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Title:
PROCESS FOR DYEING KERATIN FIBRES WITH THREE DISTINCT COMPOSITIONS
Document Type and Number:
WIPO Patent Application WO/2019/002072
Kind Code:
A1
Abstract:
The subject of the present invention is a composition for dyeing keratin fibres, consisting in: a) extemporaneously mixing, at the moment of use, at least three distinct compositions (A), (B) and (C), then b) applying said mixture to the keratin fibres; - the composition (A) comprising at least one polycondensate of ethylene oxide and of propylene oxide having the structure below H-(O-CH2-CH2)a-(O-CH(CH3)-CH2)b-(O-CH2-CH2)a-OH, in which a and a' range from 2 to 150 and b ranges from 1 to 100, and at least one cationic polymer -the composition (B) comprising at least one basifying agent and at least one oxidation dye, and -the composition (C) comprising at least one chemical oxidizing agent; the composition (B) and/or the composition (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of the composition (B) and/or (C), and/or the mixture of the three compositions (A) + (B) + (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of said mixture.

Inventors:
LAHAYE, Agathe (111 Terminal Avenue, Clark, NJ, 07066, US)
LEPTACZ, Dominique (188 rue Paul Hochart, BP553, CHEVILLY LA RUE, 94152, FR)
AGACH, Mickaël (11-13 rue Dora Maar, Saint OUEN, 93400, FR)
Application Number:
EP2018/066536
Publication Date:
January 03, 2019
Filing Date:
June 21, 2018
Export Citation:
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Assignee:
L'OREAL (14 rue Royale, PARIS, PARIS, 75008, FR)
International Classes:
A61Q5/10; A61K8/81; A61K8/86; A61Q5/12
Domestic Patent References:
WO1996015765A11996-05-30
WO1994008969A11994-04-28
WO1994008970A11994-04-28
Foreign References:
FR2968202A12012-06-08
FR2505348A11982-11-12
FR2542997A11984-09-28
EP0080976A11983-06-08
FR2077143A51971-10-15
FR2393573A11979-01-05
US4131576A1978-12-26
US3589578A1971-06-29
US4031307A1977-06-21
FR2162025A11973-07-13
FR2280361A21976-02-27
FR2252840A11975-06-27
FR2368508A21978-05-19
FR1583363A1969-10-24
US3227615A1966-01-04
US2961347A1960-11-22
FR2080759A11971-11-19
FR2190406A21974-02-01
FR2320330A11977-03-04
FR2270846A11975-12-12
FR2316271A11977-01-28
FR2336434A11977-07-22
FR2413907A11979-08-03
US2273780A1942-02-17
US2375853A1945-05-15
US2388614A1945-11-06
US2454547A1948-11-23
US3206462A1965-09-14
US2261002A1941-10-28
US2271378A1942-01-27
US3874870A1975-04-01
US4001432A1977-01-04
US3929990A1975-12-30
US3966904A1976-06-29
US4005193A1977-01-25
US4025617A1977-05-24
US4025627A1977-05-24
US4025653A1977-05-24
US4026945A1977-05-31
US4027020A1977-05-31
US4157388A1979-06-05
US4702906A1987-10-27
US4719282A1988-01-12
EP0122324A11984-10-24
GB1026978A1966-04-20
GB1153196A1969-05-29
FR2801308A12001-05-25
DE2359399A11975-06-12
JP2013169571A2013-09-02
JPH0563124A1993-03-12
EP0770375A11997-05-02
DE3843892A11990-06-28
DE4133957A11993-04-15
FR2733749A11996-11-08
DE19543988A11997-05-28
FR2886136A12006-12-01
Other References:
WALTER NOLL'S: "Chemistry and Technology of Silicones", 1968, ACADEMIC PRESS
"Cosmetics and Toiletries", vol. 91, pages: 27 - 32
TODD; BYERS, VOLATILE SILICONE FLUIDS FOR COSMETICS
Attorney, Agent or Firm:
DUVERT, Sandra (D.I.P.I, 9 Rue Pierre Dreyfus, Clichy, 92110, FR)
Download PDF:
Claims:
CLAIMS

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

a) extemporaneously mixing, at the moment of use, at least three distinct compositions (A), (B) and (C), then

b) applying said mixture to the keratin fibres;

- the composition (A) comprising at least one polycondensate of ethylene oxide and of propylene oxide having the structure below

H-(0-CH2-CH2)a-(0-CH(CH3)-CH2)b-(0-CH2-CH2)a-OH,

in which a and a' range from 2 to 150 and b ranges from 1 to 100, and at least one cationic polymer

-the composition (B) comprising at least one basifying agent and at least one oxidation dye, and

-the composition (C) comprising at least one chemical oxidizing agent;

the composition (B) and/or the composition (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of the composition (B) and/or (C), and/or the mixture of the three compositions (A) + (B) + (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of said mixture.

2. Process according to the preceding claim, characterized in that the compositions are mixed together immediately before application to the keratin fibres, preferably between 1 second and 15 minutes, preferentially between 5 seconds and 7 minutes before application to the keratin fibres.

3. Process according to either one of the preceding claims, in which the polycondensate of ethylene oxide and of propylene oxide is such that a and a' range from 5 to 130 and b ranges from 10 to 80, preferably a and a' range from 10 to 130 and b ranges from 20 to 80, better still a and a' range from 10 to 50 and b ranges from 20 to 50.

4. Process according to any one of the preceding claims, in which the polycondensate of ethylene oxide and of propylene oxide is such that a and a' are identical. Process according to any one of the preceding claims, in which the amount of polycondensate(s) of ethylene oxide and of propylene oxide ranges from 0.1 % to 30% by weight, even more preferentially from 0.5% to 20% by weight and better still from 1 % to 10% by weight relative to the total weight of the composition (A).

6. Process according to any one of the preceding claims, characterized in that the cationic polymer(s) are chosen from the following polymers, alone or as mixtures:

(1 ) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formula (I), (II), (III) or (IV) below:

in which:

R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched C1-C6 alkyl group or a hydroxyalkyl group of which the alkyl is C1-C4;

R4, R5 and R6, which may be identical or different, represent a C1-C18 alkyl group or a benzyl radical;

Ri and R2, which may be identical or different, represent hydrogen or a C1-C6 alkyl group;

(2) cationic cellulose derivatives;

(3) cationic guar gums;

(4) polymers constituted of piperazinyl units and linear or branched divalent alkyl or hydroxyalkyl radicals, optionally interrupted with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers;

(5) water-soluble polyaminoamides which are optionally cross-linked;

(6) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid; (7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, in the form of homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulae (V) or (VI):

in which formulae k and t are equal to 0 or 1 , the sum k + t being equal to 1 ; Rg denotes a hydrogen atom or a methyl radical; R7 and Rs, independently of each other, denote a d-Cs alkyi group, a hydroxyalkyi group in which the alkyi group is C1-C5, an amidoalkyl group in which the alkyi is C1-C4; R7 and Rs can also denote, together with the nitrogen atom to which they are attached, a heterocyclic group; Y" is an organic or inorganic anion;

(8) quaternary diammonium polymers containing repeating units corresponding to the formula:

^10 R12

— N+ - A. - N+- B, — (VII)

I I 1_

R-I -I X R<| 3 X

in which formula (VI I):

R10, R11 , R12 and R13, which may be identical or different, represent saturated, unsaturated or aromatic, linear, branched or cyclic, C1-C20 hydrocarbon-based radicals, linear or branched hydroxyalkyi radicals of which the alkyi part is C1-C4, linear or branched C1-C6 alkyi radicals, substituted with a nitrile, ester, acyl or amide group or a group -CO-O-

-CO-NH-R14-D with Ri4 representing an alkyi radical and D a quaternary ammonium group, or form together or separately, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen;

Ai and Bi represent linear or branched, saturated or unsaturated C2-C20 polymethylene groups which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X" denotes an anion derived from an inorganic or organic acid; Ai, Rio and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi can also denote a group - (CH2)nCO-D-OC-(CH2)n- in which n is between 1 and 100, and D denotes a glycol, bis-secondary diamine, bis-primary diamine or ureylene residue;

(9) Polyquaternary ammonium polymers constituted of repeating units of formula (IX):

in which p denotes an integer ranging from 1 to 6, D may be zero or may represent a group -(CH2)r-CO- in which r denotes a number equal to 4 or 7, and X" is an organic or inorganic anion;

(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole;

(1 1 ) polyamines,

and mixtures thereof.

7. Process according to Claim 6, characterized in that the cationic polymer(s) are chosen from the polymers (1 ), (7), (8) and (9), preferably (7), (8) and (9), alone or as mixtures.

8. Process according to one of the preceding claims, characterized in that the cationic polymer(s) has (have) a charge density of greater than 1 meq/g, preferably greater than or equal to 3 meq/g, better still greater than or equal to 4 meq/g.

9. Process according to one of the preceding claims, characterized in that the content of cationic polymer(s) represents from 0.1 % to 20% by weight, more particularly from 0.5% to 15% by weight and even more preferentially between 1 % and 10% by weight relative to the weight of the composition (A). 10. Process according to any one of the preceding claims, characterized in that the composition (B) comprises, as oxidation dyes, one or more oxidation bases chosen from para-phenylenediamines, bis(phenyl)alkylene-diamines, para- aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof, and optionally a coupler.

1 1 . Process according to any one of the preceding claims, characterized in that the basifying agent is chosen from aqueous ammonia, alkali metal carbonates or bicarbonates, sodium hydroxide, potassium hydroxide and organic amines of which the pKb at 25°C is less than 12, preferably less than 10 and even more advantageously less than 6.

12. Process according to one of the preceding claims, characterized in that the basifying agent is chosen from organic amines, in particular an alkanolamine, preferably monoethanolamine.

13. Process according to any one of the preceding claims, in which the chemical oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, such as, for example, alkali metal or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and precursors thereof; preferentially hydrogen peroxide.

14. Process according to any one of the preceding claims, in which the composition (C) comprises at least one fatty substance, the total content of fatty substance being at least 20% by weight, preferably at least 25% by weight, relative to the total weight of composition (C).

15. Process according to any one of the preceding claims, in which the composition (B) comprises at least one fatty substance, preferably liquid, the total content of fatty substance being at least 20% by weight, preferably at least 25% by weight, better still at least 30% by weight, more preferably still at least 40% by weight, better still at least 50% by weight, relative to the total weight of composition (B).

16. Process according to any one of the preceding claims, in which the mixture of the three compositions (A) + (B) + (C) comprises at least one fatty substance, at a total content of fatty substance of at least 20% by weight, preferably at least 25% by weight, at least 30% by weight, relative to the total weight of said mixture. 17. Process according to any one of the preceding claims, in which the fatty substance(s) are chosen from non-silicone fatty substances.

18. Process according to any one of the preceding claims, in which the fatty substance(s) is (are) chosen from compounds that are liquid or pasty at room temperature and at atmospheric pressure and preferably liquid at room temperature and at atmospheric pressure.

19. Process according to any one of the preceding claims, in which the fatty substance(s) are chosen from C6-C16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of plant or synthetic origin, fatty alcohols, and fatty acid and/or fatty alcohol esters, or mixtures thereof.

20. Process according to any one of the preceding claims, in which the fatty substance(s) are chosen from liquid petroleum jelly, liquid paraffins, polydecenes, fatty acid and/or fatty alcohol esters that are liquid at room temperature and at atmospheric pressure, fatty alcohols that are liquid at room temperature and at atmospheric pressure, or mixtures thereof.

21 . Process according to any one of the preceding claims, in which the distinct compositions (A), (B) and (C) are mixed in the following proportions:

(A) / (B) + (C) ranging from 0.005 to 1 , preferably from 0.01 to 0.5, better still from 0.02 to 0.1 , and/or

(B)/(C) ranging from 0.1 to 10, preferably from 0.5 to 2, better still from 0.6 to 1 .5. 22. Device comprising at least three compartments, containing:

• in a first compartment, a composition (A) as defined in any one of the preceding claims,

• in a second compartment, a composition (B) as defined in any one of the preceding claims,

· in a third compartment, a composition (C) as defined in any one of the preceding claims.

Description:
PROCESS FOR DYEING KERATIN FIBRES WITH THREE DISTINCT

COMPOSITIONS

A subject of the invention is a process for dyeing keratin fibres consisting in applying to the fibres a mixture: of a composition (A) comprising a specific polycondensate of ethylene oxide and of propylene oxide and a cationic polymer and of a composition (B) comprising a basifying agents and an oxidation dye and of an oxidizing composition (C).

Another subject of this invention is a multi-compartment device comprising the compositions (A), (B) and (C) as defined above.

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

One of the dyeing methods is "permanent" or oxidation dyeing, which uses dye compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.

Permanent dyeing processes thus consist in using, with the dye composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases. The role of this oxidizing agent is, at least in part, to degrade the melanin of the hair, which, depending on the nature of the oxidizing agent present, leads to more or less pronounced lightening of the fibres. The oxidizing agent used is generally hydrogen peroxide.

Oxidation dyeing must satisfy a certain number of requirements. Thus, it must be free of toxicological drawbacks, it must enable shades to be obtained in the desired intensity which show good resistance to external attacking factors such as light, bad weather, washing, permanent waving, perspiration and rubbing.

The colourings must also be powerful and make it possible to cover grey hair and, finally, they must be as unselective as possible, i.e. make it possible to produce the smallest possible colour differences along the same keratin fibre, which generally comprises areas that are differently sensitized (i.e. damaged) from its end to its root. The compositions obtained must also have good mixing and application properties, and in particular good rheological properties so as not to run down onto the face, the scalp or beyond the areas that it is proposed to dye, when they are applied.

Finally, the dyeing operations must, as far as is possible, respect the integrity of the keratin fibres and give said fibres the best possible cosmetic properties. Many attempts have been made in the field of hair dyeing in order to improve the dyeing properties, for example with the aid of adjuvants. However, the choice of these adjuvants is difficult in so far as they must improve the dyeing properties of dye compositions without harming the other properties of these compositions. In particular, these adjuvants must not harm the stability of the compositions, the application properties of the colouring especially or the cosmetic properties of the dyed fibres.

It is therefore sought to improve the qualities of use of these compositions, especially the qualities of application and of distribution on the keratin fibres, in particular in terms of the wetting nature, the adhesion to the roots and the ease with which the mixture can be spread along the locks of hair, and also the cosmetic properties of the keratin fibres, in particular in terms of disentangling and feel.

It is also sought to obtain dyeing compositions which have good performance from the perspective of the dyeing properties.

The aim of the present invention is to overcome the drawbacks of the prior art and therefore to propose colouring compositions which have good qualities of use, in particular good properties of application and distribution and good dyeing properties.

These aims and others are achieved by the present invention, a subject of which is thus a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, consisting in:

a) extemporaneously mixing, at the moment of use, at least three distinct compositions (A), (B) and (C), then

b) applying said mixture to the keratin fibres;

- the composition (A) comprising at least one polycondensate of ethylene oxide and of propylene oxide having the structure below

H-(0-CH2-CH 2 )a-(0-CH(CH 3 )-CH2)b-(0-CH2-CH2)a-OH,

in which a and a' range from 2 to 150 and b ranges from 1 to 100, and at least one cationic polymer

-the composition (B) comprising at least one basifying agent and at least one oxidation dye, and

-the composition (C) comprising at least one chemical oxidizing agent;

the composition (B) and/or the composition (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of the composition (B) and/or (C), and/or the mixture of the three compositions (A) + (B) + (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of said mixture. The mixture of the compositions resulting from the process according to the invention has good qualities of use, especially of application and distribution on the keratin fibres, in particular the hair; it is especially easy to use, does not run and enables easy and uniform spreading and distribution along the hair.

The process according to the invention also makes it possible to produce vibrant, intense, chromatic and sparingly selective colourings, i.e. colourings that are uniform along the length of the fibre.

In addition, the keratin fibres have a smoother feel, are softer and more supple, and disentangle more easily.

A subject of the invention is, similarly, a device comprising at least three compartments containing, in a first compartment, the composition (A) as defined previously, in a second compartment, the composition (B) as defined previously, and in a third compartment the composition (C) as defined previously. Other characteristics and advantages of the invention will emerge 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.

The human keratin fibres treated via the process according to the invention are preferably the hair.

The term "at least one" is equivalent to "one or more".

The term "fatty substance" means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They bear in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms 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 fatty substances of the invention are neither polyoxyalkylenated nor polyglycerolated.

The term "oxidizing agent" or "chemical oxidizing agent" according to the invention means an oxidizing agent other than atmospheric oxygen.

Dyeing process of the invention

The dyeing process according to the invention consists in: a) extemporaneously mixing, at the moment of use, at least three distinct compositions (A), (B) and (C), then

b) applying said mixture to the wet or dry keratin fibres, preferably immediately after preparation of said mixture,

- the composition (A) comprising at least one polycondensate of ethylene oxide and of propylene oxide having the structure below:

H-(0-CH2-CH 2 )a-(0-CH(CH 3 )-CH2)b-(0-CH2-CH2)a-OH,

in which a and a' range from 2 to 150 and b ranges from 1 to 100, and at least one cationic polymer

-the composition (B) comprising at least one basifying agent and at least one oxidation dye, and

-the composition (C) comprising at least one chemical oxidizing agent;

the composition (B) and/or the composition (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of the composition (B) and/or (C), and/or the mixture of the three compositions (A) + (B) + (C) comprising at least one fatty substance at a total content of fatty substances of at least 20% by weight relative to the total weight of said mixture. The term "extemporaneously mixing, at the moment of use" means that the distinct compositions (A), (B) and (C) are mixed together immediately before use, for example between 1 second and 15 minutes, preferentially between 5 seconds and 7 minutes, before use on the keratin fibres.

According to one embodiment, the compositions (A), (B) and (C) are mixed together simultaneously immediately before use thereof. The composition resulting from the mixing of the compositions (A), (B) and (C) according to the invention is then left in place for a time usually ranging from one minute to one hour and preferably from 5 minutes to 30 minutes.

The temperature during the process is conventionally between room temperature (between 15 and 25°C) and 80°C and preferably between room temperature and 60°C.

After the treatment, the human keratin fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.

The composition (A) preferentially does not contain any oxidation dye.

Polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensate As indicated above, the composition (A) according to the invention comprises at least one polycondensate of ethylene oxide and of propylene oxide of formula H- (0-CH2-CH2)a-(0-CH(CH 3 )-CH2)b-(0-CH2-CH2)a-OH ,

in which a and a' range from 2 to 150 and b ranges from 1 to 100, and at least one cationic polymer

[

Advantageously, the polycondensate of ethylene oxide and of propylene oxide corresponds to a polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensate.

Preferably, in the structure described above, a and a' range from 5 to 130 and b ranges from 10 to 80. In accordance with an even more particular embodiment, a and a' range from 10 to 130 and b ranges from 20 to 80, and preferably a and a' range from 10 to 50 and b ranges from 20 to 50. According to a particular embodiment, a and a' are identical.

The polycondensate of ethylene oxide and of propylene oxide that is useful in the composition of the invention preferably has a weight-average molecular weight ranging from 250 to 19 000, better still ranging from 1200 to 15 000, in particular ranging from 1500 to 10 000 and even better still ranging from 1500 to 5000.

Advantageously, said polycondensate of ethylene oxide and of propylene oxide has a cloud point, at 10 g/l in distilled water, of greater than or equal to 20°C and preferably of greater than or equal to 50°C. The cloud point is measured according to the standard ISO 1065. As polycondensates of ethylene oxide and of propylene oxide that may be used according to the invention, mention may be made of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the name Synperonic, for instance Synperonic® PE/F32 (INCI name: Poloxamer 108), Synperonic® PE/F108 (INCI name: Poloxamer 338), Synperonic® PE/ L44 (INCI name: Poloxamer 124), Synperonic® PE/L42 (INCI name: Poloxamer 122), Synperonic® PE/F127 (INCI name: Poloxamer 407), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/L64 (INCI name: Poloxamer 184), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/F87 (INCI name: Poloxamer 237) from the company Croda, or Lutrol® F68 (INCI name: Poloxamer 188) by the company BASF.

According to one embodiment of the invention, the total amount of polycondensate(s) of ethylene oxide and propylene oxide preferably ranges from 0.1 % to 30% by weight, even more preferentially from 0.5% to 20% by weight and better still from 1 % to 10% by weight relative to the total weight of the composition (A). Cationic polymer

It is recalled that, for the purposes of the present invention, the term "cationic polymer" denotes any polymer containing cationic groups and/or groups that can be ionized into cationic groups.

Preferably, the cationic polymer present in the composition (A) according to the invention is a linear, random, graft or block homopolymer or copolymer and comprises at least one cationic group and/or group that can be ionized into a cationic group chosen from primary, secondary, tertiary and/or quaternary amine groups that form part of the main polymer chain or that are borne by a side substituent directly connected thereto. Preferably, the cationic charge density of the cationic polymers according to the invention is greater than 1 meq/g, more preferentially greater than or equal to 3 meq/g, better still greater than or equal to 4 meq/g.

This charge density is determined by the Kjeldahl method. It may also be calculated from the chemical nature of the polymer.

The cationic polymers used generally have a number-average molecular weight of between 500 and 5 χ 10 6 approximately, and preferably between 10 3 and 3 χ 10 6 . Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type.

These are known products and are especially described in patents FR 2505348 or FR 2542997.

Among the cationic polymers that can be used in the context of the invention, mention may be made of the following polymers, alone or as a mixture:

(1 ) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formula (I), (II), (III) or (IV) below:

in which

R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;

A, which may be identical or different, represent a linear or branched C1-C6 and preferably C2-C3 alkyl group or a C1-C4 hydroxyalkyl group; R 4 , R5 and R6, which may be identical or different, represent a C1-C18 alkyl group or a benzyl radical, and preferably a C1-C6 alkyl group;

Ri and R2, which may be identical or different, represent hydrogen or a C1-C6 alkyl group, preferably methyl or ethyl;

X denotes an anion derived from an inorganic or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.

The polymers of family (1 ) may also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these polymers of family (1 ), mention may be made of:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,

- copolymers of acrylamide and of methacryloyloxyethyl-trimethylammonium chloride described, for example, in EP 80 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy,

- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules,

- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937. These polymers are described in FR 2 077 143 and FR 2 393 573,

- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,

- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, especially sold under the name Styleze CC 10 by ISP,

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP, and

- the crosslinked polymers of methacryloyloxy(Ci-C4)alkyl tri(Ci-C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide. Use may more particularly be made of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names of Salcare® SC 95 and Salcare® SC 96 by the company Ciba.

(2) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described especially in US 4 131 576, such as hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted especially 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.

(3) Cationic guar gums described more particularly in US 3 589 578 and US 4 031 307, such as guar gums containing trialkylammonium cationic groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, chloride).

Such products are sold especially under the trade names Jaguar C13S, Jaguar

C15, Jaguar C17 and Jaguar C162 by the company Meyhall.

(4) Polymers constituted of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers. Such polymers are described especially in FR 2 162 025 and FR 2 280 361.

(5) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis- unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis- haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may be alkylated or, if they contain one or more tertiary amine functions, they may be quaternized. Such polymers are described especially in FR 2 252 840 and FR 2 368 508. Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids, followed by an alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylene-triamine polymers in which the alkyl radical is C1-C4 and preferably denotes methyl, ethyl or propyl. Such polymers are described especially in FR 1 583 363.

Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.

(6) Polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated C3-C8 aliphatic dicarboxylic acids. The mole ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8: and 1 .4:1 ; the resulting polyaminoamide is reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5:1 and 1 .8:1 . Such polymers are described especially in US 3 227 615 and US 2 961 347.

Polymers of this type are sold in particular under the name Hercosett 57, PD 170 or Delsette 101 by the company Hercules.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (V) or (VI): -(CH 2 )t-

in which formulae k and t are equal to 0 or 1 , the sum k + t being equal to 1 ; R9 denotes a hydrogen atom or a methyl radical; R7 and Rs, independently of each other, denote a

C1-C8 alkyl group, a hydroxyalkyl group in which the alkyl group is C1-C5, an amidoalkyl group in which the alkyl is C1-C4; R7 and Rs can also denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl;

R7 and Rs, independently of each other, preferably denote a C1-C4 alkyl group; Y " is an organic or inorganic anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described especially in

FR 2 080 759 and FR 2 190 406.

The cyclopolymers preferably comprise at least one unit of formula (V). As regards the copolymers, they also comprise an acrylamide monomer.

Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name Merquat 100 by the company Nalco (and its homologues of low weight-average molecular weight) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name Merquat 550.

(8) The quaternary diammonium polymer containing repeating units corresponding to the formula:

R 10 R 12

— N+ -A. - N+- B,— (VII)

I I 1

R 11 X " R 13 X "

in which formula:

Rio, Rii , Ri2 and R13, which may be identical or different, represent C1-C20 aliphatic, alicyclic or arylaliphatic radicals or hydroxyalkylaliphatic radicals in which the alkyl radical is C1-C4, or alternatively R10, R11 , R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively R10, R11 , R12 and R13 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl or amide group or a group -CO-O-R14-D or -CO-NH-R14-D where R14 is an alkylene and D is a quaternary ammonium group;

Ai and Bi represent linear or branched, saturated or unsaturated C2-C20 polymethylene groups which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X " denotes an anion derived from an inorganic or organic acid;

Ai , R10 and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;

in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi may also denote a group -(CH2)n-CO-D-OC-(CH2) n - in which n is between 1 and 100 and preferably between 1 and 50, and D denotes: a) a glycol residue of formula: -O-Z-O-, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae:

-(CH2-CH 2 -0)x-CH2-CH 2 - and -[CH 2 -CH(CH3)-0]y-CH2-CH(CH 3 )- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue, such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the radical -CH2-CH2-S- d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X " is an anion, such as chloride or bromide.

These polymers have a number-average molecular weight generally between 1 000 and 100 000.

Polymers of this type are described especially in FR 2 320 330, FR 2 270 846, FR 2 316 271 , FR 2 336 434, FR 2 413 907, US 2 273 780, US 2 375 853, US 2 388 614, US 2 454 547, US 3 206 462, US 2 261 002, US 2 271 378, US 3 874 870, US 4 001 432, US 3 929 990, US 3 966 904, US 4 005 193, US 4 025 617, US 4 025 627, US 4 025 653, US 4 026 945 and US 4 027 020.

It is more particularly possible to use polymers that are constituted of repeating units corresponding to the following formula (VIII): (CH 2 ) p — (VIII) ^

in which R10, R11 , R12 and R13, which may be identical or different, denote a C1-C4 alkyl or hydroxyalkyl radical, n and p are integers ranging from 2 to 20 approximately, and X " is an anion derived from an inorganic or organic acid.

(9) Polyquaternary ammonium polymers constituted of repeating units of formula (IX):

in which p denotes an integer ranging from 1 to 6 approximately, D may be zero or may represent a group -(CH2)r-CO- in which r denotes a number equal to 4 or 7, and X " is an anion.

Such polymers may be prepared according to the processes described in US 4

157 388, US 4 702 906 and US 4 719 282. They are especially described in patent application EP 122 324.

Among these polymers, examples that may be mentioned include the products Mirapol A 15, Mirapol AD1 , Mirapol AZ1 and Mirapol 175 sold by the company Miranol. (10) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF.

(1 1 ) Polyamines such as Polyquart H sold by Cognis, referred to under the name polyethylene glycol (15) tallow polyamine in the CTFA dictionary.

Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, polyquaternary ureylenes and chitin derivatives.

Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use, alone or as mixtures, polymers of families (1 ), (7), (8) and (9). In accordance with a more particular embodiment of the invention, it is preferred to use polymers of families (7), (8) and (9).

According to an even more advantageous embodiment of the invention, use is made of polymers of families (7) and (8) alone or as mixtures, and even more preferentially polymers of family (7) and polymers of family (8) bearing repeating units of formulae (W) and (U) below:

CH 3 CH 3

— ^ N ± - (CH 2 ) 3 -N + -tCH 2 ) 6 ^ (W)

I CI- I Cl-

CH 3 CH 3

and especially those of which the molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;

CH 3 C 2 H 5

— ^ I N - (CH 2 ) 3 -N + — (CH 2 ) 3 ^ (U)

Br- I Br

CH 3 C 2 H 5

and especially those of which the molecular weight, determined by gel permeation chromatography, is approximately 1200.

Preferably, the cationic polymer present in the composition (A) according to the invention is chosen from polymers of families (7) and (8).

Better still, the cationic polymer present in the composition (A) according to the invention is chosen from polymers of family (7), preferably dimethyldiallylammonium chloride homopolymers, polymers of formula (VIII) above, in particular polymers of formula (U) or (W), and mixtures thereof.

The composition (A) according to the invention may advantageously comprise a total amount of cationic polymer(s) ranging from 0.1 to 20% by weight, more particularly from 0.5 to 15% by weight, and even more preferentially between 1 and 10% by weight relative to the total weight thereof of the composition (A). According to one embodiment, the composition (B) and/or the composition (C) comprises at least one cationic polymer, preferably chosen from those indicated above, preferably in the amounts indicated above.

According to one embodiment, the composition (C) comprises at least one cationic polymer, preferably chosen from those indicated above, preferably in a total amount ranging from 0.01 to 10% by weight, more preferentially from 0.05 to 6% by weight, better still from 0.1 to 5% by weight relative to the total weight of the composition (B) and/or (C) containing same.

Oxidation dyes

The oxidation dyes that are useful in the composition (B) of the invention are generally chosen from oxidation bases and couplers.

By way of example of oxidation bases, mention may be made of para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(p-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis(p-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis(p-hydroxyethyl)amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, Ν-(β- hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(p-hydroxyethyl)-para- phenylenediamine, N-(p,y-dihydroxypropyl)-para-phenylenediamine, N-(4'- aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2-p-acetylaminoethyloxy-para- phenylenediamine, N-(p-methoxyethyl)-para-phenylenediamine, 4- aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-p-hydroxyethylamino-5- aminotoluene, 3-hydroxy-1 -(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2-p-acetylaminoethyloxy-para-phenylenediamine, and addition salts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines, examples that may be mentioned include N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, Ν,Ν'- bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine, 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and addition salts thereof.

Among the para-aminophenols, examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols, examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and addition salts thereof.

Among the heterocyclic bases, examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and addition salts thereof.

Other pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2- (morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2- carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5- a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)ethanol, 2-(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1 ,5-a]pyridine, 3,4-diaminopyrazolo[1 ,5-a]pyridine, pyrazolo[1 ,5- a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5- a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1 ,5- a]pyridin-5-ol, 3-aminopyrazolo[1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[1 ,5-a]pyridin-6-ol and 3-aminopyrazolo[1 ,5-a]pyridin-7-ol and 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2- yl)oxy]ethanol, and addition salts thereof.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88-169571 , JP 05-63124 and EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy- 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5- diamino-1 -methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3- dimethylpyrazole, 4,5-diamino-3-methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3- phenylpyrazole, 4-amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3- methylpyrazole, 4,5-diamino-3-tert-butyl-1 -methylpyrazole, 4,5-diamino-1 -tert-butyl-3- methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5- diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -isopropylpyrazole, 4,5-diamino-3- methyl-1 -isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5-triaminopyrazole, 3,5-diamino-1 -methyl-4- methylaminopyrazole and 3, 5-diamino-4-(p-hydroxyethyl)amino-1 -methylpyrazole, and addition salts thereof. Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole. Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt thereof. Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and especially those described in patent application FR- A-2 886 136, such as the following compounds and the addition salts thereof: 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5- diamino-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-di(2-hydroxyethyl)-1 ,2- dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3-diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2- a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5-(pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4- amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one, 2,3- diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one. Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one and/or a salt thereof.

As heterocyclic bases, use will preferentially be made of 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-

1 - one and/or 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol and/or a salt thereof.

Among the useful couplers, mention may be made especially of meta- phenylenediamines, meia-aminophenols, meia-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Examples that may be mentioned include 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-

2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2,4-diamino-1 -(β- hydroxyethyloxy)benzene, 1 -hydroxy-3-aminobenzene, 2-methyl-5- hydroxyethylaminophenol, 5-amino-6-chloro-2-methylphenol, 2-amino-4-(3- hydroxyethylamino)-1 -methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4- diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, 1 -3-hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl- 1 -naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3- hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1 -N- (3-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(3- hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy4-methylpyridine, 1 -H3- methylpyrazol-5-one, 1 -phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1 ,5-b]- 1 ,2,4-triazole, 2,6-dimethyl[3,2-c]-1 ,2,4-triazole and 6-methylpyrazolo[1 ,5- a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof. In general, the addition salts of the oxidation bases and couplers that may be used in the context of the invention are especially chosen from the addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

According to one embodiment, the composition (B) comprises at least one oxidation base and optionally a coupler.

The oxidation base(s) each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition (B), and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The content of coupler(s), if it (they) is (are) present, each advantageously represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5 % by weight relative to the total weight of the composition (B).

Basifying agents

The composition (B) according to the invention comprises one or more basifying agents.

The basifying agent may be inorganic or organic or hybrid.

The inorganic basifying agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates, sodium hydroxide and potassium hydroxide, and mixtures thereof.

The organic basifying agent(s) are preferably chosen from organic amines with a pKb at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pKb corresponding to the function of highest basicity.

The organic basifying agent(s) is (are) chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (A1 ) below:

Rx Rz

\ /

^ N - W - N

R y X Rt (Al)

in which W is a C1-C6 alkylene radical optionally substituted by a hydroxyl group or a C-I-C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a C1-C6 alkyl, C1-C6 hydroxyalkyl, or C1-C6 aminoalkyl radical. Examples of such amines that may be mentioned include 1 ,3-diaminopropane, 1 ,3- diamino-2-propanol, spermine and spermidine.

The term "alkanolamine" is intended to mean an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C-i-Cs alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different C1-C4 hydroxyalkyl radicals are in particular suitable for performing the invention.

Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2- amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimethylamino-1 ,2- propanediol and tris(hydroxymethylamino)methane.

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

As amino acids that may be used in the present invention, mention may especially be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine. Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to formula (A2) below:

NH

/

R— CH 2 — CH X

CO 2 H

(A2)

in which R denotes a roup chosen from:

-(CH 2 ) 2 NH 2 -(CH 2 ) 2 NHCONH 2 -(CH 2 ) 2 NH C— NH 2

NH

The compounds corresponding to formula (A2) are histidine, lysine, arginine, ornithine and citrulline. The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made in particular of carnosine, anserine and balenine.

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

Preferably, the organic amine present in the composition (B) of the invention is an alkanolamine.

Even more preferentially, the organic amine is monoethanolamine. Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

Guanidine carbonate or monoethanolamine hydrochloride may be used in particular.

Advantageously, the content of basifying agent(s) ranges from 0.01 % to 30% by weight and preferably from 0.1 % to 20% by weight relative to the total weight of the composition (B).

The composition (B) of the invention preferably contains one or more alkanolamines and/or one or more basic amino acids. In a first variant of the invention, if the composition (B) comprises aqueous ammonia or a salt thereof and other basifying agents, then the amount of basifying agent(s) other than the aqueous ammonia is greater than that of aqueous ammonia (expressed as NHs).

In a second variant of the invention, the composition (B) does not comprise aqueous ammonia.

Oxidizing agents Composition (C) according to the invention comprises one or more oxidizing agents. More particularly, the oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates orferricyanides, peroxygenated salts, for instance alkali metal or alkaline-earth metal persulfates, perborates and percarbonates, and peracids and precursors thereof.

Preferably, the oxidizing agent is not chosen from peroxygenated salts.

Advantageously, the oxidizing agent is hydrogen peroxide.

Preferably, the oxidizing composition (C) comprises hydrogen peroxide as oxidizing agent, in aqueous solution, the concentration of which ranges, more particularly, from 0.1 % to 50%, more particularly between 0.5% and 20% and even more preferentially between 1 % and 15% by weight relative to the weight of the oxidizing composition (C).

The oxidizing composition (C) is preferably an aqueous composition. In particular, it comprises more than 5% by weight of water, preferably more than 10% by weight of water and even more advantageously more than 20% by weight of water.

The composition (C) may also comprise one or more organic solvents.

The organic solvents may be chosen from lower monoalcohols, polyols and polyol ethers, in particular from ethanol, propylene glycol, hexylene glycol and glycerol.

When it (they) is (are) present, the latter represent(s) more particularly from 0.01 % to 20% by weight relative to the weight of the oxidizing composition (C), and preferably from 0.1 % to 10% by weight.

The oxidizing composition (C) also preferably comprises one or more acidifying agents. Among the acidifying agents, examples that may be mentioned include inorganic or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

Usually, the pH of the oxidizing composition, when it is aqueous, is less than 7; preferably, the pH ranges from 1 to 5, better still from 1 .5 to 3. Fatty substances

As indicated above, the composition (B) and/or the composition (C) according to the invention comprises one or more fatty substances, the total content of fatty substances being at least 20% by weight relative to the total weight of the composition (B) and/or (C) comprising same, preferably at least 30% by weight, preferably at least 40% by weight, better still at least 50% by weight relative to the total weight of the composition

(B) and/or (C) and/or

the mixture of the three compositions (A) + (B) + (C) comprises at least one fatty substance, at a total content of fatty substance of at least 20% by weight, preferably at least 25% by weight, more preferentially at least 30% by weight, relative to the total weight of said mixture.

Advantageously, the composition (B) comprises at least one fatty substance, preferably liquid, with a total content of fatty substance of at least 20% by weight, preferably at least 25% by weight, better still at least 30% by weight, more preferably still at least 40% by weight, better still at least 50% by weight, relative to the total weight of composition (B).

Advantageously, the composition (C) comprises at least one fatty substance with a total content of fatty substance of at least 20% by weight, preferably at least 25% by weight, relative to the total weight of composition (C).

The total content of fatty substance in the mixture of the three compositions (A) + (B) +

(C) may range from 20% to 60%, preferably from 25% to 55%, better still from 30% to 45% by weight relative to the total weight of the mixture of the three compositions (A) + (B) + (C).

The term "fatty substance" means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They have in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms 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, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.

The term "o/T means a "fatty substance" that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg or 1.013x10 5 Pa).

The term "non-silicone o/T means an oil not containing any silicon (Si) atoms and the term "silicone o/T means an oil containing at least one silicon atom. More particularly, the fatty substances are chosen from C6-C16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of plant or synthetic origin, fluoro oils, fatty alcohols, non-salified fatty acids, esters of fatty acids and/or of fatty alcohols other than triglycerides, non-silicone waxes other than solid fatty alcohols and than solid synthetic esters, and silicones, and mixtures thereof.

It is recalled that, for the purposes of the invention, fatty alcohols, esters and acids more particularly bear at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The linear or branched hydrocarbons of inorganic or synthetic origin containing more than 16 carbon atoms are preferably chosen from liquid paraffins or liquid petroleum jelly, petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®, and mixtures thereof.

As regards the C6-C16 lower alkanes, they are linear or branched, or possibly cyclic.

Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, tridecane or isoparaffins, such as isohexadecane, isodecane or isododecane, and mixtures thereof.

A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.

The triglycerides of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or, alternatively, more particularly from those present in plant oils, for instance sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, jojoba oil, shea butter oil or synthetic caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, and mixtures thereof. The fluoro oils may be chosen from perfluoromethylcyclopentane and perfluoro-1 ,3- dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or alternatively bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.

The fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols comprising from 8 to 30 carbon atoms. Examples that may be mentioned include cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2- hexyldecanol, 2-undecylpentadecanol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, and mixtures thereof.

The fatty acids that may be used in the context of the invention are more particularly chosen from saturated or unsaturated carboxylic acids containing from 6 to 30 carbon atoms and in particular from 9 to 30 carbon atoms. They are advantageously chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid. These fatty acids are, in the composition, not salified with organic or inorganic bases, so as not to give rise to soaps.

As regards the esters of fatty acids and/or of fatty alcohols other than the triglycerides mentioned above and plant waxes, mention may especially be made of esters of saturated or unsaturated, linear C1-C26 or branched C3-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear C1-C26 or branched C3-C26 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2- ethylhexyl isononanoate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2- octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and mixtures thereof. Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C2-C26 di-, tri-, tetra- or pentahydroxy alcohols may also be used.

Mention may especially be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates, and mixtures thereof.

Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate and cetyl octanoate, and mixtures thereof.

The composition may also comprise, as fatty ester, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen- bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms.

These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may especially be chosen from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30, preferably C12-C22, fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, oleopalmitate, oleostearate and palmitostearate mixed esters. More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate.

An example that may be mentioned is the product sold under the name Glucate® DO by Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:

- the products sold under the names F160, F140, F1 10, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitostearates formed from 73% monoester and 27% diester and triester, from 61 % monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61 % diester, triester and tetraester, and sucrose monolaurate;

- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed of 20% monoester and 80% diester, triester and polyester;

- the sucrose mono-dipalmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE. The non-silicone wax(es) other than solid fatty alcohols and solid synthetic esters are chosen especially from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by the company Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that may be used according to the invention are especially marine waxes, such as the wax sold by the company Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general.

The silicones that may be used in the cosmetic compositions of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified with organic groups, having a viscosity of 5x10 "6 to 2.5 m 2 /s at 25°C, and preferably 1 x10 "5 to 1 m 2 /s.

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

Preferably, the silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMSs), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups and alkoxy groups. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile. When they are volatile, the silicones are more particularly chosen from those with a boiling point of between 60°C and 260°C, and even more particularly from:

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

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

r— D" - D' D" - D'

CH, ' ' CH 3

I

With D": —Si - O— with D': - Si - O—

CH 3 C 8 H 17

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10 "6 m 2 /s at 25°C. An example thereof is decamethyltetrasiloxane sold especially under the name SH 200 by Toray Silicone.

Silicones belonging to this category are also described in the article published in

Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, "Volatile Silicone

Fluids for Cosmetics".

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

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

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

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

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

- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

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

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

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

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

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

- mixtures of a polydimethylsiloxane gum and a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric; this product is an

SF 30 gum corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;

- mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from General Electric. The product SF 1236 is the mixture of a gum SE 30 defined above with a viscosity of 20 m 2 /s and of an oil SF 96 with a viscosity of 5x10 "6 m 2 /s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

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

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

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

Mention may also be made of the trimethyl siloxysilicate-type resins sold especially under the names X22-4914, X21 -5034 and X21 -5037 by the company Shin-Etsu. The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Besides the silicones described above, the organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by the organofunctional groups mentioned previously.

The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 x10 "5 to 5x10 "2 m 2 /s at 25°C.

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

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

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

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

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

. the silicones of the PN and PH series from Bayer, such as the products PN 1000 and

PH1000;

. certain oils of the SF series from General Electric, such as SF 1023, SF 1 154, SF 1250 and SF 1265.

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

- polyethyleneoxy and/or polypropyleneoxy groups optionally including C6-C24 alkyl groups, such as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 71 1 by the company Union Carbide, and the (Ci2)alkylmethicone copolyol sold by the company Dow Corning under the name Q2 5200;

- substituted or unsubstituted amino groups, such as the products sold under the names GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups;

- alkoxylated groups such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones, and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt.

The fatty substance(s) do not comprise any C2-C3 oxyalkylene units. Preferably, they do not contain any glycerol units. More particularly, the fatty substances are other than fatty acids.

More particularly, the fatty substances are chosen from compounds that are liquid or pasty at room temperature and at atmospheric pressure.

Preferably, the fatty substance is a compound that is liquid at a temperature of 25°C and at atmospheric pressure, or oil.

According to one preferred variant, the fatty substances are not silicone-based.

The fatty substances are preferably chosen from C6-C16 hydrocarbons, hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of plant or synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, or mixtures thereof.

Preferably, the fatty substance is chosen from liquid petroleum jelly, liquid paraffin, polydecenes, fatty acid and/or fatty alcohol esters that are liquid at room temperature and at atmospheric pressure, fatty alcohols that are liquid at room temperature and at atmospheric pressure, or mixtures thereof.

Tte_ Qi . er_a^ya_ntsi

Compositions (A), (B) and/or (C) used in the process of the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; preserving agents; opacifiers and thickeners.

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

Compositions (A), (B) and/or (C) of the process according to the invention may also comprise one or more inorganic thickeners, such as organophilic clays or fumed silicas, or organic thickeners such as fatty acid amides (coconut monoethanolamide or diethanolamide, oxyethylenated carboxylic acid alkyl ether monoethanolamide), polymeric thickeners such as cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose or carboxymethylcellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked acrylic acid or acrylamidopropanesulfonic acid homopolymers and associative polymers (polymers comprising hydrophilic regions and fatty-chain hydrophobic regions (alkyl or alkenyl comprising at least 10 carbon atoms) that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules).

According to one particular embodiment, the organic thickener is chosen from cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose or carboxymethylcellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum or scleroglucan gum) and crosslinked acrylic acid or acrylamidopropanesulfonic acid homopolymers, and preferably from cellulose-based thickeners in particular with hydroxyethylcellulose.

According to one particular embodiment, the composition (B) comprises at least one organic thickener chosen from cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose or carboxymethylcellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum, scleroglucan gum) and acrylic acid or acrylamidopropanesulfonic acid crosslinked homopolymers.

The content of organic thickener(s), if they are present, usually ranges from 0.01 % to 20% by weight relative to the weight of the compositions (A), (B) and/or (C), and preferably from 0.1 % to 5% by weight.

Compositions (A), (B) and/or (C) of the process according to the invention are media preferably comprising at least water and optionally one or more cosmetically acceptable organic solvents.

Examples of cosmetically acceptable organic solvents that may be mentioned include linear or branched and preferably saturated monoalcohols or diols, containing 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2- methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1 ,5-pentanediol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycerol; polyols or polyol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, 2- butoxyethanol, propylene glycol or ethers thereof, for instance propylene glycol, butylene glycol or dipropylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially of C1-C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

The solvents, when they are present, generally represent between 0.01 % and 40% by weight relative to the total weight of the composition containing them, and preferably between 0.1 % and 30% by weight relative to the total weight of the composition(s) containing them.

Preferably, compositions (A), (B) and/or (C) of the process of the invention contain water at a content ranging from 5% to 95% and better still from 10% to 85% of the total weight of the composition.

The compositions (A), (B) and/or (C) of the process according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.

Advantageously, compositions (A), (B) and/or (C) and the ready-to-use composition of the process according to the invention are in the most appropriate presentation form (gel, cream, etc.).

Preferably, the ready-to-use composition resulting from the mixing of compositions (A), (B) and/or (C) is in the form of a direct emulsion.

The pH of the composition after mixing compositions (A), (B) and (C) of the process according to the invention is advantageously between 3 and 12, preferably between 5 and 1 1 and preferentially between 7 and 1 1 , inclusive of limits.

It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.

The alkaline agents are, for example, those described previously.

Examples of acidifying agents that may be mentioned include inorganic or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance tartaric acid, citric acid or lactic acid, or sulfonic acids.

The compositions (A), (B) and (C) may be mixed in the following proportions:

(A) / (B) + (C) ranging from 0.005 to 1 , preferably from 0.01 to 0.5, better still from 0.02 to 0.1 , and/or

(B)/(C) ranging from 0.1 to 10, preferably from 0.5 to 2, better still from 0.6 to 1.5.

A subject of the invention is, similarly, a device comprising at least three compartments containing, in a first compartment, the composition (A) as defined previously, in a second compartment, the composition (B) as defined previously, and in a third compartment the composition (C) as defined previously.

The following example serves to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLE

Example 1 The following compositions are prepared (unless otherwise indicated, the amounts are expressed by weight, i.e. in g% active material).

Compositions (A)

Dyeing composition (B)

Monoethanolamine 4.26

2,5-Toluenediamine 0.066

2,4-diaminophenoxyethanol hydrochloride 0.014

2-Methyl-5-hydroxyethylaminophenol 0.02

N,N-Bis(2-hydroxyethyl)-p-phenylenediamine sulfate 0.015

Resorcinol 0.038

m-Aminophenol 0.023

Mixture of linear C18-24 fatty alcohols 4.6 Liquid petroleum jelly 60

Cetyl palmitate 2

Carbomer (Carbopol 980) 0.1

Oxyethylenated (60 EO) cetylstearyl alcohol ether of

0.01 myristyl glycol (Elfacos GT 282 S from Akzo Nobel)

Deceth-5 (Eumulgin BL 589 from Cognis) 1 .2

Oleth-10 (Brij 96V from Croda) 1

Oleth-20 (Brij 98V from Croda) 4

Glycerol 5

Sequestrant, reducing agent, antioxidant qs

Water qs 100

Oxidizing composition (C)

The compositions obtained are stable.

The compositions (A), (B) and (C) are mixed in a bowl in the following proportions: 4 g of composition A1 or A2

60 g of composition (B)

60 g of composition (C) The mixture is applied to the hair immediately after its preparation.

The composition resulting from the mixing is easy to apply over the whole length of the hair, has a good wetting character and good adhesion to the roots. After a leave-on time of 30 minutes, the hair is rinsed, washed with a standard shampoo and dried. Strong colouring is obtained on the hair, that is sparingly selective and intense.

Example 2

Composition (A)

Ethylene oxide/propylene oxide/ethylene oxide condensate (MW = 7.5 2900 g/mol) (13 EO/30PO/13EO) or Poloxamer 184

Tetramethyl hexamethylenediamine/1 ,3-dichloro-propylene

polycondensate (aqueous 60% solution; Hexadimethrine chloride) 2.4 AM (Mexomere PO from Chimex)

Polydimethyldiallylammonium chloride (non-stabilized aqueous

6.2 AM 33% solution, Polyquaternium-6) (Merquat 106 from Nalco)

Glycerol 4

Water qs 100 pH agent qs pH 10

Dyeing composition (B)

Carbomer (Carbopol 980) 0.1 0.1

Ethylene oxide/propylene oxide/ethylene

oxide condensate (MW = 2900 g/mol) (13 - 0.5 EO/30PO/13EO) or Poloxamer 184

Oxyethylenated (60 EO) cetylstearyl alcohol ether

of myristyl glycol (Elfacos GT 282 S from Akzo 0.01 0.01 Nobel)

Deceth-5 (Eumulgin BL 589 from Cognis) 1 .2 1 .2

Oleth-10 (Brij 96V from Croda) 1 1

Oleth-20 (Brij 98V from Croda) 4 4

Glycerol 5 5

Sequestrant, reducing agent, antioxidant qs qs

Water qs 100 qs 100

Oxidizing composition (C)

The following mixtures are produced in a bowl

Mi M2 M3

Compo A - 2 gr Compo B1 30 gr - 30 gr

Compo B2 . 30 gr .

Compo C 30 gr 30 gr 30 gr

Each mixture is applied to a 1/4 head of malleable hair immediately after its preparation (the evaluation is carried out on 2 heads), at an amount of 30 gr of mixture per 1/4 head.

The mixture M3 according to the invention is easier to apply (ease of spreading the mixture along the hair) and has a better wetting character and better adhesion to the roots than the mixtures M1 and M2.

Intense, strong colouring is obtained on the hair, that is sparingly selective and uniform.

EXAMPLE 3

Composition (A)

Dyeing composition (B)

Monoethanolamine 4.28

1 -Methyl-2,5-diaminobenzene 0.77

1 -Beta-hydroxyethyloxy-2,4-diaminobenzene dihydrochloride 0.02

1 -Hydroxy-3-aminobenzene 0.12

6-Hydroxy benzomorpholine 0.033

Resorcinol 0.67 Mixture of linear C18-24 fatty alcohols 4.6

Liquid petroleum jelly 60

Cetyl palmitate 2

Carbomer (Carbopol 980) 0.1

Oxyethylenated (60 EO) cetylstearyl alcohol ether of myristyl

0.01 glycol (Elfacos GT 282 S from Akzo Nobel)

Deceth-5 (Eumulgin BL 589 from Cognis) 1 .2

Oleth-10 (Brij 96V from Croda) 1

Oleth-20 (Brij 98V from Croda) 4

Glycerol 5

Sequestrant, reducing agent, antioxidant qs

Water qs 100

Oxidizing composition (C)

Sequestrants, stabilizers, preservatives qs qs qs qs

Phosphoric acid qs pH 2.2 qs pH 2.2 qs pH 2.2 qs pH 2.2

Water qs 100 qs 100 qs 100 qs 100

The following mixtures are produced in a bowl:

Each mixture is applied to a 1/4 head of malleable hair immediately after its preparation (the evaluation is carried out on 2 heads), at an amount of 30 gr of mixture per 1/4 head.

The mixture M4 according to the invention has a better wetting character than the mixtures M5, M6 and M7.