitrile in the presence of the alkylating agent and a mineral base such as refluxing potassium carbonate for 1 to 6 hours. After cooling, the compound (4) is obtained by filtration.

It is coated in the presence of the aromatic amine and a mixture of phosphorus oxychloride and phosphoric anhydride under reflux for 2 to 5 hours.

The reaction medium is then poured into water and then neutralized with a mineral base such as sodium hydroxide. The compound (6) is thus obtained by filtration after acidification with hydrochloric acid dissolved in an alcohol such as isopropanol.

As an example of synthesis, the synthesis of the following blue dye was carried out according to the two synthetic routes A and B

Lane A: X = Br 2- [4- (diethylamino) phenyl] -1-hexylbenzo [cd] indolium bromide Lane B: X = Cl 2- [4- (diethylamino) phenyl] -1-hexylbenzo [cd] chloride ] indolium

Synthesis of the compound (2):

2 - {[(4-methylphenyl) sulfonyl] oxy} -1H-benzo [de] isoquinoline-1,3 (2H) -dione

In a 1000 ml three-neck flask equipped with a condenser, an argon inlet, a bubbler and a magnetic stirrer, 100 grams of 1,8-naphthalic anhydride (0.505 moles), 35.1 were placed. grams of hydroxylamine hydrochloride (0.505 ml) in 300 ml of pyridine (3.7 moles), the reaction mixture was heated to complete dissolution and then refluxing for 1 hour.

The heating was stopped and spatula was then added spatula 21.6 grams of para-toluenesulfonic acid chloride (1.1 moles) to maintain reflux. The reaction medium was then refluxed for 90 minutes. The reaction medium was then poured into a beaker containing 400 ml of water with vigorous stirring. The white precipitate formed was filtered on sintered glass, washed extensively with water and 1 N sodium hydroxide solution and then dried under vacuum in the presence of P2O5 to a constant weight. There was thus obtained 180 grams of the expected compound according to mass spectrometry and NMR.

Synthesis of the compound (3)

benzo [cd] indol-2 (1H) -one

(2) (3)

In a 1000 ml three-neck flask equipped with a condenser, a dean-stark, a bubbler and a magnetic stirrer, 81 grams of sodium hydroxide were placed in 500 ml of water and then added. the compound (2) obtained above, with 200 ml of ethanol. The reaction medium was heated at reflux for 2 hours, gradually removing the solvent with dean-stark.

The reaction medium was then cooled to room temperature and then placed in a beaker and acidified to pH = 1-2 with 37% hydrochloric acid. The precipitate thus obtained was filtered on sintered glass, washed extensively with water and then dried under vacuum in the presence of P2O5.

The precipitate was recrystallized from ethyl acetate. The precipitate thus obtained was dried under vacuum in the presence of P2O5 to a constant weight to obtain 47 grams of the compound (3) conforming to mass spectrometry and NMR. WAY A:

Synthesis of the compound (5):

4- (benzo [cd] indol-2-yl) -N, N-diethylaniline

of a thermometer and a magnetic stirrer were placed 20 grams of compound (3) (0.1 18 moles) and 13.4 ml of diethylaniline (0.084 moles). The reaction medium was heated at 90 ° C. for 30 minutes. 18.1 ml of POC (0.194 moles) were then added dropwise, the reaction medium was heated to 90 ° C. by following the manipulation with UV light by means of TLC dichlomethane / methanol 9: 1. The reaction medium was solubilized in 50 ml of ethanol to which an ethanolic solution was added dropwise. 20% sodium hydroxide until color change of the reaction medium (dark blue to red). The reaction medium was then poured into a beaker containing 200 ml of water. The paste obtained was taken up in ethyl acetate. The medium was then evaporated under reduced pressure. The product was then purified on a silica column. 8.4 grams of a dark red paste, NMR-conform and mass spectrometry were thus recovered.

Synthesis of the compound (6): X = Br

2- [4- (diethylamino) phenyl] -1-hexylbenzo [cd] indolium bromide

(5) (6)

In a 100 ml tricol equipped with a refrigerant, an argon inlet, a bubbler, a thermometer and a magnetic stirrer, 1 gram of compound (5) (0.003 moles ) and 2.8 ml of bromohexane (0.020 mol) in 5 ml of acetonitrile. The reaction medium was heated to reflux by following the manipulation by TLC dichloromethane / methanol 9: 1 UV revelation. The product was then purified on a silica column to obtain, after evaporation of the fractions containing the expected product, 0.33 grams of compound (6) in the form of a dark blue powder conforming to mass spectrometry and NMR.

PATH B:

Synthesis of the compound (4)

(3) (4)

In a 100 ml three-necked flask equipped with a condenser, an argon inlet, a bubbler, a thermometer and a magnetic stirrer, 1 gram of compound (3) (0.06 moles) was placed. and 0.74 ml of bromohexane (0.005 mol) in 5 ml of acetonitrile with 0.8 gram of potassium carbonate (0.005 mol). The reaction medium was then heated to 90 ° C. following the manipulation by TLC. hepthane / ethyl acetate 5: 5 UV revelation. After evaporation under reduced pressure of the reaction medium, the product was purified on a silica column. After evaporation under reduced pressure of the fractions containing the expected product, 0.37 grams of a translucent yellow oil conforming to mass spectrometry and NMR were obtained.

Synthesis of the compound (6 '):

2- [4- (diethylamino) phenyl] -1-hexylbenzo [cd] indolium chloride

(4)

In a 100 ml three-necked flask equipped with a condenser, an argon inlet, a bubbler, a thermometer and a magnetic stirrer, 0.37 gram of compound (4) (0.0015 moles) was placed. and 0.163 ml of diethylaniline (0.001 moles). 1 ml of POC (0.01 moles) and 0.1 gram of P2O5 (0.001 moles) were then added. The reaction medium was heated to reflux by following the manipulation by TLC dichloromethane / methanol 9: 1 UV revelation. The reaction medium was cooled to room temperature and then 10 ml of water was added. The reaction medium was stirred at room temperature for 30 min and then 0.32 gram of sodium hydroxide was added. The reaction medium was again stirred at ambient temperature and then 40 ml of a solution of 5-6N hydrochloric acid in isopropanol was added. The medium was stirred for 30 minutes and then evaporated under reduced pressure. There was thus obtained 0.45 grams of a dark green blue viscous oil conforming to NMR and mass spectrometry.

By adapting the operating conditions and the alkyl halide R1-Hal, it is possible to synthesize the following compounds (a2) to (a4):

Dye (a2)

An = against anionic ion such as Cl ^" , or Br Dye (a3)

Coloring (a4) Jl JL An

An = ionic anion ion such as Cl ^" , or Br, the amino group of which can be salified, eg with HBr, or non-salified

II) EXAMPLES OF APPLICATION ON KERATIN FIBERS

In the examples which follow, all the quantities are indicated in weight percent relative to the total weight of the composition, unless otherwise indicated.

Dyes a) structures

Colorant (a1)

Structural dyes

fluorescent b) Colorant (b1)

Colorants (b2)

Compositions 1a were prepared as follows:

The study is performed on 90% white BN hair (1 g of lock of hair).

The application mode selected for the study is the one described above in the application mode section and corresponds to the one-step mode:

The studies are carried out at different pH; the pH of the blue dye solution + fluorescent dye is adjusted with:

- citric acid buffer (pH 4)

phosphate buffer (pH 7)

Ammonium buffer (pH 9.5)

Fluorescent dye composition

Reducing Composition 1 c:

Thioglycolic acid composition in 0.6% water brought to pH = 9.5 with monoethanolamine

Oxidizing composition 1 d: Solution of hydrogen peroxide at 0.6% in water.

Application Protocols: 1. Application of benzoindolinium dye (a1) and dye (b1) or (b2) in non-reducing medium:

1 g. Strand of hair is placed flat in a chute at room temperature. 4.5 ml of composition of the blue dye to be studied at 1% and 4.5 ml of solution of the 1% fluorescent dye adjusted to the desired pH with the buffers (pH = 4, 7 or 9.5) qs 10 ml are then added and kept in contact with the wick for 20 minutes.

The wick is then rinsed with water and wrung out between the fingers.

2. Application of benzoindolinium dye (a1) and dye (b1) or (b2) in a reducing medium:

1 g. Strand of hair is placed flat in a chute at room temperature. 4.5 ml of composition of blue dye to be studied at 1% and 4.5 ml of 1% fluorescent dye solution adjusted to pH 9.5 +1 ml of reducing composition qs 10 ml are then added and kept in contact with the lock for 20 minutes.

The wick is then rinsed with water and wrung out between the fingers.

3 application of the oxidizing solution (1 d)

The wick thus treated is placed flat in a chute at room temperature. 9 ml of water and 1 ml of the oxidizing solution are applied on the wick for 10 minutes. The wick is then rinsed with water and a shampoo is performed.

Visual observation The combination according to the invention thus makes it possible to obtain intense browns or blacks with excellent color increase and remaining in the shampoos.

Spectrocolorimetric results

The color of the locks was evaluated in the L ^* a ^* b ^{* system} using a MINOLTA ® CM 3600D spectrocolorimeter (Illuminant D65).

In this system L ^* a ^* b ^* , L ^* represents the brightness, a ^* indicates the green / red color axis and b ^* the blue / yellow color axis. The higher the L value, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The higher the value of a ^{* the} higher the shade is red and the higher the value of b ^* the hue is yellow.

The persistence of the color on hair corresponds to the variation of color between the strands of colored hair BN (natural white to 90% white) and the colored hair BN having undergone 10 successive shampoos is measured by (ΔΕ) according to the following equation:

ΔE = V (L ^* - L ₀ ^* ) ² + (a ^* - a ₀ ^* ) ² + (b ^* - b ₀ ^* ) ²

In this equation, L ^* , a ^* and b ^* represent the measured values after hair coloring BN and shampoos and Lo ^* , ao ^* and bo ^* represent the measured values after hair dye BN.

The lower the value of ΔΕ, the better the persistence of shampoo coloring.

Visual results

Color process

Blue dye (a1)

Colorant (a1) pH 4 blue

Colorant (a1) pH 7 blue

Colorant (a1) pH 9.5 blue

Fluorescent dye

Fluorescent dye (b1) pH4 orange

Fluorescent dye (b1) pH7 orange

Fluorescent dye (b1) pH9.5 orange

Fluorescent dye (b1) pH9.5 orange reducer

Fluorescent dyes (b2) pH 4 orange

Fluorescent dyes (b2) pH 7 orange

Fluorescent dyes (b2) pH 9.5 orange Fluorescent dyes (b2) pH 9.5 orange reducer

Fluorescent dye +

(a1) (b1) without reducing agent Example (1) pH 4 Dark brown

(a1) (b1) without reducing agent Example (1) pH 7 Dark brown a1) (b1) without reducing agent Example (1) pH 9.5 Dark brown

(a1) (b1) with reducer Example (2) Brown

(a1) (b2) without reducer Example (4) pH7 Mahogany Black

(a1) (b2) without reducer Example (4) pH9.5 Mahogany black

(a1) (b2) without reducing agent Example (4) pH9.5 + 10 shampoos Dark brown

Results L, a, b.

Visually it appears that the stains made by combining a blue-violet dye with a fluorescent dye leads to brown colors with coppery shades, mahogany but also to black mahogany shades. Moreover, for most of the colorations obtained, the colors are persistent in the shampoos themselves at high pH.

Claims

1. A process for dyeing keratin materials, in particular human keratinous fibers, such as the hair, which consists in applying to said materials:

a) one or more direct dyes of formula (I):

formula (I) in which,

R ¹ represents a radical:

C1-C10 linear or branched alkyl, optionally interrupted by one or more heteroatoms or groups selected from oxygen, sulfur, N (R), N ⁺ (R) (R ') An ^" , C (X) , S (O), S (O) ₂ or combinations thereof such as -N (R) -C (O) - or - C (O) -N (R) - and -SS-, where X represents an atom of oxygen, sulfur, or a group N (R), and R and R ', which may be identical or different, representing a hydrogen atom or a (C 1 -C 4) alkyl group, and / or said alkyl group being optionally substituted by one or more hydroxy, (di) (C 1 -C 4) (alkyl) amino groups or of formula (Γ):

an optionally substituted aryl radical, such as phenyl, or

an aryl (C 1 -C 4) alkyl radical such as benzyl, the aryl group being optionally substituted;

R ² and R ' ² , which may be identical or different, represent a group chosen from: i) (hetero) aryl- (T ¹ = T ² ) _n - and ii) ED- (T ¹ = T ² ) _n - with (hetero) aryl representing an optionally substituted aryl or heteroaryl group, ΤΊ and T2 identical or different, representing a nitrogen atom or a group C (R) with R as defined above, and n is 0, 1, 2 or 3 and ED representing an electron-donating group that (di) (C 1 -C 4) (alkyl) amino or (di) hydroxy (C 1 -C 4) alkylamino; in particular R ² , R ' ² represent i) with n being 0 and optionally substituted hetero) aryl, preferably representing optionally substituted aryl such as phenyl optionally substituted with one or more (di) (C 1 -C 4) (alkyl) amino groups or (di) hydroxy (C1-C4) alkylamino; · R ³ , R ' ³ , R ⁴ , R' ⁴ , R ⁵ , R ' ⁵ , R ⁶ , R' ⁶ , R ⁷ , R ' ⁷ , R ⁸ , and R' ⁸ , which are identical or different, representing uu hydrogen, halogen, or a group selected from (C 1 -C 6) alkyl, (C 1 -C 6) alkoxy, (C 1 -C 6) alkylthio, (di) (C 1 -C 4) (alkyl) amino, hydroxy, mercapto, nitro (so), cyano, R "- (X) _p -C (X ') - (X") _q - and R "- (X) _{p -} S (O) _r - (X") _q - X, X 'and X ", which may be identical or different, represent an oxygen atom, sulfur atom or a (C 1 -C 4) (alkyl) amino group, in particular X' represents an oxygen atom and X, X" represent a oxygen atom or amino, p and q, identical or different, are 0 or 1, r is 1 or 2, R "represents a hydrogen atom, or a (C 1 -C 4) alkyl group, preferably R ³ , R ' ³ , R ⁴ , R' ⁴ , R ⁵ , R ' ⁵ , R ⁶ , R' ⁶ , R ⁷ , R ' ⁷ , R ⁸ , and R' ⁸ represent a halogen atom;

Represents the bond which links the group (Γ) to the rest of the molecule, and

it being understood that the direct dye (s) a) and the fluorescent dye (s) b) are applied to said keratinous fibers jointly or sequentially.

2. The method of dyeing according to the preceding claim wherein the dyes of formula (I) are blue-violet dyes.

3. Coloring process according to any one of the preceding claims, in which the dye (s) of formula (I) are chosen from dyes of formula (Ia):

formula (la) in which;

R ¹ represents a radical: linear or branched C1-C10 alkyl, optionally substituted; an optionally substituted aryl radical, such as phenyl, or

an aryl (C 1 -C 4) alkyl radical such as benzyl, the aryl group being optionally substituted,

preferably, R ¹ represents a linear or branched C 1 to C 10 alkyl group, optionally substituted, more preferably a linear C 1 to C 6 alkyl group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined previously in claim 1, preferably R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ , represent a hydrogen atom;

4. Staining process according to any one of claims 1 or 2 wherein the benzimidazolium dye (s) of formula (I) are chosen from dyes of formula (Ib):

formula (Ib) in which

preferably L represents a C1-C10 alkylene group, linear or branched, particularly linear, optionally interrupted by one or more heteroatoms or groups chosen from oxygen, sulfur, N (R), N ⁺ (R) (R ' ) An ^" , C (O), or their combinations such as -N (R) -C (O) - or -C (O) -N (R) - and -SS-;

Represents the bond which links the group (Γ) to the rest of the molecule, and

5. The method of dyeing according to any one of claims 1, 2 or 4 wherein the dye (s) of formula (I) or (Ib) are chosen from those of formula (b):

formula (b) in which, An ^" , and L are as defined for (Ib), in the preceding claim, R ' ⁹ , R' ¹¹ , and R ^'13 have the same meaning as R ⁹ , R ¹¹ , and R ¹³ as defined in (Ib) in claim 3, preferably R ¹¹ and R ¹¹ are (di) (C -C ₄₎ (alkyl) amino or (di) hydroxy (Ci-C ₄₎ alkylamino and R ⁹ , R ¹³ , R ' ⁹ , R' ¹¹ , and R ^'13 , represent a hydrogen atom, preferably the dyes of formula (b) are symmetrical.

6. A process according to any one of the preceding claims, wherein the fluorescent dye (s) b) are light-absorbing dyes in the range of yellow, orange and red, especially red, preferably in the wavelength of d. absorption λ _a bs inclusively between 400 nm and 500 nm.

7. A process according to any one of the preceding claims, wherein the fluorescent dye (s) b) are fluorescent direct dyes; in particular selected from acridine dyes, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro {2 - [(2H-pyrrol-2-ylidene-kN) methyl] -1H-pyrrolato kN} borons, dipyrinones, dicetopyrrolopyrroles, fluorindines, (poly) methines (in particular cyanines and styryls / hemicyanins), naphthalimides, naphthylanilides, naphthylamine (such as dansyls), naphtholactams, oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squarans, stilbenes, xanthenes, thioxanthenes, thiazines and mixtures thereof, and preferably the fluorescent dye (s) are cationic; more preferably, the fluorescent dye (s) are direct dyes chosen from (poly) methine dyes, in particular cyanine and styryl / hemicyanine dyes, and naphthalimide dyes and their mixtures; and even more preferentially, the fluorescent dyes are direct and cationic and are chosen from styryl or hemicyanine cationic dyes.

8. Process according to any one of the preceding claims, characterized in that the fluorescent dye (s) b) are dyes which carry at least one cationic chromophore chosen from formulas (III), (IV), (Nia) and ( IVa): below:

W ⁺ - [C (R ^c ) = C (R ^d )] _m -Ar '- (*) Q- (|||)

Ar- [C (R ^d ) = C (R ^c )] _m -W ' ⁺ - ( ^* ) Q ^" (IV),

formulas (III) and (IV), in which:

W ⁺ represents a cationic heteroaryl group, comprising in particular a quaternary ammonium optionally substituted with one or more (C 1 -C 5) alkyl group (s) optionally substituted (s) in particular with one or more hydroxyl group (s) (s);

· W ' ⁺ represents a divalent heteroaryl radical as defined for W ⁺ ;

Ar represents an aryl group such as phenyl or naphthyl, optionally substituted preferably by i) one or more halogen atom (s) such as chlorine or fluorine; ii) one or more (C 1 -C 8) alkyl group (s), preferably C 1 -C 4, such as methyl; iii) one or more hydroxyl group (s); iv) one or more (C 1 -C 5) alkoxy group (s) such as methoxy; v) one or more hydroxy (C 1 -C 8) alkyl group (s) such as hydroxyethyl, vi) one or more amino or (di) (C 1 -C 8) alkylamino group (s), preferably with the alkyl part C1- _C4 optionally substituted with one or more group (s) hydroxyl (s) as (s) (di) hydroxyethylamino, vii) one or more group (s) acylamino; viii) one or more heterocycloalkyl group (s), such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;

Ar 'is a divalent aryl radical as defined for Ar; m 'represents an integer between 1 and 4 inclusive, in particular m is 1 or 2; better still 1;

R ^c and R ^d , identical or different, represent a hydrogen atom or optionally a substituted (C 1 -C 8) alkyl group, preferably C 1 -C 4, or alternatively R ^c is contiguous with W or W and / or R ^d is contiguous with Ar or Ar 'and form, with the atoms containing them, a (hetero) cycloalkyl, in particular R ^c is contiguous with W ⁺ or W' ⁺ and forms a (hetero) cycloalkyl such as cyclohexyl;

Q ^" is an organic or inorganic anionic counterion;

( ^* ) represents the part of the fluorescent chromophore linked to the rest of the dye; preferably, W ⁺ or W ' ⁺ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium radical optionally substituted with one or more identical or different C1-C4 alkyl (s) alkyl radicals; preferably the fluorescent chromophore (s) are chosen from those with m '= 1, Ar representing a phenyl group substituted para to the styryl group -C (R ^d ) = C (R ^c ) - with a group (di) (hydroxy) (C1-C6) (alkyl) amino such as dihydroxy (C1-C4) alkylamino, and W ' ⁺ representing an imidazolium or pyridinium group, preferably ortho- or para-pyridinium;

(Via) (VI la)

formulas (Via) and (Vlla), in which:

R ^e , R ^f , R ⁹ and R ^h , which may be the same or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group which is optionally substituted, preferably with a di (C 1 -C 6) group; ) alkylamino or tri (C 1 -C 6) alkylammonium such as trimethylammonium; and · 'representing the bond which connects the naphthalimydyl radical to the rest of the dye.

9. Process according to any one of the preceding claims, characterized in that the fluorescent dye (s) b) are chosen from dyes of formula (V), (VI) and (VII), and also their acid salts or basic, organic or inorganic, their optical isomers, geometrical, tautomers and their solvates such as hydrates:

formulas (V), (VI) and (VII), in which:

R 1 and R 2, which may be identical or different, represent a hydrogen atom or a C 1 -C 6 alkyl group; preferentially a hydrogen atom;

D represents a hydrogen atom, or a group selected from NH 2 or OH;

• or two groups R _a and R '_a; Rb, and R'b; carried by two adjacent carbon atoms together form a benzo, indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo cycle, indeno, heterocycloalkyl or heteroaryl being optionally substituted by a halogen atom, an amino group, (C1-C4) alkylamino, (C1-C4) dialkylamino, nitro, cyano, carboxy, hydroxy, trifluoromethyl, an acylamino radical (Ci-C4) alkoxy (poly) hydroxy (C1-C4) alkoxy, (C1-C4) alkylcarbonyloxy (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonylamino, acylamino, carbamoyl, alkoxyalkylsulfonylamino, amino-sulfonyl, (Ci-Ce ) alkyl optionally substituted with: a group selected from (C 1 -C 6) alkoxy, hydroxy, cyano, carboxy, amino, (C 1 -C 4) alkylamino, (C 1 -C 4) dialkylamino, or the two alkyl radicals borne by the atom nitrogen of the amino group form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different from that of the nitrogen atom; preferentially R _a and R '_a; together form a benzo group;

or else two groups R, and R _a and / or a group R ', and reform together a (hetero) cycloalkyl fused preferentially cycloalkyl such as cyclohexyl;

R _g represents a hydrogen atom, a (hetero) aryl (Ci-C4) alkyl group or an optionally substituted (C1-C6) alkyl group; preferentially Rb represents a hydrogen atom or a (C 1 -C 5) alkyl or benzyl group;

or when G represents -NR _c Rd, two groups R _c and R ' _a and / or Rd and R _a ; together form a heteroaryl or saturated heterocycle, optionally substituted by one or more (C 1 -C 6) alkyl groups, preferentially a heterocycle containing one or two heteroatoms selected from nitrogen and oxygen and comprising between 5 and 7 members; more preferably, the heterocycle is chosen from the morpholinyl, piperazinyl, pyperidinyl and pyrrolidinyl groups;

• R _c , and Rd, identical or different, represent a hydrogen atom, an optionally substituted a) (hetero) aryl group such as phenyl, b) (hetero) aryl (Ci-C 4) optionally substituted alkyl, c) ( hetero) cycloalkyl optionally substituted, d) (hetero) cycloalkyl (Ci-C4) alkyl optionally substituted, f) (C2-Cs) alkyl or g) (C1-Cs) alkyl optionally substituted, preferably optionally substituted by a hydroxy group, carboxy, carboxylate, sulphate or sulphonate;

Ri and R'i, which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group;

10. Process according to any one of the preceding claims, characterized in that the fluorescent dye (s) b) are chosen from the styryl dyes of formula (VIII) below, as well as their acid or base salts, organic or mineral salts. , their optical isomers, geometric, tautomers and solvates such as hydrates

(VIII)

formula (VIII), wherein G, G 1, R _a , R ' _a , R " _a , Rb, R'b, R" b, R, R'i, R 1, R 2, and m are as defined in preceding claim; in particular,

• Ri and R2, identical or different, represent a hydrogen atom;

R and R _' , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group, preferably hydrogen;

• R _a , R'a, and R " _a , identical or different, represent a hydrogen atom, halogen such as fluorine, or a -OH group, -0 ^" Q ⁺ , (Ci-C6) alkoxy, nitro, or cyano, with Q ⁺ as defined in the preceding claim;

• G1 represents a group chosen from N H2 and OH;

R 1 and R ', which are identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl group;

• - ^"" V ^ is aryl or heteroaryl fused to the phenyl ring; or else is absent from the phenyl ring; preferentially when the ring is present the ring is a benzo;

• R _c , and Rd, identical or different, represent a hydrogen atom, a group (C2-C4) alkyl, or a (C1-Cs) substituted alkyl group, preferably (C2-C4) alkyl substituted in particular with one or more groups selected from i) cyano, ii) (C1-C3) alkoxy, iii) hydroxy, and iv) (C1-C3) alkylcarbonyl, preferably by one or more hydroxy groups; and

• M 'representing an anionic counterion, derived from organic or inorganic acid salt, or an organic or inorganic base ensuring the electroneutrality of the dye;

it being understood that when the dye comprises an alcoholic group then M 'and Q ⁺ may be absent by ensuring the electroneutrality of said dye;

preferably, the fluorescent dye (s) b) are chosen from the following styryl dyes of formula (IX), as well as their organic or inorganic acid or base salts, their optical, geometric, and tautomeric isomers and their solvates, such as the hydrates:

(IX)

formula (IX), with G, d, R _a , R ' _a , Rb, R'b, and m as defined above; and preferably G is either in the para position of the group -CH = CH- ie in the 4 'position of the phenyl group or in the ortho position of the group -CH = CH- ie in the 2' position of the phenyl group, and / or the group -CH = CH- is either in the para position of the pyridinium group ie in position 4 or in the ortho position of the pydinium group ie in position 2.

11. Process according to any one of the preceding claims, characterized in that the fluorescent dye (s) b) are chosen from the following dyes, the compounds of formula (X), (XI), (XII) and (XIII), and their acid or base salts, organic or inorganic, their optical isomers, geometrical, tautomers and their solvates such as hydrates:

(XII) (XIII) formulas (X), (XI), (XII) or (XIII), wherein:

R ¹ , R ² , R ³ and R ⁴ , identical or different, represent a hydrogen atom or (C 1 -C 6) alkyl group; preferably R ² and R ³ represent a hydrogen atom and R ¹ and R ⁴ , which may be identical or different, represent a hydrogen atom or a (C 1 -C ₄ ) alkyl group;

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , which are identical or different, represent i) hydrogen atom, or ii) halogen such as Cl, Br, F iii) a group OR where R represents a hydrogen atom or Q ⁺ as defined in claim 1 1, a (C 1 -C 3) alkyl, iv) aryl group such as benzene, v) an aryl (C 1 -C 3) alkyl group such as benzyl, vi) cyano, vii) nitro, viii) (C 1 -C 3) alkylthio, ix) amino NR ¹⁰ R ¹¹ with R ¹⁰ and R ¹¹ , identical or different, representing a) a hydrogen atom, b) a group (C2-C) ₄ ) alkyl, or c) a substituted (C ₁ -C ₅ ) alkyl group, preferably (C ₂ -C ₄ ) alkyl optionally substituted with one or more groups selected from:

- cyano,

- (C1-C3) alkoxy,

- hydroxy, and

- (C 1 -C 3) alkylcarbonyl;

M represents an integer inclusive of between 1 and 18; particularly an integer inclusive inclusive between 2 and 16; preferably an integer between

3 and 10; more preferably an integer between 4 and 6;

M 'represents an anionic counterion as defined in claim 13 or 14; it being understood that when the dye comprises an alkoxide group or else M 'and Q ⁺ may be absent to ensure the electroneutrality of said dye.

Method according to the preceding claim, characterized in that the fluorescent dyes b) are chosen from:

Fluorescent dyes formula (X) with:

HH benzo HHN (CH ₂ CH ₂ OH) ₂ HH 1 as well as their acid or base salts, organic or inorganic, their optical isomers, geometric, tautomers and their solvates such as hydrates;

fluorescent dyes of formula (XI) with:

as well as their organic or inorganic acid or base salts, their geometrical isomers, tautomers and their solvates such as hydrates;

Fluorescent dyes of formulas (Χ ') and (XI'):

(Χ ') (ΧΙ') with M 'as defined in the preceding claim and:

Fluorescent dyes of formula (XII) with:

as well as their organic or inorganic acid or base salts, their optical, geometrical isomers, tautomers and their solvates such as hydrates,

Fluorescent dyes of formula (XIII) with:

as well as their organic or inorganic acid or base salts, their geometrical isomers, tautomers and their solvates such as hydrates; and

The fluorescent dyes of formulas (ΧΙΙ ') and (ΧΙΙΙ') as follows:

(Xi ") (XIII) with

and preferably, the fluorescent dye (s) b) are chosen from the following fluorescent dyes (g) and (h):

(H)

with M 'and Q ⁺ as defined in the preceding claim.

The method according to any of the preceding claims, which further comprises applying to said keratinous fibers one or more reducing agents c), said reducing agent (s) c) being applicable before, at the same time or after the application of the direct dye (s) as defined in any one of claims 1 to 5, and / or the fluorescent dye (s) such (s) as defined in any one of claims 1, 6 to 11; preferably, said reducing agent (s) c) is present with the fluorescent dye (s) as defined in any one of claims 1, 6 to 1 ; preferably, the at least one reducing agent (s) is chosen from among i) the reducing agents of the following formula (Ic), as well as their addition salts and their mixtures:

formula (the), in which,

X represents P, S or SO2,

q represents an integer number gi at 0 or 1 or 2, preferably 1 or 2 with X = S

- s represents an integer equal to 0 or 1

- 1 represents an integer equal to 1 or 2, and

R 10 represents a linear or branched, saturated or unsaturated C 1 -C 20 alkyl radical, optionally interrupted by one or more heteroatoms, and / or optionally substituted with one or more radicals chosen from hydroxyl, halogenated, aminated and carboxyl radicals; (C1-C3o) alkoxy) -carbonyl, amido, ((C1- C3o) alkyl) -amino carbonyl, (C1-C3o) acyl) -amino, mono or dialkylamino, and mono or dihydroxylamino; ii) thioglycolic acid, Ni) thiolactic acid, iv) glycerol monothioglycolate, v) cysteamine, vi) N-acetyl-cysteamine, vii) N-propionyl-cysteamine, viii) cysteine, ix ) N-acetyl-cysteine, x) thiomalic acid, xi) panthe- tine, xii) 2,3-dimercaptosuccinic acid, xiii) N-

(mercaptoalkyl) -co-hydroxyalkylamides, xiv) N-mono- or N, N-dialkylmercapto-4-butyramides, xv) amino-mercaptoalkylamides, xvi) derivatives of N- (mercaptoalkyl) -succinamic acids, xvii) derivatives N- (mercaptoalkyl) succinimides, xviii) alkylamino mercaptoalkylamides, ix) the azeotropic mixture of 2-hydroxypropyl thioglyconate and (2-hydroxy-1-methyl) ethyl thioglycolate, x) the mercaptoalkylaminoamides, xi) N -mercapto-alkylalcanediamides, xii) formamidine sulfinic acid derivatives, their addition salts and mixtures thereof; preferably the reducing agent (s) c) is (are) in the presence of the fluorescent dye (s) as defined in any one of claims 1, 6 to 1 or then the reducing agent (s) c) are applied at the same time as the fluorescent dye (s) as defined in any one of Claims 1, 6 to 11.

13. A method according to any one of claims 1 to 1 1, which does not implement reducing agent.

14. Process according to any one of claims 1 to 13, which comprises at least the two successive stages:

Is :

a first step of applying to said keratin fibers a cosmetic composition comprising one or more fluorescent dyes b), as defined in any one of Claims 1, 6 to 11, followed by

a second step of applying to said fibers a cosmetic composition comprising one or more direct dyes a) as defined in any one of Claims 1 to 5, or

Is :

a first step of applying to said keratinous fibers a cosmetic composition comprising one or more direct dyes a), as defined in any one of claims 1 to 5, followed by

a second step of applying to said fibers a cosmetic composition comprising one or more fluorescent dyes b), as defined in any one of Claims 1, 6 to 11.

15. Process according to any one of claims 12 to 14, whose pH of or cosmetic compositions, especially the composition which comprises the reducing agent (s) c), is included between 6 and 1 1, preferably between 7 and 10, more preferably between 7.5 and 9.5, and even better between 9 and 9.5.

16. Cosmetic composition comprising one or more direct dyes a), as defined in any one of claims 1 to 5, and one or more fluorescent dyes b) as defined in any one of claims 8 to 11, said composition comprising optionally furthermore one or more reducing agents c) as defined in claim 12, and optionally having a pH of between 6 and 11, preferably between 7 and 10, more preferably between 7.5 and 9.5, and better still between 9 and 9.5.

17. Compound of formula (l "a) below:

as well as their organic or inorganic acid salts, their solvates such as hydrates, formula (I "a) in which:

R ¹ represents a linear or branched, preferably linear, C6 alkyl group;

R ⁹ , R ¹¹ and R ¹³ representing a hydrogen atom or a group (di) (C 1

C4) (alkyl) amino, (di) hydroxy (C1-C4) alkylamino, it being understood that not all the radicals R ⁹ , R ¹¹ and R ¹³ may represent a hydrogen atom, in particular (l "a) re

With Antony as defined previously.

18. Compound of formula (I "'a) below:

formula (I "a) in which:

linear or branched, C 1 to C 10, preferably C 1 to C 6, linear or branched, preferably linear, alkyl substituted by one or more hydroxyl groups, (di) (C 1 -C 4) (alkyl) amino, such as amino or dimethylamino:

Wherein R ⁹ , R ¹¹ and R ¹³ represent a hydrogen atom or a (di) (C 1 -C 4) (alkyl) amino, (di) hydroxy (C 1 -C 4) alkylamino group, it being understood that all radicals

R ⁹ , R ¹¹ and R ¹³ can not represent a hydrogen atom, in particular (1 "a) represents:

Dye (a2) JL JL An

An = against anionic ion uae such as Cl ^" or Br

Dye (a3)

An = against anionic ion such as Cl ^" , or Br, whose amino group can be salified, eg with HBr, or non-salified Coloring (a4)

19. Multi-compartment device comprising a first compartment containing one or more dyes a) as defined according to any one of claims 1 to 9, 17 and 18, and a second compartment containing one or more fluorescent dyes b), such as defined according to any one of claims 1, 10 to 16; optionally a third compartment containing one or more reducing agents c) as defined in claim 16, and optionally another compartment containing one or more oxidizing agents d).

20. Use of one or more dye (s) fluorescent (s) b) as defined (s) according to any one of claims 1, 10 to 16 associated with (s) one or more dye (s) a), as defined according to any one of claims 1 to 9, 17 and 18, for the coloration of light keratinous fibers, especially human keratinous fibers, such as the hair, in chestnut, dark brown, brown, brown with reflection, even black, without using an additional dye different from dyes a) or b).