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Title:
PROCESS FOR DYEING KERATIN FIBRES USING A COMPOSITION COMPRISING AT LEAST TWO ORGANOSILANES DIFFERENT FROM ONE ANOTHER
Document Type and Number:
WIPO Patent Application WO/2018/115059
Kind Code:
A1
Abstract:
The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of applying a composition comprising at least two organosilanes, that are different from one another, and at least one step of applying a composition comprising anionic direct dyes and surfactants. The present invention also relates to the use, as pretreatment, of at least two organosilanes, that are different from one another, for improving the dyeing properties of a composition comprising anionic direct dyes.

Inventors:
CORREIA, Audrey (11-13 rue Dora Maar, Saint Ouen, 93400, FR)
BOUREL, Sophie (11-13 rue Dora Maar, Saint Ouen, 93400, FR)
COGNET, Marie (11-13 rue Dora Maar, Saint Ouen, 93400, FR)
Application Number:
EP2017/083709
Publication Date:
June 28, 2018
Filing Date:
December 20, 2017
Export Citation:
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Assignee:
L'OREAL (14 rue Royale, Paris, Paris, 75008, FR)
International Classes:
A61K8/58; A61K8/46; A61Q5/06
Attorney, Agent or Firm:
CASALONGA (8 avenue Percier, Paris, 75008, FR)
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Claims:
CLAIMS

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the following steps:

- at least one step of applying to said keratin fibres a composition (A) comprising at least two organosilanes, that are different from one another, and

- at least one step of applying to said keratin fibres a composition (B) comprising one or more anionic direct dyes and one or more surfactants;

the composition (B) being applied after the composition (A). 2. Process according to Claim 1, characterized in that the organosilanes are chosen from the compounds of formula (I), oligomers thereof, hydrolysis products thereof and mixtures thereof:

RiSi(OR2)z(R3)x(OH)y (I)

in which

Ri is a cyclic or acyclic, linear or branched, saturated or unsaturated Ci to C22, in particular Ci to C2o, hydrocarbon-based chain, which may be substituted with a group chosen from amine groups NH2 or NHR, R being a linear or branched Ci to C2o, in particular Ci to C6, alkyl, a C3 to C4o cycloalkyl or a C6 to C3o aromatic ring; the hydroxyl group; a thiol group; an aryl group, which is possibly substituted with an NH2 or NHR group; it being possible for Ri to be interrupted with a heteroatom, such as O, S or NH, or a carbonyl group,

- R2 and R3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,

- y denotes an integer ranging from 0 to 3,

- z denotes an integer ranging from 0 to 3, and

- x denotes an integer ranging from 0 to 2,

- with z + x + y = 3. 3. Process according to Claim 1 or 2, characterized in that at least one of the organosilanes is chosen from the compounds of formula (la) corresponding to the compounds of formula (I) in which Ri represents a linear alkyl group comprising from 1 to 18 carbon atoms and more particularly from 1 to 12 carbon atoms or a Ci to C6, preferably C2 to C4, aminoalkyl group, and most preferentially Ri represents a methyl group.

4. Process according to any one of the preceding claims, characterized in that at least one of the organosilanes is chosen from compounds of formula (lb) corresponding to the compounds of formula (I) in which Ri is a linear or branched, saturated or unsaturated Ci to C22 hydrocarbon-based chain, substituted with an amine group NH2 or NHR, with R being a Ci to C2o, in particular Ci to C6, alkyl, a C3 to C4o cycloalkyl or a C6 to C30 aromatic ring; preferably Ri represents a Ci to C6, and more preferentially C2 to C4, aminoalkyl group.

5. Process according to any one of the preceding claims, characterized in that the organosilanes are chosen from methyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltriethoxysilane, 3- aminopropyltriethoxysilane, 2-aminoethyltriethoxysilane, 3- aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3 -(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane, and oligomers thereof. 6. Process according to any one of the preceding claims, characterized in that the organosilanes correspond to a mixture of methyltriethoxysilane and 3- aminopropy ltriethoxy silane .

7. Process according to any one of the preceding claims, characterized in that the total content of the organosilanes ranges from 1% to 30% by weight, preferably from 5% to 25% by weight and more preferentially from 8% to 20% by weight, relative to the total weight of the composition (A).

8. Process according to any one of the preceding claims, characterized in that the anionic direct dye(s) are chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoids, natural acid dyes, and mixtures thereof.

9. Process according to any one of the preceding claims, characterized in that the anionic direct dye(s) are chosen from:

a) the diaryl anionic azo dyes of formula (II) or (ΙΓ):

in which formulae (II) and (IF)

R7, R8, R9, Rio, R'7, R'8, R'9 and R' io, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0)2S(0~), M+ with M+ representing a cationic counterion such as an alkali metal (Na, K) or an alkaline-earth metal (Ca);

- (0)CO~, M+ with M+ as previously defined;

- R"-S(0)2", with R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;

- R" '-S(0)2-X'- with R" ' representing an alkyl or optionally substituted aryl group, X' as defined previously; - (di)(alkyl)amino;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0~), M+ and iv) alkoxy with M+ as defined previously;

- optionally substituted heteroaryl; preferentially a benzothiazolyl group;

- cycloalkyl; especially cyclohexyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0)2S(0~), M+ or phenylamino groups;

- or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A'; and R'7 with R's or R's with R'9 or R'9 with R' 10 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0~), M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'- C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X" and Ar as defined previously;

• W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb together form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

it being understood that formulae (II) and (ΙΓ) comprise at least one sulfonate (0)2S(0 ), M+ or carboxylate (O)C(O ), M+ radical on one of the rings A, A', B, B' or C with M+ as defined previously; b) the pyrazolone anionic azo dyes of formulae (III) and (III'):

in which formulae (III) and (ΠΓ),

• Rii, Ri2 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or (0)2S(0~), M+ with M+ as defined previously;

· Ri4 represents a hydrogen atom, an alkyl group or a group C(0)0", M+ with M+ as defined previously;

Ri5 represents a hydrogen atom;

Ri6 represents an oxo group, in which case R'i6 is absent, or alternatively R15 with Ri6 together form a double bond;

· Ri7 and Ris, which may be identical or different, represent a hydrogen atom or a group chosen from:

- (0)2S(0~), M+ with M+ as defined previously;

- Ar-0-S(0)2" with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups;

· Ri and R20 together form either a double bond, or a benzo group D', which is optionally substituted;

• R' i6, R' i9 and R'20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy 1 group;

R21 represents a hydrogen atom or an alkyl or alkoxy group;

· Ra and Rb, which may be identical or different, are as defined previously, preferentially Ra represents a hydrogen atom and Rb represents an aryl group;

• Y represents either a hydroxyl group or an oxo group;

represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

it being understood that formulae (III) and (ΙΙΓ) comprise at least one sulfonate group (0)2S(0~), M+ on one of the rings D or E or formulae (III) and (III') comprise at least one carboxylate group (O)C(O ), M+ with M+ as defined previously; c) the anthraquinone dyes of formulae (IV) and (IV):

in which formulae (IV) and (IV):

• R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from:

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0~), M+ with M+ as defined previously;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0~), M+ with M+ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- (0)2S(0"), M+ with M+ as defined previously;

• Z' represents a hydrogen atom or a group NR28R2 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl;

- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0)2S(0~), M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group;

- cycloalkyl; especially cyclohexyl; • Z represents a group chosen from hydroxyl and NR'28R'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously;

it being understood that formulae (IV) and (IV) comprise at least one sulfonate group (0)2S(0"), M+ with M+ as defined previously; d) the dyes corresponding to the general formulae (V) and (V):

in which formulae (V) and (V),

R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;

- hydroxyl, mercapto;

- nitro, nitroso;

- (poly)haloalkyl;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously;

- (0)2S(0"), M+ with M+ as defined previously;

- (0)CO~, M+ with M+ as previously defined;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino;

• Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;

• W is as defined previously; W particularly represents a group -NH-;

• ALK represents a linear or branched divalent Ci-C6 alkylene group; in particular, ALK represents a group -CH2-CH2-;

· n is 1 or 2;

• p represents an integer inclusively between 1 and 5;

• q represents an integer inclusively between 1 and 4;

• u is 0 or 1 ;

• when n is 1 , J represents a nitro or nitroso group; particularly nitro;

· when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferentially, J represents a radical -SO2-;

• M' is as defined previously for M+; which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously;

it being understood that formulae (V) and (V) comprise at least one sulfonate group (0)2S(0 ), M+ or carboxylate group (O)C(O ), M+ with M+ as defined previously; e) the triarylmethane dyes of formula (VI):

in which formula (VI),

R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and a benzyl group optionally substituted with a group (0)mS(0~), M+ with M+ and m as defined previously;

• R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0)2S(0 ), M+ with M+ representing a hydrogen atom or a cationic counterion;

- (0)CO~, M+ with M+ as previously defined;

- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: Γ; with Γ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0~), M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix)

R°-X'-C(X)-X"-; with M+, R°, X, X' and X" as defined previously;

it being understood that at least one of the rings G, H, I or Γ comprises at least one sulfonate (0)2S(0~), M+ or carboxylate (O)C(O ), M+ group with M+ as defined previously; f) the xanthene-based dyes of formula (VII):

in which formula (VII),

R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;

• R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy 1, mercapto;

- nitro, nitroso;

- (0)2S(0 ), M+ with M+ representing a hydrogen atom or a cationic counterion;

- (0)CO~, M+ with M+ as previously defined;

• G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly, G represents an oxygen atom;

• L represents an alkoxide O", M+; a thioalkoxide S", M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M+ as defined previously; M+ is particularly sodium;

• L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom, an alkyl group or an optionally substituted aryl group; L' represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)mS(O"), M+ groups with m and M+ as defined previously;

• Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q' represent an oxygen atom;

M+ is as defined previously; it being understood that formula (VII) comprises at least one sulfonate group (0)2S(0~), M+ or carboxylate group (O)C(O ), M+ with M+ as defined previously; g) the indole-based dyes of formula (VIII):

in which formula (VIII),

R53, R54, R55, R56, R57, R58, R59 and R50, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X" , which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0)2S(0~), M+ with M+ as defined previously;

- (0)CO~, M+ with M+ as previously defined;

· G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly, G represents an oxygen atom;

• Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;

it being understood that formula (VIII) comprises at least one sulfonate group (0)2S(0~), M+ or carboxylate group (O)C(O"), M+ with M+ as defined previously; h) the quino line-based dyes of formula (IX):

in which formula (IX),

• Rei represents a hydrogen or halogen atom or an alkyl group;

Ri2, R53 and R54, which may be identical or different, represent a hydrogen atom or a group (0)2S(0~), M+ with M+ as defined previously;

• or alternatively 51 with Q, or R51 with R54, together form a benzo group optionally substituted with one or more groups (0)2S(0~), M+ with M+ representing a hydrogen atom or a cationic counterion;

it being understood that formula (IX) comprises at least one sulfonate group (0)2S(0 ), M+ with M+ as defined previously;

i) the mesomers and tautomers of formulae (II) to (IX); and

j) mixtures thereof.

10. Process according to Claim 9, characterized in that the direct anionic dye is chosen from the compounds of formula (IVa) below:

in which formula (IVa),

• Z' represents a group NR2sR29 with R28 representing a hydrogen atom or an alkyl group and R29 representing an aryl group optionally substituted particularly with one or more groups chosen from i) alkyl such as methyl and ii) (0)2S(0~), M+ with M+ as defined in Claim 9;

• Z represents a group chosen from hydroxyl and NR'2sR'29 with R'2s and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formula (IVa) comprises at least one sulfonate group (0)2S(0 ), M+;

and preferably, the anionic direct dye is Acid Violet 43.

11. Process according to any one of the preceding claims, characterized in that the total content of the anionic direct dye(s) ranges from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight, more preferentially from 0.01% to 5% by weight and even better still from 0.1% to 2% by weight, relative to the total weight of the composition (B).

12. Process according to any one of the preceding claims, characterized in that the surfactant(s) are chosen from anionic surfactants.

13. Process according to any one of Claims 1 to 11, characterized in that the surfactant(s) are chosen from cationic surfactants.

14. Process according to any one of the preceding claims, characterized in that the composition (A) also comprises one or more acids chosen from organic acids, mineral acids and mixtures thereof, preferably from organic acids, more preferentially from carboxylic acids, and even better still the acid is lactic acid.

15. Process according to any one of the preceding claims, characterized in that the composition (A) also comprises one or more silicones other than the organosilanes as defined in any one of Claims 1 to 6.

16. Process according to any one of the preceding claims, characterized in that it also comprises a step of heat-treating the keratin fibres, between the first step of applying the composition (A) and the second step of applying the composition (B). 17. Use, as pretreatment, of at least two organosilanes, that are different from one another, as defined in any one of Claims 1 to 6, for improving the dyeing properties of a composition comprising one or more anionic direct dyes, as defined in any one of Claims 1 and 8 to 10.

Description:
Process for dyeing keratin fibres using a composition comprising at least two organosilanes different from one another

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of applying a composition comprising at least two organosilanes, that are different from one another, and at least one step of applying a composition comprising anionic direct dyes and surfactants.

The present invention also relates to the use, as pretreatment, of at least two organosilanes, that are different from one another, for improving the dyeing properties of a composition comprising anionic direct dyes.

Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hair.

It is especially known practice to dye keratin fibres, in particular human keratin fibres, with dyeing compositions containing oxidation dye precursors, which are generally known as oxidation bases. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.

The shades obtained with these oxidation bases may be modified by combining them with couplers or colour modifiers. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

Another well-known method consists in obtaining "semi-permanent" dyeing by applying to the keratin fibres direct dyes, which are coloured and colouring molecules that have affinity for said fibres.

The direct dyes conventionally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes. The chemical species may be non-ionic, anionic (acidic dyes) or cationic (basic dyes). The direct dyes may also be natural dyes.

Conventional direct dyeing processes consist in applying to keratin fibres dyeing compositions comprising direct dyes. After application, a leave-on time is observed so as to allow the dyeing molecules to penetrate by diffusion into the fibres. On conclusion of the process, the fibres are rinsed. In contrast with oxidation dyeing, these direct dyeing processes have a tendency to better protect the integrity of the fibres. The resulting colourings are generally chromatic, but, however, are only semi-temporary. The nature of the interactions that bind the direct dyes to the keratin fibres and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power.

Moreover, these colourings are not sufficiently fast in the face of external agents such as light, shampooing or perspiration.

These colourings may also be too selective, i.e. the difference in colouring is too great along the same keratin fibre that is differently sensitized between its end and its root. It is therefore necessary to apply bath ratios in great excess or to add large amounts of solvents to the compositions in order to improve the colour uptake of direct dyes.

Conventional direct dyeing processes, and more particularly processes using acid direct dyes, have the drawback of staining the user's or the hairstylist's hands during application of the dyeing compositions to the hair.

These dyeing processes may also give rise to undesirable stains on the user's scalp, contour of the face and/or clothing, which may be due to application errors and/or to problems of running of the compositions used.

Thus, there is a real need to implement processes for the direct dyeing of keratin fibres, in particular of human keratin fibres such as the hair, which do not have the drawbacks mentioned above, i.e. which make it possible especially to lead to colourings that have better properties, especially in terms of chromaticity, power, intensity and selectivity, and which are persistent with respect to shampooing.

The dyeing processes must also reduce the risks of staining the user's hands, scalp, face and/or clothing.

The applicant has discovered, surprisingly, that a process for dyeing keratin fibres, comprising a step of applying a composition comprising at least two different organosilanes, followed by a step of applying a composition comprising anionic direct dyes, makes it possible to achieve the objectives set out above, in particular to produce powerful, shampooing-resistant colourings, while at the same time limiting the risk of staining.

A subject of the present invention is especially a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the following steps: - at least one step of applying to said keratin fibres a composition (A) comprising at least two organosilanes, that are different from one another, and

- at least one step of applying to said keratin fibres a composition (B) comprising one or more anionic direct dyes and one or more surfactants;

the composition (B) being applied after the composition (A).

The presence of at least two organosilanes, that are different from one another, makes it possible in particular to improve the dyeing properties of anionic direct dyes. More particularly, the presence of at least two organosilanes, that are different from one another, in the process according to the invention, makes it possible to improve the colour uptake while at the same time limiting the amount of solvents used.

Thus, the process according to the invention leads to chromatic, powerful, intense and sparingly selective colourings, that is to say colourings that are uniform along the length of the fibre while at the same time preserving the integrity of the keratin fibres.

In other words, the use of at least two organosilanes, that are different from one another, makes it possible to boost the dyeing properties of anionic direct dyes, by producing an improvement in the colouring, in particular in terms of chromaticity, power, intensity and selectivity, compared with the use of anionic direct dyes alone.

Moreover, the colourings obtained by means of the process according to the invention show good resistance to the various attacking factors to which the hair may be subjected, such as light, bad weather, washing and perspiration. They are in particular persistent with respect to shampooing, especially after at least three shampoo washes.

The process according to the invention also makes it possible to obtain satisfactory colouring, while at the same time limiting the amount of solvents in the composition, that is to say using a lower amount of solvents.

A subject of the present invention is also the use, as pretreatment, of at least two organosilanes, that are different from one another, as previously defined, for improving the dyeing properties of a composition comprising one or more anionic direct dyes, as previously defined.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow. In the text hereinbelow, and unless otherwise indicated, the limits of a range of values are included within that range, especially in the expressions "between" and "ranging from ... to

Moreover, the expressions "at least one", "at least two" and "at least" used in the present description are equivalent to the expressions "one or more", "two or more" and "greater than or equal to", respectively.

Figure 1 shows that the colour uptake is improved when the hair is treated with the process according to the present invention, using a composition comprising at least two organosilanes that are different from one another.

Composition (A)

Organosilanes

The composition (A) used in the process for dyeing keratin fibres according to the present invention comprises at least two organosilanes, that are different from one another.

For the purposes of the present invention, the term "different from one another" is intended to mean two organosilanes of which the chemical structures are different.

The organosilanes are preferably chosen from the compounds of formula (I) below, oligomers thereof, hydrolysis products thereof and mixtures thereof:

RiSi(OR 2 )z(R3)x(OH) y (I)

in which,

- Ri is a cyclic or acyclic, linear or branched, saturated or unsaturated Ci to C 22 , in particular Ci to C 2 o, hydrocarbon-based chain, which may be substituted with a group chosen from amine groups NH 2 or NHR, R being a linear or branched Ci to C 2 o, in particular Ci to C 6 , alkyl, a C 3 to C 4 o cycloalkyl or a C 6 to C 3 o aromatic ring; the hydroxyl group (OH); a thiol group; an aryl group (more particularly benzyl), which is possibly substituted with an NH 2 or NHR group; it being possible for Ri to be interrupted with a heteroatom (O, S or NH) or a carbonyl group (CO),

- R 2 and R 3 , which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms,

- y denotes an integer ranging from 0 to 3,

- z denotes an integer ranging from 0 to 3, and - x denotes an integer ranging from 0 to 2,

- with z + x + y = 3.

The term "oligomer" is intended to mean the polymerization products of the compounds of formula (I) comprising from 2 to 10 silicon atoms.

Preferably, Ri is a linear or branched, preferably linear, saturated Ci to C22 and especially Ci to C 12 hydrocarbon-based chain, which may be substituted with an amine group NH 2 or NHR, R being a Ci to C20 and especially Ci to C 6 , alkyl.

Preferably, R 2 represents an alkyl group comprising from 1 to 4 carbon atoms, better still a linear alkyl group comprising from 1 to 4 carbon atoms, and preferably an ethyl group.

Preferably, z ranges from 1 to 3.

Preferably, y = 0.

Preferentially, z=3, and therefore x=y=0.

Preferably, at least one of the organosilanes is chosen from the compounds of formula (la), corresponding to the compounds of formula (I) in which Ri represents a linear alkyl group comprising from 1 to 18 carbon atoms and more particularly from 1 to 12 carbon atoms, or a Ci to C 6 , preferably C 2 to C 4 , aminoalkyl group. More particularly, Ri represents a methyl group.

More preferentially, at least one of the organosilanes is a compound of formula (la) in which:

Ri represents a methyl group,

R 2 represents and ethyl group, and

z = 3, and therefore x=y=0.

Preferably, at least one of the organosilanes is chosen from the compounds of formula (lb), corresponding to the compounds of formula (I) in which Ri is a linear or branched, saturated or unsaturated Ci to C22 hydrocarbon-based chain, substituted with an amine group NH 2 or NHR, R being a Ci to C20 , in particular Ci to C 6 , alkyl, a C3 to C40 cycloalkyl or C 6 to C30 aromatic ring. In this variant, Ri preferably represents a Ci to C 6 , and more preferentially C 2 to C 4 , aminoalkyl group.

More preferentially, at least one of the organosilanes is a compound of formula (lb) in which:

Ri represents an aminopropyl group,

R 2 represents and ethyl group, and

z = 3, and therefore x=y=0. Preferably, the composition according to the invention comprises at least one organosilane of formula (la) chosen from methyltriethoxysilane (MTES), octyltriethoxysilane (OTES), dodecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltriethoxysilane, oligomers thereof and mixtures thereof; and at least one organosilane of formula (lb) chosen from 3-aminopropyltriethoxysilane (APTES), 2- aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2- aminoethyl)-3-aminopropyltriethoxysilane, 3-(m- aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane, oligomers thereof, and mixtures thereof.

More preferentially, the organosilanes correspond to a mixture of methyltriethoxysilane and 3-aminopropyltriethoxysilane. In other words, the organosilane of formula (la) is methyltriethoxysilane and the organosilane of formula (lb) is 3-aminopropyltriethoxysilane.

The organosilanes used in the composition (A) of the invention, especially those comprising a basic function, may be partially or totally neutralized in order to improve the water solubility thereof. In particular, the neutralizing agent can be chosen from organic acids, mineral acids or mixtures thereof, as defined below.

Preferably, the optionally neutralized organosilanes are water-soluble and especially soluble at a concentration of 2%, better still at a concentration of 5% and even better still at a concentration of 10% by weight in water at a temperature of 25°C and at atmospheric pressure (1 atm). The term "soluble" is intended to mean the formation of a single macroscopic phase.

The total amount of organosilanes present in the composition (A) according to the present invention preferably ranges from 1% to 30% by weight, more preferentially from 5% to 25% by weight, and even better still from 8% to 20% by weight, relative to the total weight of the composition (A).

The total amount of organosilane(s) of formula (la) present in the composition (A) according to the present invention preferably can range from 0.1% to 10%) by weight, more preferentially from 0.5%> to 10%> by weight, and even better still from 1% to 8% by weight, relative to the total weight of the composition (A). The total amount of organosilane(s) of formula (lb) present in the composition (A) according to the present invention preferably can range from 0.5% to 25% by weight, more preferentially from 4% to 20% by weight, and even better still from 8% to 15% by weight, relative to the total weight of the composition (A).

The weight ratio (R) between the total amount of organosilanes of formula (la) and the total amount of organosilanes of formula (lb), present in the composition (A), is preferably less than or equal to 1, more preferentially less than or equal to 0.7, better still less than or equal to 0.5 and even better still less than or equal to 0.3.

This ratio (R) can preferably be between 0.02 and 0.7, more preferentially between 0.05 and 0.5 and even better still between 0.1 and 0.3.

Acids

The composition (A) used in the process for dyeing keratin fibres according to the present invention can optionally also comprise one or more acids chosen from organic acids, mineral acids and mixtures thereof, and preferably from organic acids.

For the purposes of the present invention, the term "organic acid" is intended to mean an organic acid and/or the associated bases thereof with a pKa of less than or equal to 7, preferably less than or equal to 6, especially ranging from 1 to 6 and preferably from 2 to 5.

According to a preferred embodiment, the organic acid(s) are chosen from carboxylic acids, sulfonic acids and mixtures thereof.

Preferably, the organic acid(s) are chosen from saturated or unsaturated carboxylic acids.

Preferably, the acid(s) are chosen from organic acids, and more preferentially from carboxylic acids.

Preferably, the organic acid(s) are chosen from lactic acid, propanoic acid, butanoic acid, acetic acid, citric acid, maleic acid, gly colic acid, salicylic acid, malic acid, tartaric acid and mixtures thereof, and more preferably lactic acid.

The total content of organic acid(s), when they are present in the composition (A) according to the present invention, can preferably range from 0.1% to 10% by weight, and more preferentially from 0.5% to 5% by weight relative to the total weight of the composition (A).

Preferably, the composition (A) comprises at least one organosilane of formula (la), as previously defined, at least one organosilane of formula (lb), as previously defined, and at least one organic acid, preferably chosen from carboxylic acids. More preferentially, the composition (A) comprises at least one organosilane of formula (la), as previously defined, at least one organosilane of formula (lb), as previously defined, and lactic acid.

Even better still, the composition (A) comprises a mixture of methyltriethoxysilane and 3-aminopropyltriethoxysilane, and at least one organic acid, preferably chosen from carboxylic acids, and more preferentially the organic acid is lactic acid.

Silicones

The composition (A) used in the process for dyeing keratin fibres according to the present invention may optionally also comprise one or more silicones other than the organosilanes previously defined.

The silicones that may be used in accordance with the invention may be in the form of oils, waxes, resins or gums.

Preferably, the silicone(s) are chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMSs), and modified organopolysiloxanes (or organomodified polysiloxanes) comprising at least one functional group chosen from amino groups, aryl groups, hydroxyl groups and alkoxy groups. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those with a boiling point of between 60°C and 260°C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold especially under the name Volatile Silicone ® 7207 by Union Carbide or Silbione ® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone ® 7158 by Union Carbide, and Silbione ® 70045 V5 by Rhodia, and mixtures thereof.

Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone ® FZ 3109 sold by Union Carbide, having the formula: D" - D' D" - D" -

CH 3 with D" — Si - O - with D' : - Si - 0

I CH, C„H '«17

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-l,l '-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10 "6 m 2 /s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, "Volatile Silicone Fluids for Cosmetics".

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

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

Among these polydialkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:

- the Silbione ® oils of the 47 and 70 047 series or the Mirasil ® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

- the oils of the Mirasil ® series sold by the company Rhodia;

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

- the Viscasil ® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric. Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax ® 9800 and 9801 by the company Goldschmidt, which are poly(Ci-C2o)dialkylsiloxanes.

The silicone gums that may be used in accordance with the invention are especially polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.

Products that may be used more particularly in accordance with the invention are mixtures such as:

- mixtures formed from a polydimethylsiloxane with a hydroxy-terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2 1401 sold by the company Dow Corning;

- mixtures of a polydimethylsiloxane gum and a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric; this product is an SF 30 gum corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;

- mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of a gum SE 30 defined above with a viscosity of 20 m 2 /s and of an oil SF 96 with a viscosity of 5x 10 "6 m 2 /s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

The organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:

R2S1O2/2, R3S1O1/2, RS1O3/2 and S1O4/2, in which R represents an alkyl containing 1 to 16 carbon atoms. Among these products, the ones that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl.

Among these resins, mention may be made of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by General Electric, which are silicones of dimethyl/trimethylsiloxane structure.

Mention may also be made of the trimethyl siloxysilicate-type resins sold especially under the names X22-4914, X21-5034 and X21-5037 by Shin-Etsu.

The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organo functional groups attached via a hydrocarbon-based group.

The organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.

The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 x 10 "5 to 5 X 10 "2 m 2 /s at 25°C.

Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:

- the Silbione ® oils of the 70 641 series from Rhodia;

- the oils of the Rhodorsil ® 70 633 and 763 series from Rhodia;

- the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

- the silicones of the PK series from Bayer, such as the product PK20;

- the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH1000;

- certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

Among the organomodified silicones, mention may also be made of polyorganosiloxanes comprising:

- substituted or unsubstituted amino groups, such as the products sold under the names GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; - alkoxylated groups, such as the product sold under the name Silicone Copolymer F- 755 by SWS Silicones and Abil Wax ® 2428, 2434 and 2440 by the company Goldschmidt;

- hydroxyl groups, such as the product sold under the name Belsil DM 3560 VP by the company Wacker.

Preferably, the silicone(s) are chosen from amino silicones.

The term "amino silicone" denotes any silicone comprising at least one primary, secondary or tertiary amine or a quaternary ammonium group.

The weight-average molecular weights of these amino silicones may be measured by gel permeation chromatography (GPC) at ambient temperature (25°C), as polystyrene equivalent. The columns used are μ styragel columns. The eluent is THF and the flow rate is 1 ml/min. 200 μΐ of a 0.5% by weight solution of silicone in THF are injected. Detection is performed by refractometry and UV-metry.

Preferably, the amino silicones that can be used in the context of the invention are chosen from:

a) the polysiloxanes corresponding to formula (A):

in which x' and y' are integers such that the weight-average molecular weight (Mw) is between 5000 and 500 000 approximately.

b) the amino silicones corresponding to formula (B):

R , aG3-a-Si(OSiG 2 )n-(OSiGbR , 2-b) m -0-SiG3-a-R*a (B) in which:

- G, which may be identical or different, denotes a hydrogen atom or a phenyl, OH or C1 -C8 alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy, group,

- a, which may be identical or different, denotes 0 or an integer from 1 to 3, in particular 0,

- b denotes 0 or 1 , in particular 1 ,

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10;

- R', which may be identical or different, denotes a monovalent radical of formula -C q H 2q L in which q is a number ranging from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups:

-N(R") 2 ; -N + (R")3 A-; -NR"-Q-N(R") 2 and -NR"-Q-N + (R")3 A-,

in which R", which may be identical or different, denotes hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbon-based radical, for example a Ci- C 2 o alkyl radical; Q denotes a linear or branched group of formula C r H 2r , r being an integer ranging from 2 to 6, preferably from 2 to 4; and A- represents a cosmetically acceptable anion, in particular a halide such as fluoride, chloride, bromide or iodide.

Preferably, the amino silicones are chosen from the amino silicones of formula (B). More preferentially, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formulae (C), (D), (E), (F) and/or (G) below.

According to a first embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones known as "trimethylsilyl amodimethicone" corresponding to formula (C):

(CH 3 ) 3 S OSi(CH 3 3)/3

(C) m

in which m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10.

According to a second embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (D) below:

O— R Q (D)

(

(

in which:

- m and n are numbers such that the sum (n + m) ranges from 1 to 1000 and in particular from 50 to 250 and more particularly from 100 to 200; it being possible for n to denote a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175, and for m to denote a number from 1 to 1000 and in particular from 1 to 10, and more particularly from 1 to 5; and

- Ri, R 2 and R 3 , which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ri to R 3 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio ranges preferably from 0.2: 1 to 0.4: 1 and preferably from 0.25 : 1 to 0.35 : 1 and more particularly equals 0.3: 1.

The weight-average molecular weight (Mw) of these silicones preferably ranges from 2000 to 1 000 000 and more particularly from 3500 to 200 000.

According to a third embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (E) below: CH 3 †H 3 CH, CH,

R; Si— - O— Si - O— Si O— Si— R,

(CH 2 ) (E)

CH 3 CH 3 CH,

(CH 2 ) 2 NH 0 in which:

- p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; it being possible for p to denote a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239, and for q to denote a number from 1 to 1000, in particular from 1 to 10 and more particularly from 1 to 5; and

- Ri and R 2 , which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ri to R 2 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy mole ratio generally ranges from 1 :0.8 to 1 : 1.1 and preferably from 1 :0.9 to 1 :1 and more particularly equals 1 :0.95.

The weight-average molecular weight (Mw) of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.

The commercial products comprising silicones of structure (D) or (E) may include in their composition one or more other amino silicones of which the structure is different from formula (D) or (E).

A product containing amino silicones of structure (D) is sold by the company Wacker under the name Belsil ® ADM 652.

A product containing amino silicones of structure (E) is sold by Wacker under the name Fluid WR 1300 ® .

When these amino silicones are used, one particularly advantageous embodiment consists in using them in the form of an oil- in- water emulsion. The oil- in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and/or non-ionic. The numerical mean size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm.

Preferably, in particular as amino silicones of formula (E), use is made of microemulsions of which the mean particle size ranges from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, use may be made according to the invention of the amino silicone microemulsions of formula (E) sold under the names Finish CT 96 E ® or SLM 28020 ® by the company Wacker.

According to a fourth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (F) below:

CH 3 †H 3 CH, CH 3

Si— o- — Si - O - Si— O— Si— OH

I

A

CH 3 CH 3 I CH Q

NH

(F)

(CH 2 ) 2 NhL m

in which:

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10; and

- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical preferably is linear.

The weight-average molecular weight (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.

A silicone corresponding to this formula is, for example, the Xiameter MEM 8299 Emulsion from Dow Corning.

According to a fifth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (G) below:

in which:

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10; and

- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight-average molecular weight (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 and even more particularly from 1000 to 200 000.

A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.

c) the amino silicones corresponding to formula (H):

in which:

- R 5 represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl or C2-C18 alkenyl, for example methyl, radical; - Re represents a divalent hydrocarbon-based radical, in particular a d-d 8 alkylene radical or a divalent d-d 8, for example d-d, alkyleneoxy radical linked to the Si via an SiC bond;

- Q " is an anion such as a halide, especially chloride, ion or an organic acid salt, especially acetate;

- r represents a mean statistical value ranging from 2 to 20 and in particular from 2 to 8; and

- s represents a mean statistical value ranging from 20 to 200 and in particular from 20 to 50.

Such amino silicones are in particular described in patent US 4 185 087. d) the silicones comprising a quaternary ammonium, of formula (J):

R 7 OH -,

I '

R 8 - N - CH 2 -€H-CH - R 6 Si - O Si R fi - CH o - CH0H CH. N

I

R 7

(J)

in which:

- R 7 , which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a d-ds alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example a methyl radical;

- Re represents a divalent hydrocarbon-based radical, in particular a d-d 8 alkylene radical or a divalent d-d 8, for example d-d, alkyleneoxy radical linked to the Si via an SiC bond;

- R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl radical, a C2-C18 alkenyl radical or a radical -R6-NHCOR 7 ;

- X " is an anion such as a halide, especially chloride, ion or an organic acid salt, especially acetate; and

- r represents a mean statistical value ranging from 2 to 200 and in particular from 5 to 100.

These silicones are described, for example, in patent application EP-A 0 530

974. amino silicones of formula (K)

R 3

1

(K)

H 2 N - (C m H 2m ) - NH - (C n H 2n ) - Si O Si O Si R.

FL R, in which,

- Ri, R 2 , R3 and R 4 , which may be identical or different, denote a Ci-C 4 alkyl radical or a phenyl group,

- R5 denotes a Ci-C 4 alkyl radical or a hydroxyl group,

- n is an integer ranging from 1 to 5,

- m is an integer ranging from 1 to 5, and

- x is chosen such that the amine number ranges from 0.01 to 1 meq/g.

f) the multiblock polyoxyalkylenated amino silicones, of the type (AB)n, A being a polysiloxane block and B being a polyoxyalkylenated block comprising at least one amine group.

Said silicones preferably are constituted of repeating units of the following general formulae:

[-(SiMe 2 0) x SiMe 2 - R -N(R")- R-0(C 2 H 4 0)a(C3H 6 0)b -R-N(H)-R-]

or alternatively

[-(SiMe 2 0) x SiMe 2 - R -N(R")- R - 0(C 2 H 4 0)a(C3H 6 0)b -] in which:

- a is an integer greater than or equal to 1 , preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;

- b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;

- x is an integer ranging from 1 to 10 000 and more particularly from 10 to 5000; - R" is a hydrogen atom or a methyl;

- R, which may be identical or different, represent a linear or branched divalent C 2 - C12 hydrocarbon-based radical, optionally comprising one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a radical CH2CH 2 CH 2 OCH(OH)CH2-; preferentially, R denotes a radical - CH2CH 2 CH 2 OCH(OH)CH2-; and

- R', which may be identical or different, represent a linear or branched divalent C 2 - C 12 hydrocarbon-based radical, optionally comprising one or more heteroatoms such as oxygen; preferably, R' denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a radical CH 2 CH 2 CH 2 OCH(OH)CH 2 -; preferentially, R' denotes -CH(CH 3 )-CH 2 -.

The siloxane blocks preferably represent 50 mol% to 95 mol% of the total weight of the silicone, more particularly from 70 mol% to 85 mol%.

The amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.

The weight-average molecular weight (Mw) of the silicone is preferably between 5000 and 1 000 000 and more particularly between 10 000 and 200 000.

Mention may be made especially of the silicones sold under the names Silsoft A-843 or Silsoft A+ by Momentive.

g) and mixtures thereof.

The total amount of silicone(s), when they are present in the composition (A) according to the present invention, preferably ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight, and even better still from 0.1% to 5% by weight, relative to the total weight of the composition (A).

The total amount of amino silicone(s), when they are present in the composition (A) according to the present invention, preferably ranges from 0.01% to 10%) by weight, more preferentially from 0.05%> to 5% by weight, and even better still from 0.1% to 1% by weight, relative to the total weight of the composition (A). Composition (B)

Anionic direct dyes

The composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more anionic direct dyes.

The term "direct dye" is intended to mean natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.

The anionic direct dyes of the invention are dyes commonly called "acid dyes" for their affinity with alkaline substances (see, for example, "Industrial Dyes, Chemistry, Properties, Applications", Klaus Hunger ed.,Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2003). Anionic or acid dyes are known in the literature (see, for example, Ullman 's Encyclopedia of Industrial Chemistry, Azo Dyes, 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a03 245, point 3.2; ibid, Textile Auxiliaries, 2002 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a26 227 and Ashford's Dictionary of Industrial Chemicals, Second Edition, p. 14-p. 39, 2001).

The term "anionic direct dye" is intended to mean any direct dye comprising in its structure at least one sulfonate group SO3 " and/or at least one carboxylate group C(0)0 " and optionally one or more anionic groups G " with G " , which may be identical or different, representing an anionic group chosen from alkoxide O " , thiolate S " , carboxylate and thiocarboxylate: C(Q)Q'-, with Q and Q', which may be identical or different, representing an oxygen or sulfur atom; preferably, G " represents a carboxylate, i.e. Q and Q' represent an oxygen atom.

The preferred anionic direct dyes are chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoids, natural acid dyes, and mixtures thereof. Each of these dyes has at least one sulfonate or carboxylate group.

As anionic dyes according to the invention, mention may be made of the dyes of formulae (II), (IF), (III), (ΙΙΓ), (IV), (IV), (V), (V), (VI), (VII), (VIII) and (IX) below: a) the diaryl anionic azo dyes of formula (II) or (ΙΓ):

L which formulae (II) and (IF)

R 7 , Rs, R9, Rio, RV, R's, R¾ and R'io, which may be identical or different, represent hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0)2S(0 " )-M + with M + representing a cationic counterion such as an alkali metal (Na, K) or an alkaline-earth metal (Ca);

- (0)CO " -M + with M + as previously defined;

- R"-S(0)2 " , with R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;

- R' "-S(0)2-X'- with R" ' representing an alkyl or optionally substituted aryl group, X' as defined previously;

- (di)(alkyl)amino;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 ~ )-M + and iv) alkoxy with M + as defined previously;

- optionally substituted heteroaryl; preferentially a benzothiazolyl group;

- cycloalkyl; especially cyclohexyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0) 2 S(0 " )- M + or phenylamino groups;

- or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A'; and R' 7 with R's or R's with R'9 or R'9 with R'io together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 ~ )-M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°- X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M + , R°, X, X', X" and Ar as defined previously; • W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb together form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

it being understood that formulae (II) and (ΙΓ) comprise at least one sulfonate (0) 2 S(0 " )-M + or carboxylate (0)C(0 " )-M + radical on one of the rings A, A, B, B' or C with M + as defined previously.

As examples of dyes of formula (II), mention may be made of Acid Red 1 ,

Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 and Food Black 2; and as examples of dyes of formula (IF), mention may be made of Acid Red 111, Acid Red 134 and Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (III) and (III'):

in which formulae (III) and (ΠΓ),

• Rii, Ri2 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0) 2 S(0 ~ ), M + with M + as defined previously;

· Ri4 represents a hydrogen atom, an alkyl group or a group -C(0)0 " , M + with M + as defined previously;

Ri5 represents a hydrogen atom;

Ri6 represents an oxo group, in which case R'i 6 is absent, or alternatively R15 with Ri6 together form a double bond;

· Ri7 and Ris, which may be identical or different, represent a hydrogen atom or a group chosen from:

- (0) 2 S(0 ~ ), M + with M + as defined previously;

- Ar-0-S(0) 2 " with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups;

· Ri and R20 together form either a double bond, or a benzo group D', which is optionally substituted;

• R' i6, R' i9 and R'20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy 1 group;

R21 represents a hydrogen atom or an alkyl or alkoxy group;

· Ra and Rb, which may be identical or different, are as defined previously, preferentially Ra represents a hydrogen atom and Rb represents an aryl group;

• Y represents either a hydroxyl group or an oxo group;

represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

it being understood that formulae (III) and (III') comprise at least one sulfonate group (0) 2 S(0 ~ ), M + on one of the rings D or E or formulae (III) and (III') comprise at least one carboxylate group (O)C(O ), M + with M + as defined previously. As examples of dyes of formula (III), mention may be made of Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and, as examples of dyes of formula (III'), mention may be made of the ammonium salt derived from Acid Yellow 17;

c) the anthraquinone dyes of formulae (IV) and (IV):

in which formulae (IV) and (IV):

R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from:

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0 ~ ), M + with M + as defined previously;

- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0 ~ ), M + with M + as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- (0)2S(0 " ), M + with M + as defined previously;

• Z' represents a hydrogen atom or a group NR28R2 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl; - aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0) 2 S(0 ~ ), M + with M + as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group;

- cycloalkyl; especially cyclohexyl;

• Z represents a group chosen from hydroxyl and NR' 2 8R'2 with R' 2 8 and R' 2 s>, which may be identical or different, representing the same atoms or groups as R 2 8 and R 2 9 as defined previously;

it being understood that formulae (IV) and (IV) comprise at least one sulfonate group (0) 2 S(0 ), M + with M + as defined previously.

As examples of dyes of formula (IV), mention may be made of Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43 and Mordant Red 3; and as examples of dyes of formula (IV), mention may be made of the ammonium salt derived from Acid Black 48; d) the dyes corresponding to the general formulae (V) and (V):

in which formulae (V) and (V),

R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;

- hydroxyl, mercapto;

- nitro, nitroso;

- (poly)haloalkyl;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously;

- (0) 2 S(0 ~ ), M + with M + as defined previously;

- (0)CO ~ , M + with M + as previously defined;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino;

- in particular, R30, R31 and R32 represent a hydrogen atom;

• Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;

• W is as defined previously; W particularly represents a group -NH-;

• ALK represents a linear or branched divalent Ci-C 6 alkylene group; in particular, ALK represents a group -CH2-CH2-;

• n is 1 or 2;

• p represents an integer inclusively between 1 and 5;

• q represents an integer inclusively between 1 and 4;

• u is 0 or 1 ;

• when n is 1 , J represents a nitro or nitroso group; particularly nitro;

• when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0) m - with m representing an integer 1 or 2; preferentially, J represents a radical -SO2-;

• M' is as defined previously for M + ; which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously;

it being understood that formulae (V) and (V) comprise at least one sulfonate group (0) 2 S(0 ~ ), M + or carboxylate group (O)C(O ), M + with M + as defined previously. As examples of dyes of formula (V), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (V), mention may be made of: Acid Yellow 1, sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2- piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N(2"-hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid and 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; e) the triarylmethane dyes of formula (VI):

in which formula (VI),

• R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and a benzyl group optionally substituted with a group (0) m S(0 " )-M + with M + and m as defined previously;

R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group; - (0)2S(0 ), M + with M + representing a hydrogen atom or a cationic counterion;

- (0)CO ~ , M + with M + as previously defined;

- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: Γ; with Γ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 ~ ), M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X"-; with M + , R°, X, X' and X" as defined previously;

- particularly, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (0)2S(0 " )-M + ; and when R43 with R44 together form a benzo group, it is preferentially substituted with a group (0) 2 S(0 ;

it being understood that at least one of the rings G, H, I or Γ comprises at least one sulfonate (0)2S(0 M + or carboxylate (0)C(0 " )-M + group with M + as defined previously.

As examples of dyes of formula (VI), mention may be made of: Acid Blue

1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49 and Acid Green 50; f) the xanthene-based dyes of formula (VII):

in which formula (VII),

R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;

R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl; - alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- (0) 2 S(0 ~ ), M + with M + representing a hydrogen atom or a cationic counterion; - (0)CO ~ , M + with M + as previously defined;

- particularly, R53, R54, R55 and R 4 8 represent a hydrogen or halogen atom;

• G represents an oxygen or sulfur atom or a group NRe with R e as defined previously; particularly, G represents an oxygen atom;

• L represents an alkoxide O " , M + ; a thioalkoxide S " , M + or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M + as defined previously; M + is particularly sodium;

• L' represents an oxygen or sulfur atom or an ammonium group: N + RfR g , with Rf and Rg, which may be identical or different, representing a hydrogen atom, an alkyl group or an optionally substituted aryl group; L' represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)mS(O " ), M + groups with m and M + as defined previously;

• Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q' represent an oxygen atom;

• M + is as defined previously;

it being understood that formula (VII) comprises at least one sulfonate group (0) 2 S(0 ~ ), M + or carboxylate group (O)C(O ), M + with M + as defined previously.

As examples of dyes of formula (VII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9; g) the indole-based dyes of formula (VIII):

in which formula (VIII), R53, R54, R55, R56, R57, R58, R59 and R50, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (0) 2 S(0 ~ ), M + with M + as defined previously;

- (0)CO ~ , M + with M + as previously defined;

• G represents an oxygen or sulfur atom or a group NRe with R e as defined previously; particularly, G represents an oxygen atom;

· Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;

it being understood that formula (VIII) comprises at least one sulfonate group (0) 2 S(0 ~ ), M + or carboxylate group (O)C(O ), M + with M + as defined previously.

As examples of dyes of formula (VIII), mention may be made of the ammonium salt derived from Acid Blue 74; h) the quino line-based dyes of formula (IX):

in which formula (IX),

• Rei represents a hydrogen or halogen atom or an alkyl group;

• R52, R53 and R54, which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 ~ ), M + with M + as defined previously; • or alternatively R51 with Q, or 51 with R54, together form a benzo group optionally substituted with one or more groups (0) 2 S(0 ~ ), M + with M + representing a hydrogen atom or a cationic counterion;

it being understood that formula (IX) comprises at least one sulfonate group (0) 2 S(0 ~ ), M + with M + as defined previously.

As examples of dyes of formula (IX), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5;

i) the mesomers and tautomers of formulae (II) to (IX); and

j) mixtures thereof.

More particularly, the anionic direct dyes that are useful in the invention may be chosen from the following dyes:

(C.I. 45380) Acid Red 87 belonging to formula (VII)

salts of 2,4-dinitro-l-naphthol-7-sulfonic acid belonging to

(C.I. 10316)

formula (V)

(C.I. 10383) Acid Orange 3 belonging to formula (V)

(C.I. 13015) Acid Yellow 9 / Food Yellow 2 belonging to formula (II)

(C.I. 14780) Direct Red 45 / Food Red 13 belonging to formula (II)

(C.I. 13711) Acid Black 52 belonging to formula (II)

(C.I. 13065) Acid Yellow 36 belonging to formula (II)

salt of l-hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)naphthalene-4-

(C.I 14700)

sulfonic acid / Food Red 1 belonging to formula (II)

Acid Red 14 / Food Red 3 / Mordant Blue 79 belonging to

(C.I. 14720)

formula (II)

salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-

(C.I. 14805) (phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 belonging to formula (II)

Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49

(C.I. 15510)

belonging to formula (II)

(C.I. 15985) Food Yellow 3 / Pigment Yellow 104 belonging to formula (II)

(C.I. 16185) Acid Red 27 / Food Red 9 belonging to formula (II)

(C.I. 16230) Acid Orange 10 / Food Orange 4 belonging to formula (II)

(C.I. 16250) Acid Red 44 belonging to formula (II) (C.I. 17200) Acid Red 33 / Food Red 12 belonging to formula (II)

(C.I. 15685) Acid Red 184 belonging to formula (II)

(C.I. 19125) Acid Violet 3 belonging to formula (II)

salt of l-hydroxy-2-(4'-acetamidophenylazo)-8-

(C.I. 18055) acetamidonaphthalene-3,6-disulfonic acid / Acid Violet 7 /

Food Red 11 belonging to formula (II)

(C.I. 18130) Acid Red 135 belonging to formula (II)

(C.I. 19130) Acid Yellow 27 belonging to formula (III)

(C.I. 19140) Acid Yellow 23 / Food Yellow 4 belonging to formula (III)

4'-(sulfonato-2",4"-dimethyl)bis(2,6-phenylazo)- 1 ,3-

(C.I. 20170)

dihydroxybenzene / Acid Orange 24 belonging to formula (II) salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-

(C.I. 20470)

hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (II)

(4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl- 4-

(C.I. 23266) ((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red

111 belonging to formula (IF)

(C.I. 27755) Food Black 2 belonging to formula (II)

1 -(4'-sulfonatophenylazo)-4-((2"-hydroxy-3 "-acetylamino-

(C.I. 25440) 6",8"-disulfonato)naphthylazo)-6-sulfonatonaphthalene

(tetrasodium salt) / Food Black 1 belonging to formula (II)

(C.I. 42090) Acid Blue 9 belonging to formula (VI)

(C.I. 60730) Acid Violet 43 belonging to formula (IV)

(C.I. 61570) Acid Green 25 belonging to formula (IV)

salt of l-amino-4-cyclohexylamino-9,10-anthraquinone-2-

(C.I. 62045)

sulfonic acid / Acid Blue 62 belonging to formula (IV)

(C.I. 62105) Acid Blue 78 belonging to formula (IV)

salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-l-

(C.l. 14710)

naphthalenesulfonic acid / Acid Red 4 belonging to formula (II)

2-piperidino-5-nitrobenzenesulfonic acid belonging to formula (V)

2-(4'-N,N-(2"-hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid belonging to formula (V)

4- -Hydroxyethylamino-3-nitrobenzene

sulfonic acid belonging to formula (V) (C.I. 42640) Acid Violet 49 belonging to formula (VI)

(C.I. 42080) Acid Blue 7 belonging to formula (VI)

ammonium salts of l,2-dihydroxy-3-sulfoanthraquinone /

(C.I. 58005)

Mordant Red 3 belonging to formula (IV) salt of l-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)-2-

(C.I. 62055) anthracenesulfonic acid / Acid Blue 25 belonging to formula

(IV)

salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-l-

(C.I. 14710)

naphthalenesulfonic acid / Acid Red 4 belonging to formula (II)

Most of these dyes are described in particular in the Colour Index published by The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD12 JBN England.

The anionic direct dyes that are more particularly preferred are the dyes designated in the Colour Index under the code C.I. 58005 (monosodium salt of 1,2- dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2- [(9, 10-dihydro-4-hydroxy-9, 10-dioxo- 1 -anthracenyl)amino]-5- methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-l- naphthalenyl)azo]benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5- [(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5- amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenedisulfonic acid), C.I. 20470 (disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6- naphthalenedisulfonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3- sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2, 5-cyclohexadien- 1 - ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt), C.I. 61570 (disodium salt of 2,2'-[(9, 10-dihydro-9, 10-dioxo- 1 ,4-anthracenediyl)diimino]bis[5- methyljbenzenesulfonic acid).

More preferentially, the anionic direct dyes are chosen from those of formulae (II), (III) and (IV).

According to a particular embodiment of the invention, the direct dyes of the invention are chosen from those corresponding to formulae (Ila), (Ilia) and (IVa) below:

in which formula (Ila),

R 7 , Rs, R9, Rio, R'7, R'8, R'9 and R'io, which may be identical or different, represent a hydrogen atom or a group chosen from:

- hydroxyl,

- nitro, nitroso;

- (di)(alkyl)amino;

- (0) 2 S(0 ~ ), M + with M + representing a hydrogen atom or a cationic counterion as defined previously; and

- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl or (0) 2 S(0 ~ ), M + groups;

• or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with

R' 10 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from a) (0) 2 S(0 ~ ), M + ; b) hydroxyl; c) Ar-N=N-; with M + and Ar as defined previously;

in which formula (Ilia),

R11 , R12 and R13, which may be identical or different, represent a hydrog halogen atom, an alkyl group or (0) 2 S(0 ~ ), M + with M + as defined previously; Ri4 represents a hydrogen atom, an alkyl group or a group C(0)0 " , M + with M + as defined previously;

Ri6, Ri7, Ri8, Ri9 and R20, which may be identical or different, represent a hydrogen atom, an alkyl or hydroxyl group or (0)2S(0 ~ ), M + with M + as defined previously;

• Y represents either a hydroxyl group or an oxo group;

• represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

it being understood that formula (Ilia) comprises at least one sulfonate group (0) 2 S(0 , M + on one of the rings D or E or carboxylate (O)C(O ), M + ;

in which formula (IVa),

· Z' represents a group NR28R2 with R28 representing a hydrogen atom or an alkyl group and R29 representing an aryl group optionally substituted particularly with one or more groups chosen from i) alkyl such as methyl and ii) (0)2S(0 ~ ), M + with M + as defined previously;

• Z represents a group chosen from hydroxyl and NR'2sR'2 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously;

it being understood that formula (IVa) comprises at least one sulfonate group (0) 2 S(0 ), M + .

As examples, mention may be made of the following anionic dyes:

Commercial name Corresponding structure 0 OH

Acid Violet 43

(belonging to formulae (IV) and (IVa))

with M+, which may be identical or different, being a cationic counterion as defined previously.

Preferably, the anionic direct dye is Acid Violet 43.

The total amount of the anionic direct dye(s), present in the composition (B) according to the present invention, preferably ranges from 0.001% to 15% by weight, more preferentially from 0.005% to 10% by weight, better still from 0.01% to 5% by weight, and even better still from 0.1% to 2% by weight, relative to the total weight of the composition (B).

Surfactants

The composition (B) used in the process for dyeing keratin fibres according to the present invention also comprises one or more surfactants.

The surfactant(s) present in the composition (B) according to the present invention are advantageously chosen from anionic surfactants, amphoteric or zwitterionic surfactants, non-ionic surfactants, cationic surfactants and mixtures thereof; and preferably from anionic surfactants, amphoteric or zwitterionic surfactants, non-ionic surfactants and mixtures thereof.

More preferentially, the composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more anionic surfactants, one or more amphoteric or zwitterionic surfactants and mixtures thereof.

Preferably, the composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more anionic surfactants.

For the purposes of the present invention, the term "anionic surfactant" is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups C0 2 H, CO2 " , SO3H, SO3-, OSO3H, OSO3-, H2PO3, HPO3-, PO3 2" , H2PO2, HPO2 " , PO2 2" , POH and PO . Preferably, the anionic surfactants used in the composition according to the invention are chosen from anionic surfactants comprising in their structure one or more sulfate and/or sulfonate and/or phosphate and/or carboxylate groups, and/or mixtures thereof.

Preferentially, the composition according to the invention comprises one or more carboxylic alkyl ether anionic surfactants.

More preferentially, the composition according to the invention comprises a mixture of anionic surfactants and especially one or more anionic surfactants comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups and one or more carboxylic alkyl ether anionic surfactants.

The anionic surfactant(s) comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups may be oxyethylenated and/or oxypropylenated. The total average number of ethylene oxide (EO) and/or propylene oxide (PO) groups may then range from 1 to 50 and especially from 1 to 10.

The anionic surfactant(s) comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups may be chosen from alkyl sulfates, alkylamido sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl ether sulfates, alkyl ether sulfosuccinates, acyl isethionates and methyl acyl taurates, olefin sulfonates, and salts thereof; the alkyl or acyl group of all these various compounds preferably containing from 8 to 24 carbon atoms, and the aryl group preferably denoting a phenyl or benzyl group.

Among the anionic surfactants comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups, it is preferred to use one or more anionic sulfate surfactants, preferentially chosen from Cs-Ci4 and more particularly C12-C14 alkyl ether sulfates, and/or one or more olefin sulfonates.

Preferably, the anionic surfactant(s) comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups are in the form of salts, and in particular of alkaline salts, especially sodium salts, ammonium salts, amine salts, including amino alcohol salts, and/or magnesium salts. These salts preferably comprise from 2 to 5 ethylene oxide groups.

Among these salts, sodium, triethanolamine, magnesium or ammonium (C12- Ci4)alkyl sulfates and/or sodium, ammonium or magnesium (Ci2-Ci4)alkyl ether sulfates, which are oxyethylenated, for example with 1 or 2.2 mol of ethylene oxide, or sodium olefin sulfonates, are more preferably used. Better still, the surfactant(s) comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups are chosen from sodium, ammonium or magnesium (Ci2-Ci4)alkyl ether sulfates oxyethylenated with 2.2 mol of ethylene oxide, as sold under the name Texapon N702 by the company Cognis.

Among the anionic surfactant(s) comprising in their structure one or more sulfate and/or sulfonate and/or phosphate groups, it is preferred to use sodium or ammonium lauryl ether sulfates or sodium olefin sulfonates.

The carboxylic alkyl ether anionic surfactant(s) that may be used according to the invention preferably comprise a C6-C24 alkyl chain.

The carboxylic alkyl ether anionic surfactant(s) may be chosen, alone or as mixtures, from:

- (C6-C24)alkyl ether carboxylic acids,

- (C 6 -C24)alkylaryl ether carboxylic acids,

- (C6-C24)alkylamido ether carboxylic acids,

- and salts thereof.

The carboxylic alkyl ether anionic surfactant(s) may be oxyalkylenated, preferably oxyethylenated and/or oxypropylenated. The total average number of alkylene oxide groups then preferably ranges from 2 to 50, in particular from 2 to 24 and better still from 2 to 15.

When the carboxylic alkyl ether anionic surfactant(s) are oxyalkylenated, they preferably comprise from 2 to 50 alkylene oxide groups and in particular from 2 to 50 ethylene oxide (EO) groups.

Preferably, the carboxylic alkyl ether anionic surfactant(s) are neutralized with one or more salts. The salts are chosen in particular from alkaline salts and especially sodium salts, ammonium salts, amine salts, including amino alcohol salts such as triethanolamine or monoethanolamine salts, and magnesium salts.

The polyethoxylated carboxylic anionic surfactants more preferably used are those corresponding to formula (X) below: Ri(OC2H 4 )nOCH 2 COOA (X) in which: - Ri represents a linear or branched C8-C22 alkyl or alkenyl group or mixture of groups, a (Cs-C^alkylphenyl group, a group R2CONH-CH2-CH2- with R2 denoting a linear or branched C11-C21 alkyl or alkenyl group,

- n is an integer or decimal number (average value) that may range from 2 to 24 and preferably from 2 to 15,

- A denotes H, NH 4 , Na, K, Li, Mg or a monoethanolamine or triethanolamine residue. Mixtures of compounds of formula (X) may also be used, in particular mixtures in which the groups Ri are different.

Preferably, Ri denotes a group or a mixture of groups chosen from C 12 -C 14 alkyl, cocoyl, oleyl, nonylphenyl and octylphenyl groups; A denotes a hydrogen or sodium atom; and n ranges from 2 to 20 and preferably from 2 to 10.

Even more preferentially, use is made of compounds of formula (X) in which Ri denotes a C12 alkyl group; A denotes a hydrogen or sodium atom; and n ranges from 2 to 10.

Among the commercial products that may preferably be used are the products sold by the company KAO under the names:

Akypo ® NP 70 (Ri = nonylphenyl, n = 7, A = H)

Akypo ® NP 40 (Ri = nonylphenyl, n = 4, A = H)

Akypo ® OP 40 (Ri = octylphenyl, n = 4, A = H)

Akypo ® OP 80 (Ri = octylphenyl, n = 8, A = H)

Akypo ® OP 190 (Ri = octylphenyl, n = 19, A = H)

Akypo ® RLM 38 (Ri = (Ci 2 -Ci 4 )alkyl, n = 4, A = H)

Akypo ® RLM 38 NV (Ri = (Ci 2 -Ci 4 )alkyl, n = 4, A = Na)

Akypo ® RLM 45 CA (Ri = (Ci 2 -Ci 4 )alkyl, n = 4.5, A = H)

Akypo ® RLM 45 NV (Ri = (Ci 2 -Ci 4 )alkyl, n = 4.5, A = Na)

Akypo ® RLM 100 (Ri = (Ci 2 -Ci 4 )alkyl, n = 10, A = H)

Akypo ® RLM 100 NV (Ri = (Ci 2 -Ci 4 )alkyl, n = 10, A = Na)

Akypo ® RLM 130 (Ri = (Ci 2 -Ci 4 )alkyl, n = 13, A = H)

Akypo ® RLM 160 NV (Ri = (Ci 2 -Ci 4 )alkyl, n = 16, A = Na)

or by the company Sandoz under the names:

Sandopan DTC-Acid (Ri = (Ci 3 )alkyl, n = 6, A = H)

Sandopan DTC (Ri = (Ci 3 )alkyl, n = 6, A = Na)

Sandopan LS 24 (Ri = (Ci 2 -Ci 4 )alkyl, n = 12, A = Na)

Sandopan JA 36 (Ri = (Ci 3 )alkyl, n = 18, A = H), and more particularly the products sold under the following names:

Akypo ® RLM 45 (INCI: Laureth-5 carboxylic acid)

Akypo ® RLM 100

Akypo ® RLM 38.

Among the carboxylic alkyl ether anionic surfactants, use is preferably made of lauryl ether carboxylic acids or sodium lauryl ether carboxylates.

Preferably, the composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more non-ionic surfactants.

The non-ionic surfactant(s) that may be present in the composition (B) according to the invention are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pages 116-178.

Examples of non-ionic surfactants that may be mentioned include the following non- ionic surfactants:

- oxyalkylenated (Cs-C24)alkylphenols;

- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C8-C40 alcohols, preferably comprising one or two fatty chains;

- saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 fatty acid amides;

- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols;

- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, C 8 - C30 acids and of sorbitol;

- esters of fatty acids and of sucrose;

- (C8-C3o)alkyl(poly)glucosides, (C8-C3o)alkenyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, (C8-C3o)alkyl(poly)glucoside esters;

- saturated or unsaturated oxyethylenated plant oils;

- condensates of ethylene oxide and/or of propylene oxide;

- N-(C8-C3o)alkylglucamine and N-(C8-C3o)acylmethylglucamine derivatives;

- aldobionamides;

- amine oxides;

- oxyethylenated and/or oxypropylenated silicones;

- and mixtures thereof. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

The number of moles of ethylene oxide and/or of propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol ranges in particular from 1 to 50 and better still from 1 to 10.

Advantageously, the non-ionic surfactants according to the invention do not comprise any oxypropylene units.

As examples of glycerolated non-ionic surfactants, use is preferably made of monoglycerolated or polyglycerolated Cs to C 4 o alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.

Mention may be made, as examples of compounds of this type, of lauryl alcohol comprising 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol comprising 2 mol of glycerol, cetearyl alcohol comprising 6 mol of glycerol, oleocetyl alcohol comprising 6 mol of glycerol and octadecanol comprising 6 mol of glycerol.

Among the glycerolated alcohols, it is more particularly preferred to use the Cs to Cio alcohol containing 1 mol of glycerol, the Cio to C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.

The non-ionic surfactant(s) used in the detergent composition according to the invention are preferentially chosen from:

- saturated or unsaturated, linear or branched, oxyethylenated Cs-Oo alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and preferably comprising one or two fatty chains;

- saturated or unsaturated oxyethylenated vegetable oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;

- (C8-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated (0 to 10 EO) and comprising 1 to 15 glucose units;

- monoglycerolated or polyglycerolated Cs to C 4 o alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol; - saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 fatty acid amides;

- esters of saturated or unsaturated, linear or branched, C8-C30 acids and of polyethylene glycols;

- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, C 8 - C30 acids and of sorbitol;

- and mixtures thereof.

Preferably, the composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more amphoteric or zwitterionic surfactants.

In particular, the amphoteric or zwitterionic surfactant(s), which are preferably non-silicone, used in the detergent composition according to the present invention may in particular be derivatives of optionally quaternized, secondary or tertiary aliphatic amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Mention may in particular be made of (Cs-C2o)alkyl betaines, (Cs-C2o)alkyl sulfobetaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines and (C8-C2o)alkylamido(C6- C8)alkyl sulfobetaines.

Among the optionally quaternized derivatives of secondary or tertiary aliphatic amines that may be used, as defined above, mention may also be made of the compounds having the respective structures (XI) and (XII) below: Ra-CONHCH2CH2-N + (Rb)(Rc)-CH2COO-, M + , X " (XI) in which formula (XI),

- Pa represents a C10 to C30 alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group; - Rb represents a beta-hydroxyethyl group; and

- Rc represents a carboxymethyl group;

- M + represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and - X " represents an organic or mineral anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C4)alkyl sulfates, (Ci-C4)alkyl- or (Ci- C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M + and X " are absent;

Ra'-CONHCH2CH2-N(B)(B') (XII) in which formula (XII),

- B represents the group -CH2CH2OX;

- B' represents the group -(0¼) Ζ Υ', with z = 1 or 2;

- X represents the group -CH2COOH, -CH2-COOZ', -CH2CH2COOH or CH2CH2- COOZ', or a hydrogen atom;

- Y * represents the group -COOH, -COOZ * or -CH 2 -CH(OH)S0 3 H or the group CH 2 CH(OH)S0 3 -Z';

- Z' represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and

- Ra' represents a C10 to C 3 o alkyl or alkenyl group of an acid Ra'-COOH which is preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C 17 group, and its iso form, or an unsaturated C 17 group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol ® C2M Concentrate.

Use may also be made of compounds of formula (XIII):

Ra » - HCH(Y")-(CH2)nCO H(CH 2 )n'-N(Rd)(Re) (XIII) in which formula (XIII), - Y" represents the group -COOH, -COOZ" or -CH 2 -CH(OH)S0 3 H or the group CH 2 CH(OH)S0 3 -Z";

- Rd and R e represent, independently of each other, a Ci to C 4 alkyl or hydroxyalkyl radical;

- Z" represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;

- Ra" represents a Cio-C 3 o alkyl or alkenyl group of an acid Ra"-COOH which is preferably present in coconut oil or in hydrolysed linseed oil;

- n and n' denote, independently of each other, an integer ranging from 1 to 3.

Mention may be made, among the compounds of formula (XI), of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by Chimex under the name Chimexane HB.

These compounds may be used alone or as mixtures.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C8-C 2 o)alkylbetaines such as cocobetaine, (C 8 - C 2 o)alkylamido(C 3 -C8)alkylbetaines such as cocamidopropylbetame, and mixtures thereof, and the compounds of formula (XIII) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide).

Preferentially, the amphoteric or zwitterionic surfactants are chosen from (C8-C 2 o)alkylamido(C 3 -C8)alkylbetaines such as cocamidopropyl betaine.

Preferably, the composition (B) used in the process for dyeing keratin fibres according to the present invention comprises one or more cationic surfactants.

The term "cationic surfactant" is intended to mean a surfactant that is positively charged when it is contained in the compositions according to the invention. This surfactant may bear one or more positive permanent charges or may contain one or more cationizable functions in the compositions according to the invention.

The cationic surfactant(s) are preferably chosen from primary, secondary or tertiary fatty amines, which are optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one Cs to C 3 o hydrocarbon- based chain. Examples of quaternary ammonium salts that may especially be mentioned - those corresponding to the general formula (XIV) below:

(XIV)

in which the groups R 2 8 to R31 , which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R 2 8 to R31 denoting a group containing from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C 2 -C6)alkylene, C1-C30 alkylamide, (Ci2-C 2 2)alkylamido(C 2 - C 6 )alkyl, (Ci2-C 22 )alkyl acetate, and C1-C30 hydroxyalkyl groups, X " is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates, and (Ci-C4)alkyl- or (Ci-C4)alkylarylsulfo nates.

Among the quaternary ammonium salts of formula (XIV), the ones that are preferred are, on the one hand, tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, the palmitylamidopropyltrimethylammonium salt, the stearamidopropyltrimethylammonium salt, the stearamidopropyldimethylcetearylammonium salts, or the stearamidopropyldimethyl(myristyl acetate)ammonium salts sold under the name Ceraphyl ® 70 by the company Van Dyk. It is preferred in particular to use the chloride salts of these compounds;

- quaternary ammonium salts of imidazoline, for instance those of formula (XV) below:

(XV) in which:

R32 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids,

R33 represents a hydrogen atom, a Ci to C 4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms,

R34 represents a Ci to C 4 alkyl group,

R35 represents a hydrogen atom or a Ci to C 4 alkyl group,

- X " is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates and alkyl- or alkylarylsulfonates, the alkyl and aryl groups of which preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.

Preferably, R32 and R33 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R34 denotes a methyl group and R35 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat ® W 75 by Rewo;

- quaternary diammonium or triammonium salts, in particular of formula

(XVI):

(XVI) in which: R36 denotes an alkyl radical comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;

R37 is chosen from hydrogen, an alkyl radical comprising from 1 to 4 carbon atoms or an (R36a)(R37a)(R38a)N-(CH 2 )3 group,

R36a, R37a, R38a, R38, R39, R40 and R41 , which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and

X " is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates.

Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quatemium 89), and Finquat CT, sold by the company Finetex (Quatemium 75);

- quaternary ammonium salts containing at least one ester function, such as those of formula (XVII) below:

O (C s H 2s O) z — R 45

R 44 — C— (OC r H 2r ) y - N— (C t H 2t O) x - R 43 X R42 (XVII) in which:

- R 42 is chosen from Ci to C 6 alkyl groups and Ci to C 6 hydroxyalkyl or dihydroxyalkyl groups;

- R43 is chosen from:

O

R,

- the group 46

- groups R47, which are linear or branched, saturated or unsaturated Ci C 22 hydrocarbon-based groups,

- a hydrogen atom;

- R45 is chosen from:

- the group - groups R49, which are linear or branched, saturated or unsaturated Ci-C 6 hydrocarbon-based groups,

- a hydrogen atom;

- R44, R46 and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7 to C21 hydrocarbon-based groups,

- r, s and t, which may be identical or different, are integers ranging from 2 to 6,

- y is an integer ranging from 1 to 10,

- x and z, which may be identical or different, are integers ranging from 0 to 10,

- X " is a simple or complex and organic or inorganic anion,

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R43 denotes R47, and that when z is 0 then R45 denotes R49.

The alkyl groups R42 may be linear or branched, and more particularly linear.

Preferably, R42 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z ranges from 1 to 10.

When R43 is a hydrocarbon-based group R47, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.

When R45 is a hydrocarbon-based group R49, it preferably contains 1 to 3 carbon atoms.

Advantageously, R44, R46 and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn to C21 hydrocarbon- based groups, and more particularly from linear or branched, saturated or unsaturated Cn to C21 alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X " is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium bearing an ester function.

The anion X " is even more particularly chloride or methyl sulfate. Use is made more particularly in the dyeing composition according to the invention of the ammonium salts of formula (XVII) in which,

R42 denotes a methyl or ethyl group;

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R43 is chosen from:

O

- the group 46

- methyl, ethyl or C 14 to C22 hydrocarbon-based groups,

- a hydrogen atom;

R45 is chosen from:

- the group

- a hydrogen atom;

R44, R46 and R48, which may be identical or different, are chosen from saturated or unsaturated and linear or branched C13 to C 17 hydrocarbon-based groups and preferably from saturated or unsaturated and linear or branched C13 to C 17 alkyl and alkenyl groups.

Advantageously, the hydrocarbon-based groups are linear.

Examples that may be mentioned include the compounds of formula (XI) such as the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium,

triacyloxyethylmethylammonium and monoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, which are optionally oxyalkylenated, with C 10 to C30 fatty acids or with mixtures of Cio to C30 fatty acids of plant or animal origin, or by transesterification of their methyl esters. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart ® by the company Henkel, Stepanquat ® by the company Stepan, Noxamium ® by the company CECA or Rewoquat ® WE 18 by the company Rewo-Witco.

Among these compounds, mention may be made especially of dipalmitoylethylhydroxyethylmethylammonium methosulfate.

The composition (B) according to the present invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.

Use may also be made of the ammonium salts containing at least one ester functional group that are described in patents US-A-4 874 554 and US-A-4 137 180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts comprising at least one ester function comprise two ester functions.

Among the quaternary ammonium salts containing at least one ester function, which may be used, it is preferred to use dipalmitoylethylhydroxyethyl- methylammonium salts.

Preferably, the surfactant(s) present in the composition (B) according to the invention are chosen from behentrimonium chloride, cetrimonium chloride and mixtures thereof.

The total amount of surfactant(s) present in the composition (B) according to the present invention preferably ranges from 0.1% to 30% by weight, more preferentially from 1% to 25% by weight, and even better still from 2% to 20% by weight, relative to the total weight of the composition (B).

The total amount of anionic surfactant(s), when they are present in the composition (B) according to the present invention, preferably ranges from 1% to 25% by weight, more preferentially from 5% to 20% by weight, and even better still from 8% to 18% by weight, relative to the total weight of the composition (B). The total amount of cationic surfactant(s), when they are present in the composition (B) according to the present invention, preferably ranges from 0.1% to 15% by weight, more preferentially from 0.5%> to 10%> by weight, and even better still from 1% to 5% by weight, relative to the total weight of the composition (B).

The composition (A) used in the process for dyeing keratin fibres according to the present invention can optionally also comprise one or more surfactants, preferably chosen from cationic surfactants, as defined above, non-ionic surfactants, as defined above, and mixtures thereof.

When the composition (A) also comprises one or more non-ionic surfactant(s), the non- ionic surfactant(s) are preferably chosen from saturated or unsaturated, linear or branched, oxyethylenated Cs to C 4 o alcohols comprising from 1 to 100 mol of ethylene oxide, more preferentially from 2 to 50 mol of ethylene oxide, and even better still from 2 to 40 mol of ethylene oxide; (C 8 - C3o)alkyl(poly)glucosides which are optionally oxyalkylenated (0 to 10 EO) and which comprise 1 to 15 glucose units; saturated or unsaturated, linear or branched Cs to C30 acid esters of sorbitol, which are preferably oxyethylenated; and mixtures thereof.

Solvents

The compositions (A) and (B) used in the process for dyeing keratin fibres according to the present invention can optionally also comprise water, an organic solvent or mixtures thereof.

Examples of organic solvents that may be mentioned include linear or branched C2 to C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, such as benzyl alcohol or phenoxy ethanol, and mixtures thereof.

Preferably, the process for dyeing keratin fibres according to the present invention comprises the following steps:

- at least one step of applying to said keratin fibres a composition (A) comprising at least two organosilanes, that are different from one another, chosen from the compounds of formulae (la) and (lb), as defined previously, and at least one organic acid, as defined previously, and - at least one step of applying to said keratin fibres a composition (B) comprising at least one anionic direct dye, as defined previously, and at least one surfactant, preferably chosen from anionic surfactants, non-ionic surfactants, and amphoteric or zwitterionic surfactants, and mixtures thereof, as defined previously;

the composition (B) being applied after the composition (A).

More preferentially, the process for dyeing keratin fibres according to the present invention comprises the following steps:

- at least one step of applying to said keratin fibres a composition (A) comprising at least one organosilane of formula (la), as previously defined, at least one organosilane of formula (lb), as previously defined, and at least one organic acid, preferably chosen from carboxylic acids, as defined previously, and

- at least one step of applying to said keratin fibres a composition (B) comprising at least one anionic direct dye, as defined previously, and at least one surfactant, preferably chosen from anionic surfactants, amphoteric or zwitterionic surfactants, and mixtures thereof, as defined previously;

the composition (B) being applied after the composition (A).

Better still, the process for dyeing keratin fibres according to the present invention comprises the following steps:

- at least one step of applying to said keratin fibres a composition (A) comprising a mixture of methyltriethoxysilane and 3-aminopropyltriethoxysilane, and at least one organic acid, preferably chosen from carboxylic acids, as defined previously, and

- at least one step of applying to said keratin fibres a composition (B) comprising at least one anionic direct dye, as defined previously, and at least one surfactant, preferably chosen from anionic surfactants, as defined previously;

the composition (B) being applied after the composition (A).

Additives

The compositions (A) and (B) used in the process for dyeing keratin fibres according to the present invention can optionally also comprise one or more additives, other than the compounds of the invention and among which mention may be made of anionic, non-ionic or amphoteric polymers or mixtures thereof, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, mineral or organic thickeners, in particular polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances, preservatives, pigments and ceramides.

Needless to say, those skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the compositions (A) and (B) according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

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

Dyeing process

The process for dyeing keratin fibres according to the present invention comprises:

- at least one step of applying to said keratin fibres a composition (A), as defined previously, and

- at least one step of applying to said fibres a composition (B), as defined previously;

the composition (B) being applied after the composition (A).

In other words, composition (A) is applied before composition (B).

The composition (A) may be applied to a wet or dry, preferably dry, head of hair, with or without a leave-on time. Preferably, the composition (A) is applied for a leave-on time ranging from 5 minutes to 1 hour.

Preferably, the composition (B) is applied for a leave-on time ranging from 1 minute to 1 hour, and in particular from 2 to 10 minutes.

The dyeing process according to the present invention can optionally also comprise at least one intermediate rinsing step between the step of applying the composition (A) and the step of applying the composition (B).

According to one particular embodiment, the composition (B) is applied to the keratin fibres directly after applying the composition (A), without an intermediate rinsing step.

At the conclusion of the dyeing process, the hair is optionally rinsed, then optionally dried or left to dry. According to one particularly preferred embodiment, the treatment for dyeing keratin fibres according to the present invention also comprises at least one step of heat-treating the keratin fibres.

More preferentially, this step of heat-treating the keratin fibres is carried out between the first step of applying the composition (A) and the second step of applying the composition (B). In other words, according to this embodiment, the process for dyeing keratin fibres according to the present invention comprises:

- at least one step of applying to said keratin fibres a composition (A), as defined previously,

- at least one step of heat treating said keratin fibres, and

- at least one step of applying to said keratin fibres a composition (B), as defined previously,

the heat-treating step being carried out between the step of applying the composition (A) and the step of applying the composition (B).

After the composition (A) has been applied, the keratin fibres can optionally be rinsed.

Preferably, the step of heat-treating the keratin fibres is carried out at a temperature ranging from 40°C to 250°C, more preferentially from 90°C to 250°C, and better still from 180°C to 230°C.

Preferably, the heat treatment step is performed for a period ranging from 5 seconds to 1 hour, preferably ranging from 5 seconds to 1 minute, per lock of hair.

This heat treatment step is generally carried out by means of a heating tool such as straightening iron, a curling iron, a crimping iron, a waving iron, a hood, a hairdryer, an infrared heating system or heated rollers, and preferably by means of a straightening iron, a curling iron, a crimping iron or a waving iron, and preferably by means of a hairdryer or a straightening iron.

Thus, the heat treatment step makes it possible to dry and/or shape the keratin fibres.

Preferably, the heat treatment step can be followed and/or accompanied by a mechanical treatment carried out for example by means of a comb, a brush or a flat iron.

After application of the composition (A) according to this embodiment, the keratin fibres are optionally rinsed, then optionally wrung out, preferably wrung out. One or more heating means are applied once or in succession to the keratin fibres at a temperature preferably ranging from 40 to 250°C, more preferentially from 90 to 250°C and even better still from 180 to 230°C for a time ranging from 5 seconds to 1 hour and preferably from 5 seconds to 1 minute, per lock of hair. The heating means can optionally be combined with one or more mechanical means.

The present invention also relates to the use, as pretreatment, of at least two organosilanes, that are different from one another, as defined previously, for improving the dyeing properties of a composition comprising one or more anionic direct dyes, as defined previously.

According to the present invention, the term "keratin fibres" is intended to mean human keratin fibres and more particularly the hair.

EXAMPLES In the examples that follow, all the amounts are indicated as weight percentages relative to the total weight of the composition, unless otherwise indicated.

I. Example 1 a) Compositions tested

Compositions (Al) and (A2) according to the invention and comparative compositions (A3) and (A4) were prepared using the ingredients of which the contents are indicated in the table below.

Al A2 A3 A4 invention invention comparative comparative

3-aminopropyl

10 10

triethoxysilane - 10

Methyltriethoxysilane 1.5 3 - -

Lactic acid 3.5 3.5 3.5 3.5

Amodimethicone (and)

trideceth-6 (and) 1 1 1 1 cetrimonium chloride Water qs 100 qs 100 qs 100 qs 100

The composition (B) was prepared from the ingredients of which the contents are indicated, as weight percentages of active material relative to the total weight of the composition, in the table below.

b) Procedure

Each of the compositions (Al) to (A4) obtained above was applied to locks of 100% grey hair, in a proportion of 0.4 g per gram of lock.

The locks were then dried by blow drying, that is to say using a hairdryer and a brush, then a flat iron at a temperature of 190°C were passed over the locks, at a rate of 20 seconds per lock.

At the end of this heat and mechanical treatment step, the locks of hair were dampened and the composition (B) above was then applied to the locks of hair, in a proportion of 0.4 g per gram of lock. The locks were then rinsed with water and dried under a hood (60°C). The colour of each lock was then evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM2600D colorimeter.

In this L* a* b* system, the three parameters respectively denote the intensity of the colour (L*), the green/red colour axis (a*) and the blue/yellow colour axis (b*). The higher the value of L*, the lighter the colour. The higher the value of a*, the redder the colour and the higher the value of b*, the yellower the colour.

The variation in the colouration of the locks before and after dyeing is measured by (ΔΕ Ω δ*) which corresponds to the colour uptake according to the following equation:

Δ ab * = V(L* - L 0 *) 2 + (a* - a 0 *) 2 + (b* - b 0 *) 2

In this equation, L*, a* and b* represent the values measured after dyeing with compositions (Al) to (A4), and Lo*, ao* and bo* represent the values measured before dyeing, corresponding to an untreated control lock (100% white hair).

The greater the ΔΕ Ω δ* value, the greater the difference in colour of the lock before and after dyeing, which shows good colour uptake.

The results thus obtained are given in the table below.

In addition, Figure 1 presents the colour of the locks treated with the processes according to the invention using the compositions (Al) and (A2), or the comparative processes using the compositions (A3) and (A4), in comparison to the untreated control lock. The results thus obtained (table and figure) show that the process according to the present invention results in better dyeing properties, in particular in terms of colour uptake.

More particularly, the presence of at least two organosilanes, that are different from one another, improves the dyeing properties of the anionic direct dyes.

II. Example 2 a) Compositions tested

The following compositions (Al) and (B) were prepared from the ingredients listed in the tables above. b) Procedure

The composition (Al) was applied to four different locks of 100% grey hair, in a proportion of 0.4 g per gram of lock.

The following protocols (PI) to (P4) were carried out on each of the locks.

According to protocol (PI), after application of the composition (Al), the hair was rinsed and then dried by blow drying. The locks of hair were then dampened, and the composition (B) was applied, in a proportion of 0.4 g per gram of lock. The locks were then rinsed with water and dried under a hood (60°C).

According to protocol (P2), after application of the composition (Al), the hair was rinsed and then dried by blow drying. A flat iron at a temperature of 190°C was then passed over the hair. The locks were then dampened before application of the composition (B), in a proportion of 0.4 g per gram of lock. The locks were then rinsed with water and dried under a hood (60°C).

According to protocol (P3), after application of the composition (Al), the hair was only rinsed before application of the composition (B), in a proportion of 0.4 g per gram of lock. The locks were then rinsed with water and dried under a hood (60°C).

According to protocol (P4), after application of the composition (Al), the composition (B) is directly applied to the hair without intermediate rinsing step, in a proportion of 0.4 g per gram of lock. The locks were then rinsed with water and dried under a hood (60°C). c) Results

We show that the process according to the present invention results in better colour uptake of the anionic direct dyes. More particularly, the presence of at least two organosilanes, that are different from one another, improves the dyeing properties of the anionic direct dyes.

III. Example 3 a) Compositions tested

The compositions (Al) and (B) were prepared from the ingredients listed in the tables above. b) Procedure

The composition (Al) was applied to two different locks of 100% grey hair, in a proportion of 0.4 g per gram of lock.

The following routine protocols (Rl) and (R2) were carried out on each of the locks of hair.

According to protocol (Rl), after application of the composition (Al), the hair was rinsed and then dried by blow drying. The hair was then dampened before application of the composition (B), in a proportion of 0.4 g per gram of lock. The hair was then rinsed, and then dried. The step of applying the composition (B) was repeated three times one after the other.

According to protocol (R2), after application of the composition (Al), the hair was rinsed and then dried by blow drying. A flat iron at a temperature of 190°C was then passed over the hair and the hair was dampened, before application of the composition (B), in a proportion of 0.4 g per gram of lock. The hair was then rinsed, and then dried. The step of applying the composition (B) was repeated three times one after the other. c) Results

We show that the process according to the present invention makes it possible to obtain better dyeing properties, in particular in terms of dye uptake. The colourings obtained are persistent with respect to at least three shampooing operations. More particularly, the presence of at least two organosilanes, that are different from one another, improves the dyeing properties of the anionic direct dyes, this being even after three shampooing operations.