WO2018115450A1

WO2018115450A1 - Process for direct dyeing of keratin fibres comprising the application of two particular compositions

Info

Publication number: WO2018115450A1
Application number: PCT/EP2017/084405
Authority: WO
Inventors: Gérard Gabin; Leila Hercouet; Julia PUECH
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2016-12-22
Filing date: 2017-12-22
Publication date: 2018-06-28
Anticipated expiration: 2019-06-22
Also published as: FR3060985B1; FR3060985A1

Abstract

The present invention relates to a process for direct dyeing of keratin fibres, preferably human keratin fibres such as the hair, comprising the application to the fibres of an aqueous composition (A) which comprises a thickener, a direct dye, an organic solvent and water and of an oily composition (B) which comprises a thickener and an oil, the compositions (A) and (B) being applied either separately one after the other, or together in one and the same composition.

Description

Process for direct dyeing of keratin fibres comprising the application of two particular compositions

For a long time, many people have sought to modify the colour of their hair, and especially to dye it in order, for example, to mask their grey hair.

Two main methods exist for dyeing human keratin fibres.

The first type of dyeing is "permanent" or oxidation dyeing, which uses dyeing compositions containing oxidation dye precursors, generally referred to 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.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or colour modifiers. The variety of molecules used in the oxidation bases and couplers allows a wide range of colours to be obtained.

The second type of dyeing is "semi-permanent" dyeing or direct dyeing, which consists in applying, to the keratin fibres, direct dyes, which are coloured and colouring molecules that have affinity for said fibres, in leaving them on for a time, and then in rinsing them off.

In order to perform these dyeing operations, the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes, and natural dyes.

These dyes may be non-ionic, anionic, cationic or amphoteric.

The processes for direct dyeing of keratin fibres which use direct dyeing compositions and in particular those using compositions comprising anionic direct dyes (also known as acid direct dyes) must often be performed by professionals since they are very specific protocols, so as to minimize as much as possible the staining of the scalp. Specifically, these processes make it possible to obtain excellent performance qualities in terms of persistence of the colouring on the fibre, but often have the drawback of also pigmenting the scalp.

Furthermore, the compositions used in these dyeing processes must have good general performance qualities, especially as regards:

- their working qualities, especially in terms of texture, ease of application and ease of spreading on the hair tips;

- their dyeing qualities, especially in terms of build-up, intensity, chromaticity, fastness and/or selectivity of the colouring obtained;

- their hair-conditioning and haircare qualities especially in terms of softness, suppleness and ease of disentangling of dyed hair.

Consequently, there is a need to develop a novel direct dyeing process which does not have the above drawbacks.

In particular, there is a need to develop a novel direct dyeing process which results in excellent performance qualities in terms of dyeing and fastness of the colouring, while at the same time not staining the scalp, or minimizing as much as possible the staining of the scalp.

It has now been discovered, surprisingly, that a process for direct dyeing of keratin fibres, comprising the application to the fibres of an aqueous composition (A) which comprises a thickener, a direct dye, an organic solvent and water and of an oily composition (B) which comprises a thickener and an oil, makes it possible to address the drawbacks encountered in the prior art protocols, and to achieve the above objectives.

A subject of the invention is thus a process for direct dyeing of keratin fibres, in particular human keratin fibres such as the hair, characterized in that the following compositions are applied to said keratin fibres:

a) an aqueous composition (A) comprising:

- one or more direct dyes,

- one or more aqueous-phase thickeners,

- one or more organic solvents, and

- water representing at least 50% by weight relative to the total weight of the aqueous composition (A),

b) an oily composition (B) comprising:

- one or more oils, and - one or more fatty-phase thickeners,

the compositions (A) and (B) being applied either separately one after the other, or together in one and the same composition,

the total content of direct dyes representing at least 0.1% by weight, relative to the total weight of the compositions (A) and (B) applied to the fibres,

the total content of oil(s) representing from 8% to 50% by weight relative to the total weight of the compositions (A) and (B), and

the weight ratio of the amount of composition (B) to the amount of composition (A) being greater than 0.1.

One advantage of the process according to the invention is that it makes it possible to obtain excellent performance qualities in terms of dyeing on the fibre, while at the same time minimizing the staining of the scalp.

Specifically, when the compositions (A) and (B) are applied to the head of hair, the oily phase (B) forms a protective layer at the surface of the scalp which isolates it from the aqueous composition (A) which comprises the direct dye(s).

Furthermore, in the process according to the invention, the compositions (A) and (B) have good working qualities, especially in terms of texture, ease of application and ease of spreading on the hair tips.

The process according to the invention also makes it possible to obtain excellent dyeing qualities, especially in terms of build-up, intensity, chromaticity, fastness and/or selectivity of the colouring obtained.

Finally, the process according to the invention makes it possible to obtain very good hair-conditioning and haircare qualities especially in terms of softness, suppleness and ease of disentangling of dyed hair.

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

According to the present patent application, the term "keratin fibres" mainly denotes human keratin fibres and in particular the hair. As previously mentioned, the process according to the invention comprises the application of an aqueous composition (A) which comprises one or more direct dyes.

The term "direct dye" is intended to mean natural and/or synthetic dyes, other than oxidation dyes. They are dyes that will superficially diffuse on the fibre and dye the fibres by themselves.

The direct dye(s) that may be used according to the invention are preferentially chosen from natural or synthetic, cationic, anionic or non-ionic direct dyes.

The term "natural dyes" or "dyes of natural origin" is intended to mean dyes derived from natural materials (plant, mineral or animal origin), for instance extracts, ground material and decoctions, which have a greater or smaller concentration of dyes.

Included among the natural dyes according to the invention are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis.

The natural dyes may be chosen especially from spinulosin, orceins, polyphenols or ortho-diphenols (also referred to as ODPs in the rest of the description) and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3- dione, indigoids including indigo, phthalocyanines and porphyrins in particular complexed to a metal, glycosyl or non-glycosyl iridoids, chromene dyes, anthraquinone and naphthoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanones, flavanols; and anthocyanidols. Use may also be made of extracts or decoctions containing these natural dyes and especially plant extracts or poultices containing said dyes.

According to a preferred embodiment of the invention, the direct dye(s) that may be used according to the invention are chosen from anionic dyes, commonly referred to as "acid" direct dyes on account of their affinity for alkaline substances. The anionic direct dyes according to the invention may be natural or synthetic.

The term "anionic direct dyes" is intended to mean any direct dye comprising in its structure at least one C0₂R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes. As anionic (or acid) direct dyes that may be used according to the invention, mention may be made especially of the dyes of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) below:

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

in which formulae (I) and (II):

- R₇, Rs, R9, Rio, R'7, R's, 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, 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;

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

- 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; in particular 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 previously defined;

- W represents a sigma bond σ, 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 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 (I) and (II) comprise at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical (O)CO -, M⁺ on one of the rings A, A', B, B' or C; preferentially sodium sulfonate.

As examples of dyes of formula (I), mention may be made especially of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, 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, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 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, Food Black 2 and Food Yellow 3 or Sunset Yellow.

As examples of dyes of formula (II), mention may be made especially of: Acid Red 111, Acid Red 134 and Acid Yellow 38.

b) the pyrazolone anionic azo dyes of formulae (III) and (IV):

in which formulae (III) and (IV):

- Ri i , Ri2 and Rn, 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 Ri5 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; - Ri9 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 (IV) comprise at least one sulfonate radical (0)2S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺ on one of the rings D or E; preferentially sodium sulfonate.

As examples of dyes of formula (III), mention may be made especially of: Acid Red 195, Acid Yellow 23, Acid Yellow 27 and Acid Yellow 76.

As an example of a dye of formula (IV), mention may be made especially of: Acid Yellow 17.

c) the anthraquinone dyes of formulae (V) and (VI):

in which formulae (V) and (VI):

- 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, more 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; in particular 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 (V) and (VI) comprise at least one sulfonate radical (0)₂S(0 )-, M⁺ or one carboxylate radical C(0)0^"-, M⁺; preferentially sodium sulfonate.

As examples of dyes of formula (V), mention may be made especially 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, Mordant Red 3 and EXT Violet N° 2.

As an example of a dye of formula (VI), mention may be made especially of: Acid Black 48.

d) the nitro dyes of formulae (VII) and (VIII):

in which formulae (VII) and (VIII):

- 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;

- polyhaloalkyl;

- 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;

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

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino;

more particularly, 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 more particularly represents an -NH- group;

- ALK represents a linear or branched divalent Ci-C₆ alkylene group; more particularly, ALK represents a -CH₂-CH₂- group;

- 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; more 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; more preferentially, J represents a radical -S0₂-;

- M' represents a hydrogen atom or a cationic counterion;

, which may be present or absent, represents a benzo group optionally substituted with one or more R30 groups as defined previously;

it being understood that formulae (VII) and (VIII) comprise at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺; more preferentially sodium sulfonate.

As examples of dyes of formula (VII), mention may be made especially of: Acid Brown 13 and Acid Orange 3. As examples of dyes of formula (VIII), mention may be made of: Acid Yellow 1, the 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, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid and EXT D&C Yellow 7.

e) the triarylmethane dyes of formula (IX):

in which formula (IX):

- 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; more particularly an alkyl and 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 group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto;

- nitro, nitroso;

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

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

more 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 an (0)₂S(0 group;

it being understood that at least one of the rings G, H, I or Γ comprises at least one sulfonate radical (0)2S(0^~)- or a carboxylate radical C(0)0^"-; more preferentially sulfonate.

As examples of dyes of formula (IX), mention may be made especially of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

f) the xanthene-based dyes of formula (X):

in which formula (X):

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

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

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto; - nitro, nitroso;

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

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

preferably, R49, R50, R51 and R52 represent a hydrogen or halogen atom;

- G represents an oxygen or sulfur atom or a group NRe with R_e as defined previously; more 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 or potassium;

- L' represents an oxygen or sulfur atom or an ammonium group: N⁺RfR_g, with Rf and R^g, which may be identical or different, representing a hydrogen atom, or an alkyl group or aryl group which is optionally substituted ; L' represents more particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0)_mS(0^~)-, M⁺ groups with m and M⁺ as defined previously;

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

- M⁺ is as defined previously.

As examples of dyes of formula (X), mention may in particular be made of: Acid Yellow 73; Acid Red 51 ; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9;

g) the indole-based dyes of formula (XI):

in which formula (XI):

- 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;

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

- G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; more 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 (XI) comprises at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺; more preferentially sodium sulfonate.

As an example of a dye of formula (XI), mention may be made especially of: Acid Blue 74.

h) the quino line-based dyes of formula (XII):

in which formula (XII):

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

- or alternatively R51 with R52, or 51 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 (XII) comprises at least one sulfonate radical (0)₂S(0^~)-, more preferentially sodium sulfonate.

As examples of dyes of formula (XII), mention may be made especially of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

The anionic direct dye(s) that may be used according to the invention are preferentially chosen from those of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) as defined above.

More particularly, the dyes of formulae (I) to (X) that may be used according to the invention are chosen from:

(C.I. 45380) Acid Red 87 (formula X)

Sodium salt of of 2,4-dinitro-l-naphthol-7-sulfonic acid

(C.I. 10316)

(formula VIII)

(C.I. 10383) Acid Orange 3 (formula VII)

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

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

(C.I. 13711) Acid Black 52 (formula I)

(C.I. 13065) Acid Yellow 36 (formula I)

Sodium salt of l-hydroxy-2-(2',4'-xylyl-5-

(C.I. 14700) sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1

(formula I)

(C.I. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (formula I)

Sodium salt of 4-hydroxy-3-[(2-methoxy-5-

(C.I. 14805) nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 (formula I)

Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 /

(C.I. 15510)

Orange 4 (formula I)

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

(C.I. 16185) Acid Red 27 / Food Red 9 (formula I) (C.I. 16230) Acid Orange 10 / Food Orange 4 (formula I)

(C.I. 16250) Acid Red 44 (formula I)

(C.I. 17200) Acid Red 33 / Food Red 12 (formula I)

(C.I. 15685) Acid Red 184 (formula I)

(C.I. 19125) Acid Violet 3 (formula I)

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

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

Food Red 11 (formula I)

(C.I. 18130) Acid Red 135 (formula I)

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

(C.I. 19140) Acid Yellow 23 / Food Yellow 4 / Yellow 5 (formula III)

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

(C.I. 20170)

dihydroxybenzene / Acid Orange 24 (formula I)

Sodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-

(C.I. 20470) 8-hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1

(formula I)

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

(C.I. 23266) 4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid

Red 111 (formula II)

(C.I. 27755) Food Black 2 (formula I)

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

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

(tetrasodium salt) / Food Black 1 (formula I)

(C.I. 42090) Acid Blue 9 (formula IX)

(C.I. 60730) Acid Violet 43 / Ext Violet 2 (formula V)

(C.I. 61570) Acid Green 25 (formula V)

Sodium salt of l-amino-4-cyclohexylamino-9,10-

(C.I. 62045)

anthraquinone-2-sulfonic acid / Acid Blue 62 (formula V) (C.I. 62105) Acid Blue 78 (formula V)

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

(C.I. 14710)

naphthalenesulfonic acid / Acid Red 4 (formula I)

2-Piperidino-5-nitrobenzenesulfonic acid (formula VIII)

2-(4'-N,N-(2"-Hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid (formula VIII)

4- -hydroxyethylamino-3-nitrobenzene

sulfonic acid (formula VIII)

(C.I. 42640) Acid Violet 49 (formula IX)

(C.I. 42080) Acid Blue 7 (formula IX)

Sodium salt of l,2-dihydroxy-3-sulfoanthraquinone /

(C.I. 58005)

Mordant Red 3 (formula V)

Sodium salt of l-amino-9,10-dihydro-9,10-dioxo-4-

(C.I. 62055) (phenylamino) 2-anthracenesulfonic acid / Acid Blue 25

(formula V)

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

(C.I. 14710)

naphthalenesulfonic acid / Acid Red 4 (formula I)

(C.I. 16255) Acid Red 18 (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, BD 12 JBN England.

The anionic direct dye(s) that are particularly preferred according to the invention are chosen from l,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid (C.I. 58005), the monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l- anthracenyl)amino]-5-methylbenzenesulfonic acid (C.I. 60730), the monosodium salt of 4-[(2-hydroxy- 1 -naphthyl)azo]benzenesulfonic acid (C.I. 15510), the disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid (C.I. 15985), the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenedisulfonic acid (C.I. 17200), the disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8- hydroxy-3,6-naphthalenedisulfonic acid (C.I. 20470), the disodium salt of N-ethyl-N- [4-[[4-[ethyl[3-sulfophenyl]methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5- cyclohexadien-l-ylidene]-3-sulfobenzenemethanaminium hydroxide (C.I. 42090), the disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)diimino]bis[5- methyl] -benzenesulfonic acid (C.I. 61570), the trisodium salt of 5 -hydroxy- 1 -(4- sulfophenyl)-4-(4-sulfophenylazo)pyrazole-3-carboxylic acid (C.I. 19140), sodium 4- [(9, 10-dihydro-4-hydroxy-9, 10-dioxo- 1 -anthryl)amino]toluene-3-sulfonate (C.I. 60730), the trisodium salt of 7-hydroxy-8-[(4-sulfo-l-naphthalenyl)azo]-l,3- naphthalenedisulfonic acid (C.I. 16255), and a mixture of these compounds.

Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of structures (I) to (XII).

In a preferred variant of the invention, the direct dye(s) are chosen from anionic direct dyes.

The direct dye(s) represent(s) a total content of at least 0.1% by weight, preferably at least 0.15% by weight, preferably from 0.2%> to 5%> by weight, relative to the total weight of the compositions (A) and (B) applied to the fibres.

As indicated previously, the aqueous composition (A) used in the process according to the invention comprises one or more aqueous-phase thickeners.

According to the present invention, the term "aqueous-phase thickener" is intended to mean compounds which, by their presence at a concentration of 0.05% by weight, increase the viscosity of an aqueous composition into which they are introduced by at least 20 cps, preferably by at least 50 cps, at ambient temperature (25°C), at atmospheric pressure and at a shear rate of 1 s^"1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheo meter or the like).

The aqueous-phase thickener(s) are preferentially chosen from non- associative thickening polymers bearing sugar units, non-associative thickening polymers without sugar units, associative thickening polymers, and mixtures of these compounds.

For the purposes of the present invention, the term "sugar unit" is intended to mean an oxygen-bearing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and which comprises at least 4 carbon atoms.

The sugar units may be optionally modified by substitution, and/or by oxidation and/or by dehydration. The sugar units that may be included in the composition of the aqueous-phase thickening polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.

Non-associative thickening polymers bearing sugar units that may especially be mentioned include native gums such as:

a) tree or shrub exudates, including:

- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);

- ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);

- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);

- gum tragacanth (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);

b) gums resulting from algae, including:

- agar (polymer derived from galactose and anhydrogalactose);

- alginates (polymers of mannuronic acid and of glucuronic acid);

- carrageenans and furcellerans (polymers of galactose sulfate and of anhydrogalactose sulfate);

c) gums resulting from seeds or tubers, including:

- guar gum (polymer of mannose and galactose);

- locust bean gum (polymer of mannose and galactose);

- fenugreek gum (polymer of mannose and galactose);

- tamarind gum (polymer of galactose, xylose and glucose);

- konjac gum (polymer of glucose and mannose);

d) microbial gums, including:

- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);

- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);

- scleroglucan gum (glucose polymer);

e) plant extracts, including: - cellulose (glucose polymer);

- starch (glucose polymer) and

- inulin.

These polymers can be physically or chemically modified. As physical treatment, mention may in particular be made of the temperature.

Chemical treatments that may be mentioned include esterification, etherification, amidation and oxidation reactions. These treatments make it possible to produce polymers that may especially be non-ionic, anionic or amphoteric.

Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.

The non- ionic guar gums that may be used according to the invention may be modified with Ci-C₆ (poly)hydroxyalkyl groups.

Among the Ci-C₆ (poly)hydroxyalkyl groups, mention may be made, by way of example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance, propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functional groups present on the guar gum.

Such non-ionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by the company Rhodia Chimie.

The botanical origin of the starch molecules that may be used in the present invention may be cereals or tubers. Thus, the starches are chosen, for example, from corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.

The starches may be chemically or physically modified, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.

Distarch phosphates or compounds rich in distarch phosphate will preferentially be used, for instance the product sold under the references Prejel VA- 70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) or Prejel 200 (gelatinized acetyl cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

According to the invention, amphoteric starches may also be used, these amphoteric starches comprising one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites; they are preferably bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.

The starch molecules may be derived from any plant source of starch, in particular such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above. The starch is preferably derived from potato.

The nonassociative thickening polymers of the invention may be cellulose- based polymers not comprising a C10-C30 fatty chain in their structure.

According to the invention, the term "cellulose-based polymer" is intended to mean any polysaccharide compound having in its structure sequences of glucose residues linked together via β-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives may be anionic, cationic, amphoteric or non-ionic.

Thus, the cellulose polymers that may be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers.

Among these cellulose-based polymers, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

Among the cellulose esters are mineral esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.), and mixed organic/mineral esters of cellulose, such as cellulose acetatebutyrate sulfates and cellulose acetatepropionate sulfates. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

Among the non-ionic cellulose ethers without a C10-C30 fatty chain, i.e. which are "non-associative", mention may be made of (Ci-C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example, Ethocel standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci-C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxy ethylcelluloses (for example, Natrosol 250 HHR provided by Aqualon) and hydroxypropylcelluloses (for example, Klucel EF from Aqualon); mixed (poly)hydroxy(Ci-C4)alkyl-(Ci-C4)alkylcellulose celluloses, such as hydroxypropylmethylcelluloses (for example, Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example, Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses.

Among the anionic cellulose ethers without a fatty chain, mention may be made of (poly)carboxy(Ci-C4)alkylcelluloses and salts thereof. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.

Among the cationic cellulose ethers without a fatty chain, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in patent US 4 131 576, such as (poly)hydroxy(Ci-C4)alkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted in particular with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® H 100 by the company National Starch.

Among the non-associative thickening polymers not bearing sugar units that may be used according to the invention, mention may be made of crosslinked acrylic acid or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2- methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or ash mixtures.

A first family of nonassociative thickening polymers that is suitable for use is represented by crosslinked acrylic acid homopolymers.

Among the homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, for instance, the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA. These polymers have the INCI name Carbomer.

The nonassociative thickening polymers may also be crosslinked (meth)acrylic acid copolymers, such as the polymer sold under the name Aqua SF1 by the company Noveon.

The nonassociative thickening polymers may be chosen from crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked acrylamide copolymers thereof.

Among the partially or totally neutralized crosslinked copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to said document as regards these polymers.

The aqueous composition (A) may similarly comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.

An example of an ammonium acrylate homopolymer that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide that may be mentioned is the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst. Reference may be made in particular to documents FR 2 416 723, US 2 798 053 and US 2 923 692 as regards the description and preparation of such compounds.

Use may also be made of cationic thickening polymers of acrylic type.

Among the aqueous-phase-thickening polymers, mention may also be made of associative polymers that are well known to those skilled in the art and especially of non-ionic, anionic, cationic or amphoteric nature.

It is recalled that "associative polymers" are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

The term "hydrophobic group" is intended to mean a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms. Preferably, the hydrocarbon-based group is derived from a mono functional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, such as, for example, polybutadiene.

Among the associative polymers of anionic type that may be mentioned are:

- (a) those comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those of which the hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly still a vinylcarboxylic acid and most particularly an acrylic acid or a methacrylic acid or mixtures thereof.

Among these anionic associative polymers, the ones that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methy lenebisacrylamide .

Among the latter polymers, the ones most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 OE) stearyl alcohol ether (Steareth 10), especially those sold by the company CIBA under the names Salcare SC80® and Salcare SC90®, which are aqueous 30%> emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth- 10 allyl ether (40/50/10).

- (b) those comprising i) at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the (C10-C30) alkyl ester of an unsaturated carboxylic acid type.

(C10-C30) alkyl esters of unsaturated carboxylic acids that are useful in the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949. Use will more particularly be made, among anionic associative polymers of this type, of those composed of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4%) to 40%) by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0%> to 6%> by weight of crosslinking polymerizable monomer, or else of those composed of 98%> to 96%o by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, preference is very particularly given, according to the present invention, to the products sold by the company Goodrich under the trade names Pemulen TRl®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TRl®, and to the product sold by the company SEPPIC under the name Coatex SX®.

Mention may also be made of the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

- (c) maleic anhydride/C3o-C38 a-olefin/alkyl maleate terpolymers, such as the product (maleic anhydride/C3o-C38 a-olefm/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies.

- (d) acrylic terpolymers comprising:

i) about 20%> to 70%> by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],

ii) about 20% to 80% by weight of an α,β-monoethylenically unsaturated non- surfactant monomer other than [A],

iii) about 0.5% to 60% by weight of a non-ionic monourethane which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,

such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 OE) terpolymer, as an aqueous 25% dispersion.

(e) copolymers comprising among their monomers an α,β- monoethylenically unsaturated carboxylic acid and an ester of an α,β- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol. Preferentially, these compounds also comprise as monomer an ester of an α,β- monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by the company Rohm & Haas.

- (f) amphiphilic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part. These polymers may be crosslinked or non- crosslinked. They are preferably crosslinked.

The ethylenically unsaturated monomers bearing a sulfonic group are especially chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci- C22)alkylsulfonic acids, N-(Ci-C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

(Meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will more particularly be used.

The polymers of this family may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00/31154. These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. The preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer.

These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, β- substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

These copolymers are described in particular in patent application EP-A-750 899, patent US 5 089 578 and in the following publications from Yotaro Morishima:

- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

- Micelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, 2000, Vol. 33, No. 10, 3694-3704;

- Solution properties of micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, 2000 Vol. 16, No. 12, 5324-5332;

- Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221.

Among these polymers, mention may be made of:

- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide or (C8-Ci6)alkyl(meth)acrylate units relative to the polymer, such as those described in patent application EP-A750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C₆- Ci8)alkylacrylamide units, such as those described in patent US-5 089 578.

Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above. Among the cationic associative polymers, mention may be made of:

(a) cationic associative polyurethanes;

(b) the compound sold by the company Noveon under the name Aqua CC and which corresponds to the INCI name Polyacrylate-1 Crosspolymer.

Polyacrylate-1 Crosspolymer is the product of polymerization of a monomer mixture comprising:

- a di(Ci-C₄ alkyl)amino(Ci-C6 alkyl) methacrylate,

- one or more C1-C30 alkyl esters of (meth)acrylic acid,

- a polyethoxylated C10-C30 alkyl methacrylate (20-25 mol of ethylene oxide units),

- a 30/5 polyethylene glycol/polypropylene glycol allyl ether,

- a hydroxy(C2-C₆ alkyl) methacrylate, and

- an ethylene glycol dimethacrylate.

(c) quatemized (poly)hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the above quatemized celluloses or hydroxy ethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quatemized alkylhydroxyethylcelluloses containing C₈- C30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18-B® (C12 alkyl) and Quatrisoft LM-X 529-8® (Ci8 alkyl) sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (C₁₈ alkyl) sold by the company Croda and the product Softcat SL 100® sold by the company Aqualon.

(d) cationic polyvinyllactam polymers.

Such polymers are described, for example, in patent application WO- 00/68282.

As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacryl- amidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylami dopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamid -opropylammonium tosylate or chloride terpolymers are used in particular. The amphoteric associative polymers are preferably chosen from those comprising at least one noncyclic cationic unit. Even more particularly, those prepared from or comprising 1 mol% to 20 mol%, preferably 1.5 to 15 mol% and even more particularly 1.5 to 6 mol% of fatty-chain monomer relative to the total number of moles of monomers are preferred.

Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.

The associative polymers of non- ionic type that may be used according to the invention are preferably chosen from:

(a) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers, of which examples that may be mentioned include:

- the products Antaron V216® or Ganex V216®

(vinylpyrrolidone/hexadecene copolymer), sold by the company ISP,

the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer), sold by the company ISP;

(b) copolymers of Ci-C₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, for instance, the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®;

(c) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer;

(d) polyurethane poly ethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;

(e) polymers with an aminoplast ether backbone containing at least one fatty chain, such as the Pure Thix® compounds sold by the company Sud-Chemie;

(f) celluloses or derivatives thereof, modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof wherein the alkyl groups are of C₈, and in particular: * non-ionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (C₁₆ alkyl) sold by the company Aqualon;

* non- ionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500 sold by the company Amerchol;

* non- ionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the company Berol Nobel;

(g) associative guar derivatives, for instance hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a C₁₄ alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie.

Preferably, the polyurethane polyethers comprise at least two hydrocarbon- based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being side chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer having a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer). These same polymers may also be graft polymers or star polymers.

The non-ionic fatty-chain polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups. The non- ionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, hence the origin of the name.

By extension, also included among the non-ionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.

As examples of non- ionic fatty-chain polyurethane polyethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®. Mention may also be made of the product Elfacos T210® bearing a C₁₂-C₁₄ alkyl chain, and the product Elfacos T212® bearing a C₁₈ alkyl chain, from Akzo.

The product DW 1206B® from Rohm & Haas bearing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.

Use may also be made of solutions or dispersions of these polymers, in particular in water or in aqueous/alcoholic medium. Examples of such polymers that may be mentioned include Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.

The polyurethane polyethers which can be used according to the invention are in particular those described in the paper by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380.389 (1993).

It is even more particularly preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a poly condensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%>) and water (26%>)].

Preferably, the aqueous-phase thickener(s) are chosen from polymers not comprising any sugar units.

More preferentially, the aqueous-phase thickener(s) are chosen from associative or non-associative thickening polymers bearing acrylic or methacrylic units, and polymers bearing 2-acrylamido-2-methylpropanesulfonic acid units and/or the salified form thereof.

In a preferred variant of the invention, the aqueous-phase thickener(s) are chosen from acrylic acid homopolymers or copolymers, in particular acrylic acid homopolymers, homopolymers or copolymers of 2-acrylamido-2- methylpropanesulfonic acid and/or the salified form thereof, in particular copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof, more particularly copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof and of acrylamide or copolymers of 2-acrylamido-2- methylpropanesulfonic acid and/or the salified form thereof and of hydroxyethyl acrylate, said polymers possibly being crosslinked or non-crosslinked.

The aqueous-phase thickener(s) generally represent a total content ranging from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight and better still from 1.5% to 10%> by weight, relative to the total weight of the aqueous composition (A).

The aqueous-phase thickener(s) generally represent a total content ranging from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight and better still from 1% to 5% by weight, relative to the total weight of the compositions (A) and (B).

The aqueous composition (A) used in the process according to the invention also comprises one or more organic solvents.

According to the invention, the organic solvents which can be used are liquid at ambient temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013^x 10⁵ Pa).

Preferably, the organic solvent(s) are chosen from linear or branched monoalcohols containing from 1 to 8 carbon atoms, polyols, polyethylene glycols, aromatic alcohols, and mixtures of these compounds.

Preferably, the organic solvents are chosen from ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, benzyl alcohol and phenoxy ethanol, and mixtures of these compounds.

Most particularly preferably, the organic solvent(s) are chosen from ethanol, dipropylene glycol and benzyl alcohol, and a mixture of these compounds.

The organic solvent(s) generally represent a total content ranging from 1% to 30% by weight, preferably from 2% to 25% by weight and better still from 10% to 20%) by weight, relative to the total weight of the aqueous composition (A).

The organic solvent(s) generally represent a total content ranging from 0.5% to 20% by weight, preferably from 1% to 15% by weight and better still from 5% to 10% by weight, relative to the total weight of the compositions (A) and (B).

The aqueous composition (A) used in the process according to the invention also comprises water. The water represents at least 50% by weight, preferably from 50%> to 95% by weight, more preferably from 60% to 90% by weight and even better from 65% to 80% by weight relative to the total weight of the aqueous composition (A).

The water generally represents from 20% to 85% by weight, preferably from 30% to 70% by weight and more preferentially from 40% to 60% by weight relative to the total weight of the compositions (A) and (B).

As previously mentioned, the process according to the invention comprises the application of an oily composition (B).

The oily composition (B) used in the process according to the invention comprises one or more oils.

The term "oil" is intended to mean any fatty substance that is in liquid form at ambient temperature (25°C) and at atmospheric pressure.

The term "fatty substance" is intended to mean an organic compound that is insoluble in water at ambient temperature (25°C) and at atmospheric pressure (1.013x 10⁵ Pa) (solubility of less than 5% by weight, preferably less than 1 % by weight and even more preferably less than 0.1% by weight). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms and/or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.

The oil(s) present in the oily composition (B) used in the process according to the invention may be volatile or non-volatile.

The volatile or non-volatile oils may be hydrocarbon-based oils, especially of animal or plant origin, synthetic oils, silicone oils or fluoro oils, or mixtures thereof.

For purposes of the present invention, the term "silicone oil" is intended to mean an oil comprising at least one silicon atom and in particular at least one Si-0 group.

The term "hydrocarbon-based oil" is intended to mean an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and/or phosphorus atoms. A hydrocarbon-based oil does not comprise any silicon atoms.

The oil(s) present in the oily composition (B) used in the process according to the invention may be non-volatile. For the purposes of the present invention, the term "non-volatile oil" is intended to mean an oil having a vapour pressure of less than 0.13 Pa (0.01 mmHg).

The non- volatile oils may be chosen especially from non- volatile hydrocarbon-based oils, which may be fluorinated, and/or non-volatile silicone oils.

As non- volatile hydrocarbon-based oils that are suitable for use in the invention, mention may be made especially of:

- hydrocarbon-based oils of animal origin,

- hydrocarbon-based oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutanate, for example sold under the name Eldew PS203 by Ajinomoto, triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially heptanoic or octanoic triglycerides, sweet almond oil, argan oil, avocado oil, groundnut oil, camellia oil, safflower oil, beauty- leaf oil, rapeseed oil, copra oil, coriander oil, marrow oil, wheatgerm oil, jojoba oil or liquid jojoba wax, linseed oil, macadamia oil, corn germ oil, hazelnut oil, walnut oil, vernonia oil, apricot kernel oil, olive oil, evening primrose oil, palm oil, passion flower oil, grapeseed oil, rose oil, castor oil, rye oil, sesame oil, rice bran oil, camelina oil, soybean oil, sunflower oil, pracaxi oil, babassu oil, mongongo oil, marula oil, arara oil, shea butter oil, Brazil nut oil; or alternatively caprylic/capric acid triglycerides, for instance those sold by by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by by the company Dynamit Nobel, and the refined plant perhydrosqualene sold under the name Fitoderm by the company Cognis; the plant squalene sold, for example, under the name Squalive by the company Biosynthis;

- hydrocarbon-based oils of mineral or synthetic origin, for instance:

(a) synthetic ethers containing from 10 to 40 carbon atoms;

(b) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and squalane, and mixtures thereof, and in particular hydrogenated polyisobutene;

(c) synthetic esters, for instance oils of formula RiCOOR₂ in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R₂ represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that Ri + R₂ > 10. The esters may be chosen especially from fatty acid esters, for instance:

- cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate, and mixtures thereof, C₁₂ to C₁₅ alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters, for instance isostearyl lactate and diisostearyl malate;

- polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate;

- esters of diol dimers and of diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-DA7® sold by the company Nippon Fine Chemical and described in patent application FR 03/02809;

(d) fatty alcohols that are liquid at ambient temperature, bearing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol and 2-undecyl-pentadecanol;

(e) non-salified higher fatty acids such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof; and

(f) dialkyl carbonates, the two alkyl chains possibly being identical or different, such as the dicaprylyl carbonate sold under the name Cetiol CC® by Cognis;

(g) and mixtures thereof.

The non- volatile silicone oils are chosen, for example, from non- volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the ends of a silicone chain, these groups each having from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxy silicates, and dimethicones or phenyl trimethicones with a viscosity of less than or equal to 100 cSt, and mixtures thereof.

The non- volatile oils may be chosen from mixtures of hydrocarbon-based and silicone non- volatile oils.

The oil(s) present in the oily composition (B) used in the process according to the invention may be volatile.

For the purposes of the present invention, the term "volatile oil" is intended to mean an oil (or non-aqueous medium) that is capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at ambient temperature, especially having a non-zero vapour pressure, at ambient temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10^~3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffms), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar® or Permethyl®.

Volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethyl- cyclopentane, and mixtures thereof, may also be used.

Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity < 8 centistokes (8x 10^"6 m²/s), and especially having from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of dimethicones with a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

It is also possible to use a mixture of hydrocarbon-based and silicone volatile oils. Preferably, the oil(s) are chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, non-silicone oils of animal origin, oils of plant origin, fluoro oils, liquid fatty alcohols, liquid fatty esters, non-salified liquid fatty acids, silicone oils, and mixtures of these compounds.

For the purposes of the present invention, the term "fatty alcohol, ester or acid" is intended to mean an alcohol, ester or acid comprising a linear or branched, saturated or unsaturated alkyl chain, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and more preferentially from 12 to 24 carbon atoms.

Particularly preferably, the oil(s) are chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, liquid fatty esters, oils of plant origin, especially hydrocarbon-based oils of plant origin, and mixtures of these compounds.

Most particularly preferably, the oil(s) are chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, oils of plant origin, especially hydrocarbon-based oils of plant origin, and mixtures of these compounds.

The oil(s) generally represent a total content ranging from 50% to 99% by weight, preferably from 70%> to 98%> by weight and better still from 80%> to 95% by weight, relative to the total weight of the oily composition (B).

The oil(s) represent a total content ranging from 8% to 50% by weight, preferably from 10% to 45% by weight and better still from 15% to 40% by weight, relative to the total weight of the compositions (A) and (B).

The oily composition (B) used in the process according to the invention also comprises one or more fatty-phase thickeners.

According to the present invention, the term "fatty-phase thickener" is intended to mean compounds which, by their presence in a content of 0.05%> by weight, increase the viscosity of an oily composition into which they are introduced by at least 20 cps, preferably by at least 50 cps, at 25°C, at atmospheric pressure and at a shear rate of 1 s^"1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheo meter or the like).

The notion of a fatty-phase thickener is analogous to the notion of a lipophilic thickener. The fatty-phase thickener(s) used in the oily composition (B) used in the process according to the invention may be chosen from mineral fatty-phase thickeners and organic fatty-phase thickeners, and mixtures of these compounds.

The mineral fatty-phase thickeners that may be used in the oily composition (B) used in the process according to the invention are preferably mineral particles constituted essentially of mineral oxides and/or hydroxides.

These particles are preferably insoluble in water at ambient temperature (25°C). The term "insoluble" is intended to mean a solubility of less than 0.5% by weight.

Preferably, the number-average primary size of these mineral particles ranges from 0.01 to 500 μιη, it preferably ranges from 0.1 to 200 μιη and even more preferentially it ranges from 1 to 100 μιη.

For the purposes of the present invention, the term "primary particle size" is intended to mean the maximum dimension that it is possible to measure between two diametrically opposite points on an individual particle.

The size of the mineral particles may be determined by transmission electron microscopy or by measuring the specific surface area via the BET method or by laser particle size analysis.

The mineral particles that may be used in accordance with the invention may be in various forms, for example in the form of spheres, needles, flakes or platelets.

In a preferred variant of the invention, the mineral fatty-phase thickener(s) are platelet-shaped particles.

The mineral fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may preferably be chosen from silicas and silicates.

The silicates of the invention may be natural or chemically modified (or synthetic).

The silicates correspond to optionally hydrated silica in which some of the silicon atoms are replaced with metal cations such as Al³⁺, B³⁺, Fe³⁺, Ga³⁺, Be²⁺, Zn²⁺, Mg²⁺, Co³⁺, Ni³⁺, Na⁺, Li⁺, Ca²⁺, Cu²⁺.

More particularly, the silicates that may be used in the context of the invention are chosen from clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the vermiculite, stevensite and chlorite families. These clays may be of natural or synthetic origin. Clays that are cosmetically compatible and acceptable with keratin materials are preferably used.

The silicate may be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof.

Mention may thus be made of the compounds sold by Laporte under the name

Laponite XLG and Laponite XLS.

The silicate(s) are preferably chosen from bentonites and hectorites.

The silicates may be modified with a compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.

As silicates that are suitable for use, mention may be made of quaternium-18 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; quaternium-18/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay; quaternium-18 hectorites, such as those sold under the names Bentone Gel DO A, Bentone Gel EC05, Bentone Gel EUG, Bentone Gel IPP, Bentone Gel ISD, Bentone Gel SS71, Bentone Gel VS8 and Bentone Gel VS38 by Rheox, and Simagel M and Simagel SI 345 by Biophil.

The silicates that may be used in the oily composition (B) used in the process according to the invention may be chosen, in particular, from modified hectorites such as hectorite modified with C₁₀-C₁₂ fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.

As explained previously, the mineral fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may be silicas.

The silica(s) that may be used in the oily composition (B) used in the process according to the invention are preferably fumed.

The fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas bearing a large number of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by the company Degussa, and Cab-O-Sil HS-5®, Cab-O-Sil EH- 5®, Cab-O-Sil LM-130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by the company Cabot.

It is possible to chemically modify the surface of said silicas, via a chemical reaction generating a reduction in the number of silanol groups. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be:

(a) trimethylsiloxy groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as Silica silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;

(b) dimethylsilyloxy or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as Silica dimethyl silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O- Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.

Preferably, the fumed silicas that may be used in the oily composition (B) used in the process according to the invention are hydrophilic, such as the product sold under the name Aerosil 200®.

Preferably, the mineral fatty-phase thickener(s) are chosen from organophilic clays and hydrophilic fumed silicas, and mixtures thereof.

More preferentially, the mineral fatty-phase thickener(s) are chosen from hectorites modified with C₁₀-C₁₂ fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride, and hydrophilic fumed silicas such as the hydrophilic silicas sold under the name Aerosil 200®.

Even more preferentially, the mineral fatty-phase thickener(s) are chosen from hectorites modified with C₁₀-C₁₂ fatty acid ammonium chloride, especially hectorite modified with distearyldimethylammonium chloride, such as the product sold under the name Bentone 38VCG by Elementis, and the hectorite modified with stearylbenzyldimethylammonium chloride, such as the product sold under the name Bentone 27V by Elementis.

As explained previously, the fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may also be chosen from organic fatty-phase thickeners.

Preferably, the organic fatty-phase thickener(s) are chosen from semi- crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, N-acylamino acid amide derivatives, polymers comprising an alkylene and/or styrene block, such as polystearyl acrylates, elastomeric organopolysiloxanes, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds. These copolymers may be diblock, triblock or multi-block polymers, radial-block polymers, also known as star copolymers, or alternatively comb polymers.

Among the C8-C30 and preferably C18-C24 fatty acid esters, mention may be made of mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of polyols, more particularly mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids of glycerol. Use may especially be made of a mixture of these compounds such as a mixture of mono-, di and triesters of behenic acid and of glycerol.

Most particularly, the organic fatty-phase thickener(s) are chosen from semi- crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, polymers comprising an alkylene and/or styrene block, such as polystearyl acrylates, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds.

Even more preferentially, the organic fatty-phase thickener(s) are chosen from saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, C8-C30 and preferably C18-C24 fatty acid esters and mixtures thereof, better still mono- , di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of polyols, more particularly mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of glycerol.

Preferably, the fatty-phase thickener(s) are chosen from organic thickeners.

The fatty-phase thickener(s) generally represent a total content ranging from 1% to 40% by weight, preferably from 2% to 30% by weight and better still from 5% to 20% by weight, relative to the total weight of the oily composition (B). The fatty-phase thickener(s) generally represent a total content ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 1%) to 8%) by weight, relative to the total weight of the compositions (A) and (B).

The oily composition (B) used in the process according to the invention may also comprise any usual liposoluble or lipodispersible additive, for instance other solid or pasty fatty substances such as waxes, fatty alcohols or fatty acids. It may also comprise compounds such as alkylene carbonates, for instance propylene carbonate, which can reinforce the efficacy of certain fatty-phase thickeners such as silicates.

As explained previously, the weight ratio of the amount of oily composition (B) to the amount of aqueous composition (A) is greater than 0.1.

Advantageously, this ratio is greater than 0.10 and less than or equal to 1, and preferably ranges from 0.15 to 0.7 and more preferentially from 0.25 to 0.5.

Preferably, the aqueous composition (A) and the oily composition (B) used in the process according to the invention do not comprise surfactant. When said compositions do comprise surfactant, the content of surfactants is less than 2% by weight, relative to the total weight of each composition containing them.

The aqueous composition (A) and the oily composition (B) used in the process according to the invention may contain additives conventionally used in the cosmetics field other than those described previously, and chosen from UV-screening agents, resins, fragrances, peptizers, vitamins, amino acids, preservatives, alkaline agents, acidifying agents, etc.

Needless to say, those skilled in the art will take care to select the optional additional compounds and/or the amount thereof such that the advantageous properties of the process according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

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

Preferably, the aqueous composition (A) and the oily composition (B) are in the form of gels.

Preferably, each of the two compositions (A) and (B) has a viscosity of greater than or equal to 0.1 Pa.s, preferentially ranging from 0.1 to 500 Pa.s, more preferentially ranging from 0.5 to 300 Pa.s and even more preferentially ranging from 1 to 200 Pa.s, at a temperature of 25°C, at atmospheric pressure and at a shear rate of 1 s^"1 (measurable, for example, with a Haake RS600 rheometer).

Preferably, each of the two compositions (A) and (B) has a threshold stress at 25°C ranging from 0.1 to 300 Pa, preferably from 1 to 250 Pa and more preferably from 10 to 200 Pa.

The threshold stress is determined by scanning under stress at 25°C. An imposed-stress Thermo Haake RS600 rheometer with sandblasted cone-plate geometry is used. The temperature is regulated by a Peltier-effect plate and an anti-evaporation device (solvent trap filled with water for the measurements at 25°C).

A logarithmic stress elevation from 0.5 to 500 Pa is performed over a period of 3 minutes. Two adjustment lines corresponding to the stationary regimes (solid and liquid behaviours) are plotted on the curve representing the strain as a function of the stress (logarithmic coordinates). The intersection of these two lines gives the value of the stress threshold.

The pH of the aqueous composition (A) used in the process according to the invention generally ranges from 1.5 to 10 and preferably from 2 to 7. Even more preferentially, the pH of the aqueous composition (A) used in the process according to the invention is less than or equal to 5, better still ranging from 1.5 to 4 and even better still from 2 to 3.

As described previously, the compositions (A) and (B) used in the process according to the invention are applied either separately one after the other, or together in one and the same composition.

In a first variant of the invention, the compositions (A) and (B) are applied separately one after the other.

Preferably, in this variant, these two compositions are applied without intermediate rinsing.

Preferably, in this variant, the oily composition (B) is applied before the aqueous composition (A).

In a second variant of the invention, the compositions (A) and (B) are applied together in one and the same composition.

Preferably, in this second variant, the compositions (A) and (B) are applied together in one and the same composition prepared previously or obtained by extemporaneous mixing before application, and preferably prepared previously. In this variant, the composition resulting from the mixing of the compositions

(A) and (B) as defined previously can be prepared previously in the following way: a) a step of preparing, separately from each other, the compositions (A) and

(B) as described above, by mixing the constituents of each composition, then

b) a step of bringing the compositions (A) and (B) into contact.

The step of bringing the various compositions into contact can be carried out by means of one or more static or non-static mixers.

Thus, in order to prepare the mixture of the compositions (A) and (B), the ingredients of the composition (A) are mixed separately from the ingredients of the composition (B). Each of the compositions is prepared in a tank specifically dedicated thereto. Each composition is then separately introduced into a static or non- static mixer.

In the process according to the invention, the compositions (A) and (B) can be applied to dry or wet keratin fibres, having optionally undergone washing with a shampoo. Preferably, the compositions (A) and (B) are applied to dry keratin fibres.

On conclusion of the dyeing operation, the keratin fibres are generally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.

The compositions (A) and (B), whether they are applied one after the other or in one and the same composition, are left on for from 1 to 30 minutes, preferably from 2 to 20 minutes.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1 :

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

I. Characteristics of the compositions

The following aqueous compositions Al and A2 were prepared from the ingredients of which the contents are indicated in the table below.

The oily composition (B) was prepared from the ingredients of which the contents are indicated in the table below. Ingredients B

Mineral oil 90

Dextrin palmitate 10

II. Protocol for preparing the final compositions

At the time of use, 70% by weight of the aqueous composition Al and 30% by weight of the oily composition B are mixed together. A composition CI is obtained. The pH of this composition is equal to 3.

The process of applying this composition CI is according to the invention and is compared with the process of applying the composition A2 only. The pH of the composition A2 is also equal to 3.

The composition CI contains the same concentration of direct dyes as the composition A2.

III. Characterization methods

The dyeing performance qualities and the staining of the process according to the invention comprising the application of the composition CI and of a comparative process comprising the application of the composition A2 only were evaluated.

In vitro evaluations

The dyeing performance qualities are evaluated according to the protocol below:

Compositions CI and A2 are applied to locks of natural hair containing 90% grey hairs, on a hotplate at 40°C (4 g of composition per gram of lock of hair).

After a leave-on time of 15 minutes at 40°C, the locks of hair are rinsed. A standard shampoo is applied.

The colorimetric measurements are taken using a CM-3660d spectrophotometer in the CIELab system (illuminant D65, angle 10°). The colour variation ΔΕ is calculated from the following equation:

Δ E * = (L* - L₀ *)² + (a* - a₀ *)² + (b* - b₀ *)²

In this equation, the parameters L*, a* and b* represent the values measured on locks of hair after dyeing and the parameters Lo*, ao* and bo* represent the values measured on locks of untreated hair. The higher the ΔΕ value, the better the colour build-up on the keratin fibres.

The performance qualities in terms of staining of the scalp are evaluated according to the protocol below:

A standardized amount (50 μΐ in an Eppendorf pipette) of composition CI or A2 is deposited on a polyurethane membrane (scalp model).

Leave-on time: 15 min at 40°C (on a hotplate).

Rinsing, shampooing.

The colour variation ΔΕ' between the dyed membrane and the non-dyed membrane is then evaluated in the CIELab system using standardized photographs and then analysed with colorimetric measurement software.

ΔΕ' is calculated according to the preceding equation, L*, a* and b* representing here the values measured for the membrane after dyeing and the parameters Lo*, ao* and bo* representing the values measured for the untreated membrane. The greater the value of ΔΕ', the greater the staining.

IV. Results

In vitro results

The results obtained show that the process according to the invention which comprises the application of the composition CI which comprises the same amount of direct dyes as the composition A2 makes it possible to result in staining of the scalp two times less significant than with the comparative process, while at the same time exhibiting a very good colour build-up that is almost equivalent to the colour build-up obtained by means of the comparative process which comprises the application of the composition A2.

Example 2:

I. Characteristics of the compositions

The following aqueous compositions Al and A2 were prepared from the ingredients of which the contents are indicated in the table below. Ingredients Al A2

Hydroxyethylcellulose 0,4 0,33

Lactic acid 2,2 1,79

2-Phenoxyethano 1 0,8 0,65

Acrylamide / sodium acrylamido 2- methyl propane sulfonate /

4 3,25 hydroxyethylacrylate copolymer in

powder

Ext. Violet 2 (CI 60730) 0,09 0,07

Acid Black 1 (CI 20470) 0,07 0,06

Orange 4 (CI 15510) 0,26 0,21

Yellow 5 (CI 19140) 0,05 0,04

Benzyl Alcohol 4,2 3,41

Ethanol 7 5,69

Water Qs 100 Qs 100

The oily composition (B) was prepared from the ingredients of which the contents are indicated in the table below.

Ingredients B

Mixture of C15-C19 branched alkanes

Qs 100

(EMOGREEN L19 from SEPPIC)

Glyceryl dibehenate (and) tribehenin (and)

10

glyceryl behenate II. Protocols

At the time of use:

- 76.5% by weight of the aqueous composition Al and 23.5% by weight of the oily composition B are mixed together. A composition C 1 is obtained;

- 94.1% by weight of the aqueous composition A2 and 5.9% by weight of the oily composition B are mixed together. A composition C2 is obtained;

The process comprising the application of this composition CI is according to the invention and is compared with the comparative process comprising the application of the composition C2.

Compositions CI and C2 have a black phase and a white phase. They have the same contents of ingredients, with the exception of the total content of oils which is of 23.5%) by weight relative to the total weight of the composition CI , and of 5.9%> by weight relative to the total weight of the composition C2.

Compositions CI and C2 are respectively applied to two identical locks of natural hair containing 90% grey hairs (one composition per lock).

The dyeing performance and the staining of the scalp achieved with the process of the invention comprising the application of the composition CI and achieved with the comparative process comprising the application of the composition C2 as described above, were evaluated.

The hair dyeing obtained according to the process of the invention comprising the application of the composition CI , leads to a staining of the scalp which is significantly less important than the hair dyeing obtained according to the comparative process comprising the application of the composition C2 containing less than 6% by weight of oils relative to the total weight of the composition C2, while presenting equivalent dyeing performances.

Claims

1. Process for direct dyeing of keratin fibres, in particular human keratin fibres such as the hair, characterized in that the following compositions are applied to said keratin fibres:

a) an aqueous composition (A) comprising:

- one or more direct dyes,

- one or more aqueous-phase thickeners,

- one or more organic solvents, and

b) an oily composition (B) comprising:

- one or more oils, and

- one or more fatty-phase thickeners,

2. Process according to Claim 1, characterized in that the direct dye(s) are chosen from natural or synthetic, cationic, anionic or non-ionic direct dyes, and are preferably chosen from anionic direct dyes.

3. Process according to Claim 1 or 2, characterized in that the direct dye(s) are anionic direct dyes chosen from those of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) below, and the mesomeric or tautomeric forms thereof:

in which formulae (I) and (II):

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

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

- 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;

- cycloalkyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group;

- 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 previously defined;

- W represents a sigma bond σ, 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 form, with the carbon atom that bears them, a spiro cycloalkyl; it being understood that formulae (I) and (II) comprise at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical (O)CO -, M⁺ on one of the rings A, A', B, B' or C; preferentially sodium sulfonate;

in which formulae (III) and (IV):

- Ri i, 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 Ri5 with Ri6 together form a double bond;

- (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;

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

- Ra and Rb, which may be identical or different, are as defined previously;

- Y represents either a hydroxy 1 group or an oxo group;

it being understood that formulae (III) and (IV) comprise at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺ on one of the rings D or E; preferentially sodium sulfonate;

in which formulae (V) and (VI):

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or arylthio;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

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

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl;

- aryl optionally substituted with one or more groups, more 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;

- cycloalkyl; - Z represents a group chosen from hydroxyl and NR'2sR'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 (V) and (VI) comprise at least one sulfonate radical (0)2S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺; preferentially sodium sulfonate;

in which formulae (VII) and (VIII):

- alkyl;

- hydroxyl, mercapto;

- nitro, nitroso;

- polyhaloalkyl;

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

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

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino; - heterocycloalkyl;

- W is as defined previously;

- ALK represents a linear or branched divalent Ci-C₆ alkylene group;

- 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;

- 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;

- M' represents a hydrogen atom or a cationic counterion;

it being understood that formulae (VII) and (VIII) comprise at least one sulfonate radical (0)₂S(0^~)-, M⁺ or one carboxylate radical C(0)0^"-, M⁺;

in which formula (IX):

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

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto;

- nitro, nitroso;

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

- 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 radical (0)2S(0^~)- or a carboxylate radical C(0)0^"-;

(X) in which formula (X):

- 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;

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

preferably, R49, R50, R51 and R52 represent a hydrogen or halogen atom;

- G represents an oxygen or sulfur atom or a group NRe with R_e as defined previously;

- 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;

- L' represents an oxygen or sulfur atom or an ammonium group: N⁺RfR_g, with Rf and R_g, which may be identical or different, representing a hydrogen atom, or an alkyl group or aryl group which is optionally substituted;

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

+ is as defined previously;

in which formula (XI):

- 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;

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

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

it being understood that formula (XI) comprises at least one sulfonate radical (0)₂S(0 , M⁺ or one carboxylate radical C(0)0^"-, M⁺;

in which formula (XII):

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

- or alternatively R51 with R52, or 51 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 (XII) comprises at least one sulfonate radical (0)₂S(0 .

4. Process according to any one of the preceding claims, characterized in that the direct dye(s) are chosen from l,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid, the monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l- anthracenyl)amino]-5-methylbenzenesulfonic acid, the monosodium salt of 4-[(2- hydroxy- l-naphthyl)azo]benzenesulfonic acid, the disodium salt of 6-hydroxy-5-[(4- sulfophenyl)azo]-2-naphthalenesulfonic acid, the disodium salt of 5-amino-4-hydroxy-

3- (phenylazo)-2,7-naphthalenedisulfonic acid, the disodium salt of l-amino-2-(4'- nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid, the 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, the disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4- anthracenediyl)diimino]bis [5 -methyl] -benzenesulfonic acid, the trisodium salt of 5- hydroxy- 1 -(4-sulfophenyl)-4-(4-sulfophenylazo)pyrazole-3-carboxylic acid, sodium

4- [(9, 10-dihydro-4-hydroxy-9, 10-dioxo- 1 -anthryl)amino]toluene-3-sulfonate, the trisodium salt of 7-hydroxy-8-[(4-sulfo-l-naphthalenyl)azo]-l,3- naphthalenedisulfonic acid, and a mixture of these compounds.

5. Process according to any one of the preceding claims, characterized in that the direct dye(s) represent a total content of at least 0.15% by weight and preferably from 0.2% to 5% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

6. Process according to any one of the preceding claims, characterized in that the aqueous-phase thickener(s) are chosen from non-associative thickening polymers bearing sugar units, non-associative thickening polymers without sugar units, associative thickening polymers, and mixtures of these compounds, preferably are chosen from polymers not comprising any sugar units, and more particularly are chosen from associative or non-associative thickening polymers bearing acrylic or methacrylic units, and polymers bearing 2-acrylamido-2-methylpropanesulfonic acid units and/or the salified form thereof.

7. Process according to any one of the preceding claims, characterized in that the aqueous-phase thickener(s) are chosen from acrylic acid homopolymers or copolymers, in particular acrylic acid homopolymers, homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof, in particular copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof, more particularly copolymers of 2-acrylamido-2- methylpropanesulfonic acid and/or the salified form thereof and of acrylamide or copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof and of hydroxy ethyl acrylate, said polymers possibly being crosslinked or non- crosslinked.

8. Process according to any one of the preceding claims, characterized in that the aqueous-phase thickener(s) represent a total content ranging from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

9. Process according to any one of the preceding claims, characterized in that the aqueous-phase thickener(s) represent a total content ranging from 0.1% to 20% by weight, preferably from 0.5%> to 15% by weight and better still from 1.5% to 10%> by weight relative to the total weight of the aqueous composition (A).

10. Process according to any one of the preceding claims, characterized in that the organic solvent(s) are chosen from linear or branched monoalcohols containing from 1 to 8 carbon atoms, polyols, polyethylene glycols, aromatic alcohols, and mixtures of these compounds, and are more preferentially chosen from ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, benzyl alcohol and phenoxy ethanol, and mixtures of these compounds, and in particular are chosen from ethanol, dipropylene glycol and benzyl alcohol, and a mixture of these compounds.

11. Process according to any one of the preceding claims, characterized in that the organic solvent(s) represent a total content ranging from 0.5% to 20% by weight, preferably from 1% to 15% by weight and better still from 5% to 10% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

12. Process according to any one of the preceding claims, characterized in that the organic solvent(s) represent a total content ranging from 1% to 30% by weight, preferably from 2% to 25% by weight and better still from 10% to 20% by weight relative to the total weight of the aqueous composition (A).

13. Process according to any one of the preceding claims, characterized in that water represents from 20%> to 85% by weight, preferably from 30% to 70% by weight and more preferentially from 40% to 60% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

14. Process according to any one of the preceding claims, characterized in that water represents from 50% to 95% by weight, preferably from 60% to 90% by weight and more preferentially from 65% to 80% by weight relative to the total weight of the aqueous composition (A).

15. Process according to any one of the preceding claims, characterized in that the oil(s) are chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, non- silicone oils of animal origin, oils of plant origin, fluoro oils, liquid fatty alcohols, liquid fatty esters, non-salified liquid fatty acids, silicone oils, and mixtures of these compounds, and are preferably chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, liquid fatty esters, oils of plant origin, especially hydrocarbon-based oils of plant origin, and mixtures of these compounds, and more preferentially are chosen from C₆-Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, oils of plant origin, especially hydrocarbon- based oils of plant origin, and mixtures of these compounds.

16. Process according to any one of the preceding claims, characterized in that the oil(s) represent a total content ranging from 10% to 45% by weight and preferably from 15% to 40% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

17. Process according to any one of the preceding claims, characterized in that the oil(s) represent a total content ranging from 50% to 99% by weight, preferably from 70% to 98% by weight and better still from 80% to 95% by weight relative to the total weight of the oily composition (B).

18. Process according to any one of the preceding claims, characterized in that the fatty-phase thickener(s) are chosen from mineral fatty-phase thickeners, organic fatty-phase thickeners, and mixtures of these compounds, preferably are chosen from semi-crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, N-acylamino acid amide derivatives, polymers comprising one or more alkylene and/or styrene blocks, such as polystearyl acrylates, elastomeric organopolysiloxanes, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds, and are more preferentially chosen from semi-crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, polymers comprising an alkylene and/or styrene block, such as polystearyl acrylates, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds.

19. Process according to any one of the preceding claims, characterized in that the fatty-phase thickener(s) are chosen from saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, C8-C30 and preferably C₁₈- C24 fatty acid esters and mixtures thereof, better still mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of polyols, more particularly mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of glycerol.

20. Process according to any one of the preceding claims, characterized in that the fatty-phase thickener(s) generally represent a total content ranging from 0.05% to 20% by weight, preferably from 0.1 % to 15% by weight and better still from 1 % to 8% by weight relative to the total weight of the compositions (A) and (B) applied to the fibres.

21. Process according to any one of the preceding claims, characterized in that the fatty-phase thickener(s) represent a total content ranging from 1% to 40% by weight, preferably from 2% to 30% by weight and better still from 5% to 20% by weight relative to the total weight of the oily composition (B).

22. Process according to any one of the preceding claims, characterized in that the weight ratio of the amount of oily composition (B) to the amount of aqueous composition (A) is greater than 0.10 and less than or equal to 1, preferably ranges from 0.15 to 0.7 and more preferentially from 0.25 to 0.5.

23. Process according to any one of the preceding claims, characterized in that the two compositions (A) and (B) each have a viscosity of greater than or equal to

0.1 Pa.s, preferably ranging from 0.1 to 500 Pa.s, more preferentially ranging from 0.5 to 300 Pa.s, and even more preferentially ranging from 1 to 200 Pa.s, at a temperature of 25°C, at atmospheric pressure and at a shear rate of 1 s^"1.

24. Process according to any one of the preceding claims, characterized in that the compositions (A) and (B) are applied together in one and the same composition prepared previously or obtained by extemporaneous mixing before application, and preferably prepared previously.