Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
PROCESS FOR PREPARING A DYE COMPOSITION, COMPRISING THE MIXING OF AT LEAST TWO TYPES OF SOLID PARTICLES WITH AN AQUEOUS COMPOSITION, AND USE THEREOF
Document Type and Number:
WIPO Patent Application WO/2021/083901
Kind Code:
A1
Abstract:
The present application relates to a process for preparing a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the mixing of at least two different types of solid particles comprising different dyes with at least one aqueous composition comprising an associative polymer, and also to the use of the composition obtained for dyeing keratin fibres.

Inventors:
GUERIN FRÉDÉRIC (FR)
LOGIN GÉRALDINE (FR)
HUCHER ARNAUD (FR)
Application Number:
PCT/EP2020/080192
Publication Date:
May 06, 2021
Filing Date:
October 27, 2020
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
OREAL (FR)
International Classes:
A61K8/02; A61K8/81; A61Q5/10
Domestic Patent References:
WO1996015765A11996-05-30
WO1994008969A11994-04-28
WO1994008970A11994-04-28
WO1995015144A11995-06-08
WO1995001772A11995-01-19
WO2000031154A12000-06-02
WO2000068282A12000-11-16
WO1998044012A11998-10-08
Foreign References:
US20150089751A12015-04-02
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
EP0714954A21996-06-05
US3915921A1975-10-28
US4509949A1985-04-09
EP0173109A21986-03-05
EP0750899A21997-01-02
US5089578A1992-02-18
Other References:
"Cosmetic Nanotechnology", vol. 961, 12 April 2007, AMERICAN CHEMICAL SOCIETY, Washington, DC, ISBN: 978-0-8412-2079-9, article ROBERT Y. LOCHHEAD: "The Role of Polymers in Cosmetics: Recent Trends", pages: 3 - 56, XP055262998, DOI: 10.1021/bk-2007-0961.ch001
CHINESE JOURNAL OF POLYMER SCIENCE, vol. 18, no. 40, 2000, pages 323 - 336
MACROMOLECULES, vol. 33, no. 10, 2000, pages 3694 - 3704
LANGMUIR, vol. 16, no. 12, 2000, pages 5324 - 5332
POLYM. PREPRINT, DIV. POLYM. CHEM., vol. 40, no. 2, 1999, pages 220 - 221
G. FONNUMJ. BAKKEFK. HANSEN, COLLOID POLYM. SCI., vol. 271, 1993, pages 380 - 389
Attorney, Agent or Firm:
MARTIN-CHARBONNEAU, Virginie et al. (FR)
Download PDF:
Claims:
CLAIMS

1. Process for preparing a composition for dyeing keratin fibres, comprising the mixing:

(i) of one or more solid particles of a first type PI containing at least one dye Cl in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type PI containing it; with

(ii) one or more solid particles of a second type P2 containing at least one dye C2 in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type P2 containing it; and

(iii) at least one aqueous composition comprising at least one associative polymer; it being understood that the dye(s) Cl are different from the dye(s) C2.

2. Process according to the preceding claim, characterized in that the dyes Cl and C2 are chosen from direct dyes and/or oxidation dye precursors; preferably from oxidation dye precursors; more preferentially from oxidation bases and oxidation couplers; even more preferentially, Cl and C2 are chosen from oxidation bases; better still, Cl is chosen from oxidation bases and C2 is chosen from oxidation couplers.

3. Process according to the preceding claim, characterized in that the oxidation base(s) are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols ortho-aminophenols and heterocyclic bases, and the corresponding addition salts; more preferentially from para- phenylenediamine, para-toluenediamine, para-aminophenol, N,N-bis(P- hydroxyethyl)-para-phenylenediamine, 4,5-diamino- 1 -(b-hydiOxycthyljpyrazolc, 2,3- diamino-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2 - b - h y d ro x y c t h o x y - 3 - aminopyrazolo[l,5-a]pyridine, and the addition salts thereof.

4. Process according to any one of Claim 2 or Claim 3, characterized in that the oxidation coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene -based coupling agents, heterocyclic coupling agents, the corresponding addition salts thereof or the solvates thereof; more preferentially from 1,3-dihydroxybenzene, l,3-dihydroxy-2-methylbenzene, 3-aminophenol, 6- hydroxybenzomorpholine, 5-N-(P-hydroxyethyl)amino-2-methylphenol, 2,4-diamino- l-(P-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 6-hydroxyindole, 4-chloro- 1,3-dihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-chloro-6- methylphenol, a-naphthol, 2-[3-amino-4-methoxyphenyl]amino)ethanol and the addition salts thereof. 5. Process according to any one of the preceding claims, characterized in that the content of dye(s) (Cl, C2) represents 0.1% to 50% by weight, preferably 0.3% to 25% by weight, more preferentially 0.4% to 22% by weight, relative to the total weight of each solid particle containing it.

6. Process according to any one of the preceding claims, characterized in that the solid particles PI and/or P2 comprise at least one binder; preferably chosen from saccharides and derivatives thereof, oligosaccharides and derivatives thereof, polysaccharides and derivatives thereof, polyvinyl alcohol (PVA), and mixtures thereof; more preferentially from lactose, notably in anhydrous or hydrated form, polyvinyl alcohol (PVA), microcrystalline cellulose (MCC), notably in anhydrous or hydrated form, cellulose ethers such as hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC), and mixtures thereof.

7. Process according to the preceding claim, characterized in that the total content of binder(s) is greater than or equal to 30% by weight; preferably greater than or equal to 50% by weight; more preferentially between 50% and 99.9% by weight, even more preferentially between 60% and 99.9% by weight, and better still between 70% and 99.9% by weight, relative to the total weight of each solid particle containing same.

8. Process according to any one of the preceding claims, characterized in that the solid particle(s) PI and/or P2 comprise at least one disintegrant; preferably a polymeric disintegrant; even more preferentially at least one disintegrant polymer; better still at least one superdisintegrant polymer; even better still at least one superdisintegrant polymer chosen from crosslinked polymers of vinylpyrrolidone and derivatives thereof, and mixtures thereof; more preferentially from crosslinked polyvinylpyrrolidones, crosslinked copolymers of vinylpyrrolidone/vinyl acetate, and mixtures thereof. 9. Process according to the preceding claim, characterized in that the total content of disintegrant(s) is between 0.5% and 15% by weight, preferably between 1% and 12% by weight, and more preferentially between 2% and 10% by weight, relative to the total weight of each solid particle containing it. 10. Process according to any one of the preceding claims, characterized in that the solid particles PI and/or P2 comprise an upper coating layer comprising at least one cellulose ether; preferably a cellulose ether chosen from carboxymethylcellulose (CMC), ethylcellulose (EC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), methylhydroxy ethylcellulose (MHEC), and mixtures thereof, better still from hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), and mixtures thereof.

11. Process according to the preceding claim, characterized in that the upper coating layer comprises one or more pigments; more preferentially one or more pigments chosen from zirconium oxides, zinc oxides, cerium oxides, iron oxides, titanium oxides, chromium oxides, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof; even more preferentially one or more pigments chosen from titanium oxides such as titanium dioxide, iron oxides, chromium oxides, notably green chromium oxide, and mixtures thereof.

12. Process according to any one of the preceding claims, characterized in that the solid particles PI and/or P2 comprise at least one antioxidant; preferably chosen from (a) ascorbic acid, salts thereof and derivatives thereof such as sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, (b) salicylic acid, salts thereof and derivatives thereof such as sodium salicylate, (c) mercaptan and inorganic sulfites such as sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite and thioglycolic acid, and mixtures thereof; more preferentially chosen from ascorbic acid, sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium salicylate, and mixtures thereof; even more preferentially in a total content of between 0.1% and 15% by weight, better still between 0.3% and 12% by weight, even better still between 0.4% and 10% by weight, or even between 0.5% and 5% by weight, relative to the total weight of each solid particle containing same.

13. Process according to any one of the preceding claims, characterized in that the solid particles are anhydrous. 14. Process according to any of the preceding claims, characterized in that the solid particles have a mean volume of between 25 and 125 mm3; preferably between 30 and 90 mm3; more preferentially between 45 and 65 mm3.

15. Process according to any one of the preceding claims, characterized in that the solid particles are of spherical or spheroidal shape; preferably of spherical shape.

16. Process according to any one of the preceding claims, characterized in that the aqueous composition comprises at least one alkaline agent; preferably chosen from aqueous ammonia, alkali metal or alkaline-earth metal metasilicates, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, compounds including a guanidine function, and mixtures thereof; more preferentially, the alkaline agent is arginine.

17. Process according to the preceding claim, characterized in that the total content of alkaline agent(s) is between 0.05% and 25% by weight, preferably between 0.1% and 20% by weight, more preferentially between 0.5% and 15% by weight, better still between 1% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition.

18. Process according to any one of the preceding claims, characterized in that the aqueous composition comprises at least one chemical oxidizing agent; preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids, and oxidase enzymes, for instance peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases, and mixtures thereof; more preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide and persalts, and mixtures thereof.

19. Process according to any one of the preceding claims, characterized in that the associative polymer(s) are chosen from anionic associative polymers, nonionic associative polymers and mixtures thereof; more preferentially from (i) copolymers including among their monomers an a,b-monoethylenically unsaturated carboxylic acid and an ester of an a,b-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol, (ii) celluloses or derivatives thereof, modified with groups including at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are C8-C30 and in particular nonionic alkylhydroxyethylcelluloses, and (iii) mixtures thereof; even more preferentially from acrylates/beheneth-25 methacrylate copolymer, cetyl hydroxyethylcellulose, and mixtures thereof.

20. Process according to any one of the preceding claims, characterized in that it comprises the mixing of n types of solid particles PI to Pn, with n representing an integer greater than or equal to 3, and preferably between 3 and 20, more preferentially between 3 and 15 and even more preferentially between 4 and 10; each type of solid particle PI to Pn containing at least one dye respectively Cl to Cn, preferably only one dye, as defined in any one of Claims 2 to 5, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particles PI to Pn, respectively, and it being understood that said dyes C 1 to Cn are all different from each other. 21. Process according to any one of Claims 1 to 15, characterized in that it comprises the mixing:

- of one or more solid particles PI and of one or more solid particles P2, as defined according to any one of Claims 1 to 15, with

- at least one aqueous composition C comprising at least one associative polymer, preferably chosen from those defined in Claim 19; and with

- at least one different aqueous composition A comprising at least one chemical oxidizing agent, preferably chosen from those defined in Claim 18, more preferentially from hydrogen peroxide, persalts and mixtures thereof, and/or

- at least one different aqueous composition B comprising at least one alkaline agent, preferably chosen from those defined in Claim 16; more preferentially, the alkaline agent is arginine.

22. Process according to the preceding claim, characterized in that it comprises the mixing:

- of one or more solid particles PI and of one or more solid particles P2, as defined according to any one of Claims 1 to 15; with

- at least one aqueous composition A, at least one aqueous composition B and at least one aqueous composition C, as defined according to Claim 21. 23. Process for dyeing the keratin fibers, comprising the implementation of a step of applying to said fibers the composition obtained according to the preparation process as defined in any one of claims 1 to 22, less than two hours, preferably less than an hour, more preferably less than 30 minutes, after obtaining said composition according to said preparation process.

24. Use of the composition obtained via the process as defined in any one of Claims 1 to 23, for the dyeing, preferably for the oxidation dyeing, of keratin fibres.

Description:
DESCRIPTION

TITLE: PROCESS FOR PREPARING A DYE COMPOSITION, COMPRISING THE MIXING OF AT LEAST TWO TYPES OF SOLID PARTICLES WITH AN AQUEOUS COMPOSITION, AND USE THEREOF

The present application relates to a process for preparing a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the mixing of at least two different types of solid particles with one or more aqueous compositions, and also to the use of the composition obtained for dyeing keratin fibres.

It is known practice to dye keratin fibres and in particular human hair with dye compositions containing oxidation dye precursors, such as oxidation bases, notably ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, are able to produce coloured compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or colour modifiers, the latter being notably chosen from aromatic meta-diaminobenzenes, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

At the present time, it is difficult to customize the permanent dyeing of keratin fibres. Specifically, a user wishing to dye his or her hair only has a choice from a catalogue of predefined dye compositions, each generally comprising a set mixture of oxidation base(s) and of oxidation couplers(s) in predefined contents.

Thus, each of these dye compositions makes it possible to obtain only one colour shade and the user has a choice from only a limited number of shades preselected by the manufacturers, which do not always correspond to his or her desires.

Furthermore, the predefined dye compositions do not always lead exactly to the production of the corresponding preselected shade: as a function of the natural shade (more or less light or dark) and of the condition of the user’s hair (more or less damaged or sensitized), the final rendering in terms of colouring may vary substantially from one user to another. The current oxidation dyeing processes thus do not make it possible rapidly to obtain (for example during a user's appointment at the hair salon) customized colourings as a function of the pre-existing shade of the user's keratin fibres, or according to his or her desires. There is thus a real need to develop a process for preparing, just before dyeing, a composition for dyeing keratin fibres which makes it possible to offer the user a very wide choice of possible shades, and enabling him or her to be able to choose, for example in a hair salon, the shade that he or she desires rather than as a default the closest available shade. The process will also have to make it possible to prepare, just before dyeing, a composition for dyeing keratin fibres which makes it possible to offer the user a tailored colouring, notably taking into account his or her specificities such as the pre existing shade and the nature of the keratin fibres.

Moreover, the process must also make it possible to obtain a composition that can dye keratin fibres in an intense, fast, sparingly selective and chromatic manner, with good build-up of the colour, and which is capable of giving colourings that are resistant to the various attacking factors to which the fibres may be subjected, such as bad weather, washing and perspiration.

These aims are achieved by the present invention, one subject of which is notably a process for preparing a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the mixing:

(i) of one or more solid particles of a first type PI containing at least one dye Cl in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type PI containing it; with (ii) one or more solid particles of a second type P2 containing at least one dye C2 in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type P2 containing it; and

(iii) at least one aqueous composition comprising at least one associative polymer; it being understood that the dye(s) Cl are different from the dye(s) C2.

It has been found that the preparation process according to the invention allows the production of a customized and ready-to-use composition for dyeing keratin fibres. Specifically, the process according to the invention makes it possible to prepare, for each use, a specific dye composition containing precise amounts of dye precursors specifically chosen so as to obtain the exact shade desired by the user.

It has notably been found that the process according to the invention makes it possible to prepare compositions that are capable of combining a very large number of different dyes, in different respective contents, and thus to dye the keratin fibres in a very wide range of possible colours while at the same time taking into account the nature and condition of said fibres.

The composition obtained via the process according to the invention can also satisfactorily dye keratin fibres, notably producing powerful, fast, chromatic and sparingly selective colourings, and/or colourings with good colour build-up.

Moreover, the composition obtained via the process according to the invention may lead to colourings that are resistant to the various attacking factors to which keratin fibres may be subjected, such as bad weather, light, washing and/or perspiration.

Moreover, the process according to the invention gives a reproducible dyeing result time after time, the solid particles containing a dose of predetermined dye having very good stability on storage. Furthermore, the solid particles used in the process of the invention disintegrate rapidly and lead rapidly and easily to a homogeneous mixture with the aqueous composition(s) used in the process.

A subject of the invention is also the use of the composition obtained via the preparation process according to the invention, for dyeing keratin fibres, in particular human keratin fibres such as the hair.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the example that follows.

In the present description, and unless otherwise indicated:

- the expression "at least one" is equivalent to the expression "one or more" and can be replaced therewith;

- the expression "between" is equivalent to the expression "ranging from" and can be replaced therewith, and implies that the limits are included;

- the term "keratin fibres", according to the present patent application, preferably denotes human keratin fibres and more particularly the hair.

The solid particles The process according to the present invention comprises the mixing of at least two different types of solid particles, namely one or more solid particles of a first type PI and one or more solid particles of a second type P2, containing, respectively, at least one dye Cl and C2 of different nature, each of the particles comprising a content of dye(s) of between 0.001 % and 50% by weight relative to the total weight of each solid particle, with at least one aqueous composition comprising at least one associative polymer.

According to a preferred embodiment of the invention, the process comprises the mixing: (i) of one or more solid particles of a first type PI containing only one dye Cl in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type PI containing it; with

(ii) one or more solid particles of a second type P2 containing only one dye C2 in a content of between 0.001% and 50% by weight relative to the total weight of the particle of the type P2 containing it; and

(iii) at least one aqueous composition comprising at least one associative polymer; it being understood that the dye Cl is different from the dye C2.

It is understood that each type of solid particle according to the invention comprises at least one dye in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle containing it. It is also understood that at least two types of solid particles used in the process according to the invention do not comprise the same dye(s).

According to a particular embodiment of the invention, the process also comprises mixing with one or more solid particles of a third type P3, containing at least one dye C3, preferably only one dye C3, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) P3. It is thus possible to mix as many dyes as necessary, and in the necessary respective proportions, to achieve the desired shade. Thus, according to another preferred embodiment, the process according to the invention comprises the mixing of n types of solid particles PI to Pn (with n representing an integer greater than or equal to 3, and preferably between 3 and 20, more preferentially between 3 and 15 and even more preferentially between 4 and 10), each type of solid particle PI to Pn containing at least one dye (respectively Cl to Cn), better still only one dye, even better still only one oxidation dye precursor, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particles PI to Pn, respectively, and it being understood that said dyes Cl to Cn are all different from each other. According to a particular embodiment of the invention, the composition for dyeing keratin fibres also comprises one or more solid particles of the type P’x (with x representing an integer greater than 1, and preferably between 1 and 20, more preferentially between 1 and 15 and even more preferentially between 1 and 10) containing at least one dye Cx, better still only one dye, in a content of between 0.1% and 50% by weight relative to the total weight of the solid particle(s) of the type P’x; said solid particle of the type P’x corresponding to the solid particle Px described previously apart from the content of dye Cx.

By way of example of this particular embodiment of the invention, the composition for dyeing keratin fibres may comprise: (i) one or more solid particles of a first type PI containing at least one dye Cl, better still only one dye Cl, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type PI;

(ii) one or more solid particles of a second type P2 containing at least one dye C2, better still only one dye C2, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type P2;

(iii) one or more solid particles of the type P’l containing said dye(s) Cl in a content of between 0.1% and 50% by weight relative to the total weight of the solid particle(s) of the type P’l; and

(iv) at least one aqueous composition comprising at least one associative polymer; it being understood that:

- the dye(s) Cl are different from the dye C2;

- the content of dye(s) Cl contained in the solid particle(s) PI is different from the content of dye(s) Cl contained in the solid particle(s) P’l.

The dyes

Preferably, the dyes Cl and C2 (and more generally Cl to Cn) as mentioned above are chosen from direct dyes and/or oxidation dye precursors; more preferentially from oxidation dye precursors; even more preferentially from oxidation bases and oxidation couplers; better still, Cl and C2 are chosen from oxidation bases; even better still, Cl is chosen from oxidation bases and C2 is chosen from oxidation couplers (or vice versa). Preferably, the content of dye(s) (Cl, C2, and more generally Cl to Cn) advantageously represents from 0.1% to 50% by weight, more preferentially from 0.3% to 25% by weight and even more preferentially from 0.4% to 22% by weight, relative to the total weight of each solid particle containing it (PI, P2, and more generally PI to Pn, respectively).

By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols ortho- aminophenols and heterocyclic bases, and the corresponding addition salts.

Among the para-phenylenediamines that may be mentioned are, for example, para-phenylenediamine, para-toluenediamine, 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, N,N -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-hydroxycthyl)ami no-2- mcthylani line, 4-N,N- bis(P-hydroxyethyl)amino-2-chloroaniline, 2- b- h y dro x y ct h y \-pa ra- phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para- phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ( b - h y d ro x y p ro p y 1 ) - p a ra - phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3- methyl-para-phenylenediamine, N-ethyl-N-^-hydroxyethyl)-para-phenylenediamine,

N-(b,g-dihydroxypropyl) -para-phenylenediamine, N-(4’-aminophenyl)-para- phenylenediamine, N-phenyl-para-phenylenediamine, 2^-hydroxyethyloxy-para- phenylenediamine, 2-b-acetylaminoethyloxy-para-phenylenediamine, N-(b- methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para- phenylenediamine, 2-b-hydroxyethylamino-5-aminotoluene and 3 -hydroxy- 1 -(4’- aminophenyl)pyrrolidine, and the corresponding addition salts with an acid.

Among the para-phenylenediamines mentioned above, para- phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-b- hydroxyethyl-para-phenylenediamine, 2^-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 the corresponding addition salts with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-l,3-diamin opropanol, N,N'- 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 and l,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the corresponding addition salts.

Among the para-aminophenols that are mentioned are, for example, 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 corresponding addition salts with an acid. Among the ortho-aminophenols that may be mentioned, for example, are 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the corresponding addition salts.

Among the heterocyclic bases that may be mentioned, for example, are pyridine, pyrimidine and pyrazole derivatives. Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for example 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and the corresponding addition salts.

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

(morpholin-4-yl)pyrazolo[l,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[l,5-a]pyrid-5- yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[l,5-a]pyrid-7-yl)(2- hydroxyethyl)amino] ethanol, 3 -aminopyrazolo [ 1 ,5-a]pyridin-5-ol, 3 - aminopyrazolo[l,5-a]pyridin-4-ol, 3-aminopyrazolo[l,5-a]pyridin-6-ol, 3- aminopyrazolo[l,5-a]pyridin-7-ol, 2-P-hydroxyethoxy-3-aminopyrazolo[l,5- a]pyridine and 2-(4-dimethylpiperazinium-l-yl)-3-aminopyrazolo[l,5-a]pyridi ne, and the corresponding addition salts.

More particularly, the oxidation bases that are useful in the present invention are chosen from 3-aminopyrazolo[l,5-a]pyridines and are preferably substituted on carbon atom 2 with: a) a (di)(Ci-C 6 )(alkyl)amino group, said alkyl group possibly being substituted with at least one hydroxyl, amino or imidazolium group; b) an optionally cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (Ci- C 6 )alkyl groups such as a di(Ci-C4)alkylpiperazinium group; or c) a (Ci-C 6 )alkoxy group optionally substituted with one or more hydroxyl groups, such as a b-hydroxyalkoxy group, and the corresponding addition salts.

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; 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 that may be mentioned are 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- l-(P-hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 4,5-diamino- l-(4'-chlorobenzyl)pyrazole, 4,5-diamino- 1,3- dimethylpyrazole, 4,5-diamino-3-methyl- 1-phenylpyrazole, 4,5-diamino- l-methyl-3- phenylpyrazole, 4-amino- l,3-dimethyl-5-hydrazinopyrazole, 1 -benzyl-4, 5-diamino-3- methylpyrazole, 4, 5-diamino-3-/ <? / -butyl- 1 -mcthylpyrazolc, 4,5-diamino- 1 -lerl- butyl-3-methylpyrazole, 4,5-diamino- l-(P-hydroxyethyl)-3-methylpyrazole, 4,5- diamino-l-ethyl-3-methylpyrazole, 4,5-diamino- l-ethyl-3-(4'- methoxyphenyl)pyrazole, 4,5-diamino- l-ethyl-3-hydroxymethylpyrazole, 4,5- diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-l- isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5- triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4-

(b-hydiOxycthyljamino- 1 -mcthylpyrazolc, and the corresponding addition salts. Use may also be made of 4,5-diamino- l-(P-methoxyethyl)pyrazole.

A 4,5-diaminopyrazole will preferably be used and even more preferentially 4,5-diamino-l -(b-hydiOxycthyljpyrazolc and/or a corresponding salt. The pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR- A-2 886 136, such as the following compounds and the corresponding addition salts: 2, 3-diamino-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3- ethylamino-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3- isopropylamino-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3-

(pyrrolidin-l-yl)-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-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- l,2-bis(2-hydroxyethyl)-l,2-dihydropyrazol-3-one, 2-amino-3-(2- hydroxyethyl)amino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol- l-one, 2-amino-3- dimethylamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one , 2,3-diamino-

5,6,7,8-tetrahydro-lH,6H-pyridazino[l,2-a]pyrazol-l-one, 4-amino-l,2-diethyl-5- (pyrrolidin-l-yl)-l,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin- 1-yl)- 1, 2-diethyl- l,2-dihydropyrazol-3-one and 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- 1H,5H- pyrazolo[l,2-a]pyrazol-l-one and/or a corresponding salt.

Heterocyclic bases that will preferably be used are 4,5-diamino- 1-(b- hydroxyethyl)pyrazole and/or 2, 3-diamino-6, 7-dihydro- lH,5H-pyrazolo[l, 2- a]pyrazol-l-one and/or 2^-hydroxyethoxy-3-aminopyrazolo[l,5-a]pyridine and/or a corresponding salt.

According to a preferred embodiment of the invention, the oxidation dye precursor is an oxidation base; more preferentially an oxidation base chosen from para- phenylenediamine, para-toluenediamine, para-aminophenol, N,N-bis(P- hydroxyethyl)-para-phenylenediamine, 4,5-diamino- l-(P-hydroxyethyl)pyrazole, 2,3- diamino-6, 7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2 - b - h y d ro x y c t h o x y - 3 - aminopyrazolo[l,5-a]pyridine, and the addition salts thereof.

Preferably, when the oxidation dye precursor is an oxidation base, the oxidation base advantageously represents 0.1% to 50% by weight, more preferentially 0.3% to 25% by weight, even more preferentially 0.4% to 22% by weight, relative to the total weight of the solid particle containing it.

By way of example, the oxidation couplers may be chosen from meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene -based coupling agents and heterocyclic coupling agents, and also the geometrical or optical isomers thereof, the tautomers thereof, the corresponding addition salts or the solvates thereof according to the invention.

Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3- dihydroxy-2-methylbenzene, 4-chloro- 1,3-dihydroxybenzene, 2,4-diamino- 1 -(b- hydroxyethyloxy)benzene, 2-amino-4-^-hydroxyethylamino)-l-methoxybenzene, 1,3-diaminobenzene, l,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- 1-dimethylaminobenzene, sesamol, l^-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-(b- hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis^- hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1- H-3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2,6- dimethylpyrazolo[l,5-b]-l, 2, 4-triazole, 2, 6-dimethyl[3,2-c]- 1,2, 4-triazole and 6- methylpyrazolo[l,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(b- hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 3-amino-2-chloro-6- methylphenol and 2-[3-amino-4-methoxyphenyl]amino)ethanol, and the corresponding addition salts with an acid. According to a preferred embodiment of the invention, the oxidation dye precursor is an oxidation coupler; more preferentially an oxidation coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene- based coupling agents, heterocyclic coupling agents, the corresponding addition salts thereof or the solvates thereof; even more preferentially 1,3-dihydroxybenzene, 1,3- dihydroxy-2-methylbenzene, 3-aminophenol, 6-hydroxybenzomorpholine, 5-N-(b- hydroxyethyl)amino-2-methylphenol, 2,4-diamino- l-(P-hydroxyethyloxy)benzene, 2- methyl-5-aminophenol, 6-hydroxyindole, 4-chloro- 1,3-dihydroxybenzene, 2-amino-3- hydroxypyridine, 3-amino-2-chloro-6-methylphenol, a-naphthol, 2-[3-amino-4- methoxyphenyl]amino)ethanol and the addition salts thereof.

Preferably, when the oxidation dye precursor is an oxidation coupler, the oxidation coupler advantageously represents 0.1% to 50% by weight, more preferentially 0.3% to 25% by weight, even more preferentially 0.4% to 22% by weight, relative to the total weight of the solid particle containing it.

In general, the addition salts of oxidation bases or of oxidation couplers that may be used in the context of the invention are chosen in particular from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The direct dyes

The dyes Cl and C2, (and more generally Cl to Cn) may be chosen from direct dyes; preferably chosen from cationic, anionic and nonionic direct dyes, and mixtures thereof; more preferentially from cationic and nonionic direct dyes and mixtures thereof.

The direct dyes may be synthetic or natural.

Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

Mention may notably be made, by way of example, of the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. In particular, the useful direct dyes may be chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:

Basic Red 51

Basic Orange 31 , n Basic Yellow 87

Among the natural direct dyes that may be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts may also be used.

Preferably, when the direct dye(s) are present in one type of solid particle, the direct dye(s) advantageously represent 0.001% to 10% by weight, more preferentially 0.005% to 5% by weight, relative to the total weight of the solid particle containing it. The binders

Each type of solid particle PI and/or P2 (and more generally PI to Pn) according to the invention also preferably comprises at least one binder.

For the purposes of the invention, the term “binder” means a compound which contributes towards the cohesion of the solid particle. The binder notably enables the agglomeration of the various components constituting the solid particle.

Examples of binders that may notably be mentioned include proteins (such as gelatin); saccharides and derivatives thereof, oligosaccharides and derivatives thereof including disaccharides (such as sucrose and lactose), notably in the anhydrous or hydrated forms thereof, and sugar alcohols (such as xylitol, sorbitol and maltitol); polyvinyl alcohol (PVA); polysaccharides and derivatives thereof (for example starches, cellulose and/or modified cellulose); alginate; and gums (for example acacia gum or guar gum).

Examples of suitable modified celluloses include microcrystalline cellulose (MCC), notably in the anhydrous or hydrated forms thereof, and cellulose ethers such as hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC).

Preferably, the binder(s) are chosen from saccharides and derivatives thereof, oligosaccharides and derivatives thereof, polysaccharides and derivatives thereof, polyvinyl alcohol (PVA), and mixtures thereof; more preferentially from lactose, notably in anhydrous or hydrated form, microcrystalline cellulose (MCC), notably in anhydrous or hydrated form, polyvinyl alcohol (PVA), cellulose ethers such as hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC), and mixtures thereof.

Preferably, when the binder(s) are present in one type of solid particle, the total content of binder(s) is greater than or equal to 30% by weight relative to the total weight of said solid particles; more preferentially, the content of binder(s) is greater than or equal to 50% by weight; even more preferentially between 50% and 99.9% by weight, better still between 60% and 99.9% by weight, even better still between 70% and 99.9% by weight, relative to the total weight of each solid particle containing it.

The disintesrants Each type of solid particle PI and/or P2 (and more generally PI to Pn) also preferably comprises at least one disintegrant.

For the purposes of the present invention, the term “disintegrant” refers to a class of agents, preferably a class of polymers, which are particularly effective for inducing the disintegration of a solid particle (for example a tablet). One particular category of disintegrants is known as “superdisintegrants” since they are generally effective at low concentrations.

Disintegrants may be hygroscopic compounds which act by absorbing the liquid of a medium when they are placed in contact with said medium (for example the water of an aqueous medium). Such an absorption may then induce disintegration by bringing about considerable swelling of the disintegrant and/or by reinforcing the capillary action. The swelling pressure exerted by a disintegrant swollen in an external or radial direction can bring about the splitting of a solid particle (for example a tablet). Examples of disintegrants, or even of superdisintegrants, that may notably be mentioned include crosslinked celluloses such as croscarmellose (or crosslinked carboxymethylcellulose, which is generally used in sodium salt form) and derivatives thereof, sold, for example, under the references Ac-Di-Sol ® , Explocel ® , Nymcel ZSX ® , Pharmacel ® XL, Primellose ® , Solutab ® and Vivasol ® ; crospovidone (or crosslinked polyvinylpyrrolidone) and derivatives thereof, sold, for example, under the references Crospovidone M ® , Kollidon ® and Polyplasdone ® ; crosslinked starch such as sodium starch glycolate, sold, for example, under the references Explotab ® , Explotab ® CLV, Explosol ® , Primojel ® , Tablo ® and Vivastar ® ; crosslinked alginic acids, sold, for example, under the reference Satialgine ® ; crosslinked polyacrylic compounds such as ion-exchange resins, sold, for example, under the references Indion ® 414, Tulsion ® 339 and Amberlite ® IRP; and certain polysaccharides, such as soybean polysaccharide, sold, for example, under the reference Emcosoy ® superdisintegrant.

Preferably, the disintegrant(s) are polymeric; more preferentially, each type of solid particle comprises at least one disintegrant polymer, better still at least one superdisintegrant polymer; even more preferentially at least one superdisintegrant polymer chosen from crosslinked polymers of vinylpyrrolidone and derivatives thereof, and mixtures thereof; better still from crosslinked polyvinylpyrrolidones, crosslinked copolymers of vinylpyrrolidone/vinyl acetate, and mixtures thereof. Preferably, when the disintegrant(s) are present in one type of solid particle, the total content of disintegrant(s) is between 0.5% and 15% by weight, more preferentially between 1% and 12% by weight, and even more preferentially between 2% and 10% by weight, relative to the total weight of each solid particle containing it.

The antioxidants

Each type of solid particle PI and/or P2 (and more generally PI to Pn) also preferably comprises at least one antioxidant.

Examples of antioxidants that may notably be mentioned include ascorbic acid, salts thereof and derivatives thereof (such as sodium ascorbate, erythorbic acid, ascorbyl palmitate or ascorbyl laurate); salicylic acid, salts thereof and derivatives thereof (such as sodium salicylate); mercaptans and inorganic sulfites (such as sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite and thioglycolic acid); 2,6-di-tert-butyl-4-methylphenol (BHT); butylated hydroxyanisole (BHA); sodium dithionite; and mixtures thereof.

Preferably, the antioxidants are chosen from ascorbic acid, salts thereof and derivatives thereof (such as sodium ascorbate, erythorbic acid, ascorbyl palmitate or ascorbyl laurate); salicylic acid, salts thereof and derivatives thereof (such as sodium salicylate); mercaptans and inorganic sulfites (such as sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite and thioglycolic acid), and mixtures thereof; more preferentially from ascorbic acid, sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium salicylate, and mixtures thereof.

Preferably, when the antioxidant(s) are present in one type of solid particle, the total content of antioxidant(s) is between 0.1% and 15% by weight, more preferentially between 0.3% and 12% by weight, even more preferentially between 0.4% and 10% by weight, better still between 0.5% and 5% by weight, relative to the total weight of said solid particles.

Lubricants and/or nonstick agents Each type of solid particle PI and/or P2 (and more generally PI to Pn) also preferably comprises at least one lubricant and/or nonstick agent.

For the purposes of the invention, the term “lubricant and/or nonstick agent” means a compound for reducing, or even preventing, the agglomeration of the ingredients of the solid particles, for reducing the adhesion (notably during a compression step) and/or for improving the flow of the ingredients of the solid particles by reducing the friction and the cohesion between the ingredients.

Preferably, the lubricant(s) and/or nonstick agent(s) are chosen from magnesium stearate, calcium silicate, magnesium silicate, magnesium carbonate, silicon dioxide, talc, silica, stearic acid, sodium stearoyl fumarate, and mixtures thereof; more preferentially from silica, magnesium stearate, and mixtures thereof.

Preferably, when the lubricant(s) and/or nonstick agent(s) are present in one type of solid particle, the total content of lubricant(s) and/or nonstick agent(s) is between 0.1% and 10% by weight, more preferentially between 0.3% and 8% by weight, and even more preferentially between 0.5% and 5% by weight, relative to the total weight of said solid particles. The upper coating layer

Each type of solid particle PI and/or P2 (and more generally PI to Pn) also preferably comprises an upper coating layer (also known as the upper film layer).

The upper coating layer according to the invention may optionally comprise cellulose ethers such as those described previously. The upper coating layer according to the invention may optionally comprise one or more other compounds such as polyethylene glycol (PEG); polyvinyl alcohol (PVA); polyvinylpyrrolidone (PVP); copolymers thereof (for example a copolymer of polyvinyl alcohol-polyethylene glycol PV A/PEG); sugars such as xanthan; and mixtures thereof. Preferably, the upper coating layer comprises at least two different cellulose ethers.

According to a preferred embodiment of the invention, the upper coating layer comprises at least one cellulose ether as described previously; more preferentially a cellulose ether chosen from carboxymethylcellulose (CMC), ethylcellulose (EC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), methylhydroxyethylcellulose (MHEC), and mixtures thereof, better still from hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), and mixtures thereof. More preferentially, the upper coating layer comprises hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC).

Preferably, according to this embodiment of the invention, the total content of cellulose ether(s) present in the upper coating layer is between 30% and 99% by weight, more preferentially between 40% and 90% by weight, even more preferentially between 50% and 70% by weight, relative to the total weight of the upper coating layer.

According to another preferred embodiment according to the invention, the upper coating layer comprises at least one lubricant and/or nonstick agent such as those described previously; more preferentially at least one lubricant and/or nonstick agent chosen from calcium silicate, magnesium silicate, magnesium carbonate, silicon dioxide, talc, silica, and mixtures thereof; more preferentially, the lubricant and/or nonstick agent is talc.

Preferably, according to this embodiment, the total content of lubricant(s) and/or nonstick agent(s) present in the upper coating layer is between 1% and 40% by weight, more preferentially between 2% and 30% by weight, relative to the total weight of the upper coating layer.

Preferably, the upper coating layer according to the invention also comprises one or more pigments. By way of example, the pigments may be white or coloured, mineral and/or organic, and coated or uncoated. Among the mineral pigments that may be mentioned are metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, titanium oxide or chromium oxide, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof. Among the organic pigments that may be mentioned are carbon black, pigments of D & C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium, and mixtures thereof. According to a preferred embodiment of the invention, the upper coating layer according to the invention also comprises one or more pigments chosen from zirconium oxides, zinc oxides, cerium oxides, iron oxides, titanium oxides, chromium oxides, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof; more preferentially one or more pigments chosen from titanium oxides such as titanium dioxide, iron oxides, chromium oxides, notably green chromium oxide, and mixtures thereof.

When the upper coating layer comprises one or more pigments, the pigment(s) advantageously represent a total content ranging from 1% to 50% by weight, more preferentially 5% to 40% by weight, relative to the total weight of the upper coating layer.

Preferably, the solid particles according to the invention are anhydrous. The term "anhydrous solid particle" means that the solid particle contains less than 2% by weight of water, preferably less than 1% by weight of water, and even more preferentially less than 0.5% by weight of water relative to the total weight of the solid particle, or even said solid particle is free of water. In particular, the water that may be present is not added during the preparation of the solid particle, but corresponds to the residual water provided by the mixed ingredients.

The solid particles according to the invention may advantageously be in a spherical or spheroidal form; more preferentially in a spherical form, such as in the form of a bead. Preferably, the solid particles according to the invention have a mean volume of between 25 and 125 mm 3 , more preferentially between 30 and 90 mm 3 , even more preferentially between 45 and 65 mm 3 .

The volume V of a solid particle in substantially spherical or spheroidal form may notably be calculated by means of the following equation: V = (4/3). p.G 3 in which r represents the radius of the solid particle. Preferably, the solid particles have a mean mass of between 30 and 120 mg, more preferentially between 40 and 80 mg, even more preferentially between 50 and 70 mg.

Preferably, the mean hardness of the solid particles is between 2 and 15 kPa, more preferentially between 2 and 11 kPa.

The mean hardness of the solid particles may be measured, for example, using a semiautomatic tablet testing system commonly used in the pharmaceutical field, notably using the Pharmatron ST50 device. Preferably, the solid particles according to the invention have a mean disintegration time in 25 mL of aqueous hydrogen peroxide solution (containing 6% by weight of H2O2) at 25°C and at atmospheric pressure of less than 60 seconds, more preferentially less than 40 seconds, better still between 1 and 30 seconds.

By way of example, the mean disintegration time may be measured according to the following method:

1) 25 mL of an aqueous oxidizing composition comprising 6% by weight of hydrogen peroxide are poured into a 50 mL beaker; and then

2) 10 identical colouring solid particles according to the invention are added in a single portion; the contents of the beaker are not stirred; and then 3) the chronometer is started;

4) the chronometer is stopped, once all the solid particles are visually fully deaggregated, i.e. once it is observed that the solid particles form a soft mass no longer containing a firm core; and finally

5) the mean disintegration time on the chronometer is recorded.

The solid particles according to the invention are advantageously prepared according to the conventional processes for preparing tablets, which may be film- coated, such as the processes used in the pharmaceutical industry.

More particularly, the solid particles according to the invention may be prepared via a dry route according to the following steps: milling of the ingredients of the solid particle; and then screening of the powder obtained; and then mixing of said powder; and then direct compression of the mixture obtained as a solid particle; and optionally coating of the solid particles obtained. According to another particular preparation method, the solid particles according to the invention may be prepared via wet granulation according to the following steps: premixing the binder(s) (for example lactose, microcrystalline cellulose and polyvinyl alcohol (PVA)), and the dye(s); and then - spraying onto the premix the disintegrant(s) (for example a crosslinked polyvinylpyrrolidone) dissolved in one or more solvents such as those described in the paragraph below for the coating composition, in particular in water, for the production of the desired granulate; and then drying of the granulate; and then - milling of the other ingredients of the solid particle; and then screening of the powder obtained by milling and of the granulate; and then mixing of the powders obtained by screening; and then direct compression of the mixture obtained as a solid particle; and optionally coating of the solid particles obtained.

The coating composition for coating the solid particles comprises one or more cellulose ethers as described previously for the upper coating layer. Preferably, said coating composition also comprises one or more of the preferred ingredients of the upper coating layer as described previously; more preferentially in contents as described previously in the upper coating layer.

More preferentially, said coating composition also comprises one or more solvents chosen from water, C \ -Ce alcohols, and mixtures thereof; even more preferentially chosen from water, ethanol, and mixtures thereof.

By way of example, the coating composition may be prepared from one or more solvents, in particular as described above, and from a mixture containing hydroxypropylmethylcellulose and hydroxypropylcellulose. According to this example, the coating composition may optionally contain one or more fatty substances, which are preferably liquid at 25°C and at atmospheric pressure, such as one or more fatty alcohols, fatty esters and/or triglycerides, for example chosen from octyldodecanol, isopropyl myristate, a plant oil and/or caprylic/capric acid triglyceride.

The composition may also optionally contain talc and/or pigments for colouring the coating, preferably talc and pigments such as titanium dioxide.

The milling step may notably be performed using a mill, for instance a U5 Quadro ® Comil ® .

The screening step may notably be performed using a granulator, for instance a Roto P50 (Zanchetta) or High Shear Mixer P/VAC- 10 (Diosna).

The mixing step may notably be performed using a blender, for instance an MB015 Blender (Pharmatech).

The step of direct compression of the mixture may notably be performed using a compression table, for instance a PR-1500 (PTK). The step of coating said particles may notably be performed using a film coating station, for instance an LDCS-Pilot Hi-Coater ® (Freund-vector).

Aqueous conwosition(s):

The process according to the present invention comprises the mixing of at least two types of solid particle (PI, P2, and more generally PI to Pn) with at least one aqueous composition comprising at least one associative polymer.

Preferably, the aqueous composition(s) comprising at least one associative polymer according to the invention comprise at least one alkaline agent, at least one oxidizing agent and/or at least one cationic polymer other than the associative polymer. Preferably, the water content of the aqueous composition according to the invention is between 30% and 99% by weight, more preferentially between 50% and 99% by weight and better still between 50% and 90% by weight, relative to the total weight of the aqueous composition. The alkaline agents

The aqueous composition according to the invention also preferably comprises at least one alkaline agent.

Preferably, the alkaline agent(s) may be chosen from organic alkaline agents and inorganic alkaline agents. Preferably, the organic alkaline agent(s) are chosen from organic amines, the pK b of which at 25°C is less than 12, more preferentially less than 10 and even more advantageously less than 6. It should be noted that it is the pK b corresponding to the function which has the highest basicity. In addition, the organic amines do not comprise any alkyl or alkenyl fatty chains comprising more than ten carbon atoms.

The organic alkaline agent(s) are preferably chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different C1-C4 hydroxy alkyl radicals.

The term “alkanolamine” means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched Ci to Cs alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N- dimethylethanolamine, 2-amino-2-methyl-l -propanol, triisopropanolamine, 2-amino- 2-methyl- 1,3 -propanediol, 3-amino- 1,2-propanediol, 3-dimethylamino- 1,2- propanediol and tris(hydroxymethyl)aminomethane are in particular suitable for performing the invention. Among the alkanolamines, it is most particularly preferred to use monoethanolamine.

The organic alkaline agent(s) may be chosen from amino acids of natural or synthetic origin, in their L, D or racemic form, and include 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 notably 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. 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 in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be chosen from compounds including 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 notably 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-l-sulfonic acid.

Among the inorganic alkaline agents that may be used in the process according to the invention, mention may be made of mineral hydroxides.

The mineral hydroxides may be chosen from alkali metal, alkaline-earth metal, transition metal and ammonium hydroxides. Examples of mineral hydroxides that may be mentioned include ammonium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, manganese hydroxide and zinc hydroxide.

Among the mineral hydroxides, ammonium hydroxide, also known as aqueous ammonia, is preferred.

The inorganic alkaline agent(s) may also be chosen from urea, ammonium salts such as ammonium chloride, ammonium sulfate, ammonium phosphate or ammonium nitrate, and silicates, phosphates or carbonates of alkali metals or alkaline- earth metals, such as lithium, sodium, potassium, magnesium, calcium and barium, and mixtures thereof, preferably from alkali metal or alkaline-earth metal silicates, in particular alkali metal or alkaline-earth metal metasilicates such as sodium metasilicate.

Preferably, the alkaline agent(s) that are useful in the invention are chosen from aqueous ammonia, alkali metal or alkaline-earth metal metasilicates, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, compounds including a guanidine function, and mixtures thereof.

More preferentially, the aqueous composition comprises arginine.

According to a preferred embodiment of the invention, the aqueous composition comprises one or more alkaline agents; more preferentially chosen from basic amino acids; even more preferentially, the alkaline agent is arginine.

According to another preferred embodiment of the invention, the aqueous composition comprises several alkaline agents, at least one of which is chosen from basic amino acids, preferably arginine, and at least one other of which is chosen from alkaline agents other than basic amino acids, preferably chosen from aqueous ammonia, alkanolamines, and alkali metal or alkaline-earth metal metasilicates.

Preferably, when the alkaline agent(s) are present in the aqueous composition, the total content of alkaline agent(s) is between 0.05% and 25% by weight, more preferentially between 0.1% and 20% by weight, even more preferentially between 0.5% and 15% by weight, better still between 1% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition.

Preferably, when arginine is present in the aqueous composition, the arginine content is between 0.05% and 25% by weight, more preferentially between 0.1% and 15% by weight, even more preferentially between 0.5% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition.

Advantageously, when the aqueous composition(s) according to the invention comprise one or more alkaline agents, the pH generally ranges from 8 to 13, preferably from 9 to 12.5 and better still from 10 to 12.5.

Chemical oxidizing agents

The aqueous composition according to the invention also preferably comprises at least one chemical oxidizing agent.

For the purposes of the present invention, the term “ chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.

The chemical oxidizing agent(s) (or decolourizing agents) that may be used in the present invention may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with the optional cofactors thereof), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; more preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof.

Preferably, when the chemical oxidizing agent(s) are present in the aqueous composition, the total content of chemical oxidizing agent(s) is between 0.1% and 35% by weight, more preferentially between 0.1% and 30% by weight, even more preferentially between 0.5% and 25% by weight and better still 2% to 12% by weight, relative to the total weight of the aqueous composition.

Associative polymers The aqueous composition according to the invention comprises at least one associative polymer.

Preferably, the associative polymer(s) are chosen from anionic, nonionic, cationic and amphoteric associative polymers, and mixtures thereof.

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

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

The term “hydrophobic zone” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

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

- (a) those including at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit is formed by an ethylenic unsaturated anionic monomer, more particularly a vinylcarboxylic acid and most particularly an acrylic acid or a methacrylic acid or mixtures thereof.

Among these anionic associative polymers, the ones that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide. Among the latter polymers, those most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), notably those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);

- (b) those including i) at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the (C10-C30) alkyl ester of an unsaturated carboxylic acid type. (C10-C30) Alkyl esters of unsaturated carboxylic acids that are useful in the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate. Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509949.

Among the anionic associative polymers of this type that will be used more particularly are those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those constituted of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.

Among said polymers above, the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially Pemulen TR1®, and the product sold by the company SEPPIC under the name Coatex SX®.

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

- (c) maleic anhydridc/Cso-Csx a-olefin/alkyl maleate terpolymers, such as the product (maleic anhydridc/Cso-Csx a-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies. - (d) acrylic terpolymers comprising: i) about 20% to 70% by weight of an a,b-monoethylenically unsaturated carboxylic acid [A], ii) about 20% to 80% by weight of an a,b- monoethylenically unsaturated non- surfactant monomer other than [A], iii) about 0.5% to 60% by weight of a nonionic monourethane which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 OE) terpolymer, as an aqueous 25% dispersion.

- (e) copolymers including among their monomers an a,b- monoethylenically unsaturated carboxylic acid and an ester of an a,b- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of an a,b- monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

As examples of compounds of this type, mention may be made of Aculyn 22® (INCI name: Acrylates/steareth-20 methacrylate copolymer) sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/stearyl methacrylate oxyalkylenated terpolymer, and also Aculyn 88 (INCI name: Acrylates/steareth-20 methacrylate crosspolymer) or Aculyn 28 (INCI name: Acrylates/beheneth-25 methacrylate copolymer) also sold by the company Rohm & Haas.

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

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

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

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

The polymers of this family may be chosen notably from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n- alkylamine, and such as those described in patent application WO 00/31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer. These same copolymers may also contain one or more ethylenically unsaturated monomers not including a fatty chain, such as (meth)acrylic acids, b- substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. These copolymers are described notably in patent application EP-A 750 899, patent US 5 089578 and in the following publications from Yotaro Morishima:

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

- Micelle formation of random copolymers of sodium 2- (acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704; - Solution properties of micelle networks formed by nonionic moieties covalently bound to a poly electrolyte: salt effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000), 5324-5332;

- Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym.

Preprint, Div. Polym. Chem., 40(2), (1999), 220-221.

Among these polymers, mention may be made of:

- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, including from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C 8 -Ci 6 )alkyl(meth)acrylamide or (Cx-Ci 6) alkyl(mcth)acrylatc units relative to the polymer, such as those described in patent application EP-A 750899;

- terpolymers including from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C 6 - Ci 8 )alkylacrylamide units, such as those described in patent US-5089 578. Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.

Among the cationic associative polymers, mention may be made of: (a) cationic associative polyurethanes;

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

Polyacrylate- 1 Crosspolymer is the product of polymerization of a monomer mixture comprising: - a di(Ci-C4 alkyl)amino(Ci-C6 alkyl) methacrylate,

- one or more C 1 -C 30 alkyl esters of (meth)acrylic acid,

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

- a 30/5 polyethylene glycol/polypropylene glycol allyl ether, - a hydroxy(C2-C6 alkyl) methacrylate, and

- an ethylene glycol dimethacrylate.

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

(d) cationic polyvinyllactam polymers. Such polymers are described, for example, in patent application WO-

00/68282.

As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldi methylmethacrylam idopropylammonium to sy late terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldim ethylmethacrylami dopropylammonium to sy late terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldim ethylmethacrylamid opropylammonium tosylate or chloride terpolymers are notably used.

The amphoteric associative polymers are preferably chosen from those including at least one noncyclic cationic unit. Even more particularly, those prepared from or comprising 1 to 20 mol%, preferably 1.5 to 15 mol% and even more particularly 1.5 to 6 mol% of fatty-chain monomer relative to the total number of moles of monomers are preferred.

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

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

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

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

- the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer), sold by the company ISP; - the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer), sold by the company ISP;

(b) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers including at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®;

(c) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers including at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer; (d) polyurethane poly ethers including in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;

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

(f) celluloses or derivatives thereof, modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are of C8-C30, and in particular:

* nonionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (Ci 6 alkyl) sold by the company Aqualon;

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

* nonionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the company Berol Nobel; (g) associative guar derivatives, for instance hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a Ci4 alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie. Preferably, the polyurethane polyethers include at least two hydrocarbon- based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being side chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more side chains to be envisaged. In addition, the polymer may include a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

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

The nonionic fatty-chain polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain including from 50 to 1000 oxy ethylene groups. The nonionic polyurethane poly ethers include a urethane bond between the hydrophilic blocks, whence the origin of the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds. As examples of nonionic fatty-chain polyurethane poly ethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® bearing a C12-C14 alkyl chain, and the product Elfacos T212® bearing a Cis alkyl chain, from Akzo. The product DW 1206B® from Rohm & Haas bearing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.

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

The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Set, 271, 380-389 (1993). It is even more particularly preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate. Such polyurethane polyethers are notably sold by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)]. Preferably, the associative polymer(s) are chosen from nonionic associative polymers and anionic associative polymers.

More preferentially, the nonionic associative polymers are chosen from celluloses or derivatives thereof, modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are of C8-C30, and in particular nonionic alkylhydroxyethylcelluloses.

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

According to one embodiment of the invention, the anionic associative polymer(s) are chosen from copolymers including among their monomers an a,b- monoethylenically unsaturated carboxylic acid and an ester of an a,b- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

According to a preferred embodiment of the invention, the associative polymer(s) are chosen from anionic associative polymers, nonionic associative polymers and mixtures thereof; more preferentially from (i) copolymers including among their monomers an a,b-monoethylenically unsaturated carboxylic acid and an ester of an a,b-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol, (ii) celluloses or derivatives thereof, modified with groups including at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are C8-C30 and in particular nonionic alkylhydroxyethylcelluloses, and (iii) mixtures thereof; even more preferentially from acrylates/beheneth-25 methacrylate copolymer, cetyl hydroxyethylcellulose, and mixtures thereof. Preferably, the content of associative polymer(s) is between 0.01% and 10% by weight, more preferentially between 0.05% and 5% by weight and even more preferentially between 0.1% and 2% by weight, relative to the total weight of the aqueous composition.

The aqueous composition according to the invention may optionally also comprise at least one cationic polymer other than the associative polymers described previously.

Preferably, the cationic polymer(s) may be chosen from:

(1) cyclopolymers of alkyldiallylamine or of dialky ldiallylammonium, such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to formula (I) or (II): in which

- k and t are equal to 0 or 1, the sum k + t being equal to 1;

- Ri2 denotes a hydrogen atom or a methyl radical;

- Rio and Rn, independently of one another, denote a C1-C6 alkyl group, a Ci- C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively Rio and Rn may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; Rio and Rn, independently of each other, preferably denote a C1-C4 alkyl group;

- Y is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.

Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) for example sold under the name Merquat 100 by the company Nalco and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, notably sold under the name Merquat 550 or Merquat 7SPR. (2) quaternary diammonium polymers comprising repeating units of formula (III) below: in which: - Ri 3 , Ri 4 , Ri 5 and Ri 6 , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C 1 -C 12 hydroxy alkyl aliphatic radicals; or else R 13 , R 14 , R 15 and Ri 6 , together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non- nitrogen heteroatom; or else R 13 , R 14 , R 15 and Ri 6 represent a linear or branched C 1 -C 6 alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-Rn-D or -CO-NH-Rn-D group, where Rn is an alkylene and D is a quaternary ammonium group;

- Ai and Bi represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted 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 a mineral or organic acid; it being understood that Ai, R 13 and R 15 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 hydroxy alkylene radical, Bi may also denote a group (CH2)n2-CO-D-OC- (CH 2 )p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CHiCHiC x-CHiCHi- and -[CH 2 CH(CH3)0] y -CH 2 CH(CH3)-, 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-, in which Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -CH2-CH2-S-S-CH2-CH2-; 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 molar mass (Mn) generally of between 1000 and 100000.

Mention may be made more particularly of polymers that are constituted of repeating units corresponding to the formula: in which Ri, R 2 , R 3 and R 4 , which may be identical or different, denote an alkyl or hydroxy alkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X is an anion derived from a mineral or organic acid.

A compound constituted by units of formula (IV) that is particularly preferred is the one for which Ri, R 2 , R 3 and R 4 represent a methyl radical and n = 3, p = 6 and X = Cl, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

More preferentially, the cationic polymer(s) may be chosen from Polyquaternium-6, hexadimethrine chloride, and mixtures thereof.

Preferably, when the cationic polymer(s) other than the associative polymers described previously are present in the aqueous composition, the content of cationic polymer(s) is between 0.01% and 15% by weight, more preferentially between 0.05% and 10% by weight, even more preferentially between 0.1% and 5% by weight, or even between 0.5% and 2% by weight, relative to the total weight of the aqueous composition. The aqueous composition(s) that may be used in the process according to the present invention may also comprise one or more additives such as nacres; fatty substances; vitamins or provitamins; surfactants, notably nonionic surfactants; pH stabilizers; preserving agents; fragrances. A person skilled in the art will take care to select the optional additives and the amount thereof so that they do not harm the properties of the processes and compositions of the present invention.

These additives, when they are present, are generally present in the aqueous composition(s) according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the aqueous composition.

The aqueous composition(s) used in the process according to the present invention may optionally also comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include linear or branched C2 to C4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxy ethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The process

Advantageously, the process according to the invention comprises the mixing of a number Ni of solid particle(s) of a first type PI with a number N2 of solid particles(s) of a second type P2, Ni and N2 being integers greater than or equal to 1 defined before the use of the ready-to-use composition, as a function of the shade desired by the user and/or of the user’s specificities such as the pre-existing shade and/or the nature of the keratin fibres.

More preferentially, the numbers Ni and N2 are defined by means of computer software.

Thus, according to a particular preferred embodiment, the process according to the invention comprises the mixing of numbers Ni to N n of solid particle(s) of, respectively, the type PI to Pn (with n representing an integer greater than or equal to 3), the numbers Ni to N n being integers greater than or equal to 1 defined before the use of the ready-to-use composition, as a function of the shade desired by the user and/or of the user’s specificities such as the pre-existing shade and/or the nature of the keratin fibres.

More preferentially according to this embodiment, the numbers Ni to N n are defined by means of computer software.

According to a particular embodiment of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention also comprises the mixing of said particles P with one or more solid particles of the type P’x (with x representing an integer greater than 1, and preferably between 1 and 20, more preferentially between 1 and 15 and even more preferentially between 1 and 10) containing at least one dye Cx, better still only one dye Cx, even better still only one oxidation dye precursor Cx, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type P’x; said solid particle of the type P’x corresponding to the solid particle Px described previously apart from the content of dye Cx.

By way of example of this particular embodiment of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention may comprise the mixing:

(i) of one or more solid particles of a first type PI containing at least one dye Cl, better still only one dye Cl, even better still only one oxidation dye precursor Cl, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type PI; with

(ii) one or more solid particles of a second type P2 containing at least one dye C2, better still only one dye C2, even better still only one oxidation dye precursor C2, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type P2; with

(iii) one or more solid particles of the type P’l containing said dye(s) Cl in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type P’l; and (iv) at least one aqueous composition comprising at least one associative polymer; it being understood that:

- the dye(s) Cl are different from the dye C2; - the content of dye Cl contained in the solid particle(s) PI is different from the content of dye Cl contained in the solid particle(s) P’l.

Preferably, the process according to the invention is performed less than 2 hours, more preferentially less than 1 hour and even more preferentially less than 30 minutes before the application of the composition resulting from said mixing to the keratin fibres.

According to a preferred embodiment of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention comprises the mixing:

(i) of several solid particles of a first type PI as described previously; with

(ii) several solid particles of a second type P2 as described previously; with

(iii) several aqueous compositions, including at least one aqueous composition comprising at least one associative polymer, as described previously. According to another preferred embodiment of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention comprises the mixing:

- of one or more solid particles PI and one or more solid particles P2 (and more generally one or more particles PI to Pn), as described previously, with - at least one aqueous composition C comprising at least one associative polymer, preferably chosen from those described previously, more preferentially from (i) copolymers including among their monomers an a,b- monoethylenically unsaturated carboxylic acid and an ester of an a,b- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol, (ii) celluloses or derivatives thereof, modified with groups including at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are Cs and (iii) mixtures thereof; even more preferentially from acrylates/beheneth-25 methacrylate copolymer, cetyl hydroxyethylcellulose, and mixtures thereof; and with - at least one different aqueous composition A comprising at least one chemical oxidizing agent, preferably chosen from those described previously, more preferentially from hydrogen peroxide, persalts and mixtures thereof; and/or

- at least one different aqueous composition B comprising at least one alkaline agent, preferably chosen from those described previously; more preferentially, the alkaline agent is arginine.

Preferably according to this embodiment, the content of chemical oxidizing agent(s) present in the aqueous composition A is between 0.1% and 35% by weight, more preferentially between 0.1% and 30% by weight, even more preferentially between 0.5% and 25% by weight, and better still between 2% and 12% by weight, relative to the total weight of the aqueous composition A.

Preferably according to this embodiment, the content of alkaline agent(s) present in the aqueous composition B is between 0.05% and 25% by weight, more preferentially between 0.1% and 20% by weight, even more preferentially between 0.5% and 15% by weight, better still between 1% and 10% by weight, or even between

1% and 5% by weight, relative to the total weight of the aqueous composition B.

Preferably according to this embodiment, when arginine is present in the aqueous composition B, the arginine content is between 0.05% and 25% by weight, more preferentially between 0.1% and 15% by weight, even more preferentially between 0.5% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition B.

Preferably according to this embodiment, the content of associative polymer(s) present in the aqueous composition C is between 0.01% and 10% by weight, more preferentially between 0.05% and 5% by weight and even more preferentially between 0.1% and 2% by weight, relative to the total weight of the aqueous composition C.

According to another preferred embodiment of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention comprises the mixing:

(i) of one or more solid particles of a first type PI containing at least one dye Cl, better still only one dye Cl, even better still only one oxidation dye precursor Cl, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type PI; with (ii) one or more solid particles of a second type P2 containing at least one dye C2, better still only one dye C2, even better still only one oxidation dye precursor C2, in a content of between 0.001% and 50% by weight relative to the total weight of the solid particle(s) of the type P2; then with (iii) at least one aqueous oxidizing composition A comprising at least one chemical oxidizing agent, then with

(iv) at least one aqueous composition C comprising at least one associative polymer; it being understood that the dye(s) Cl are different from the dye C2.

According to a particularly preferred variant of the invention, the process for preparing the composition for dyeing keratin fibres according to the invention comprises the mixing:

- of one or more solid particles PI and one or more solid particles P2 (and more generally one or more particles PI to Pn), as described previously, with

- at least one aqueous composition A, at least one aqueous composition B and at least one aqueous composition C, as described previously.

According to another variant of the present invention, the process for preparing the composition for dyeing keratin fibres according to the invention comprises the mixing:

- of one or more solid particles PI and one or more solid particles P2 (and more generally one or more particles PI to Pn), as described previously, with

- at least one aqueous composition E comprising: a. at least one chemical oxidizing agent, preferably chosen from those described previously, more preferentially from hydrogen peroxide, persalts and mixtures thereof, and b. at least one alkaline agent, preferably chosen from those described previously; more preferentially, the alkaline agent is arginine, and c. at least one associative polymer, preferably chosen from those described previously, more preferentially from the anionic associative polymers as described previously.

Preferably according to this variant, the total content of chemical oxidizing agent(s) present in the aqueous composition E is between 0.1% and 35% by weight, more preferentially between 0.1% and 30% by weight, even more preferentially between 0.5% and 25% by weight, and better still between 2% and 12% by weight, relative to the total weight of the aqueous composition E.

Preferably according to this variant, the total content of alkaline agent(s) present in the aqueous composition E is between 0.05% and 25% by weight, more preferentially between 0.1% and 20% by weight, even more preferentially between 0.5% and 15% by weight, better still between 1% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition E.

Preferably according to this variant, when arginine is present in the aqueous composition E, the arginine content is between 0.05% and 25% by weight, more preferentially between 0.1% and 15% by weight, even more preferentially between 0.5% and 10% by weight, or even between 1% and 5% by weight, relative to the total weight of the aqueous composition E.

Preferably according to this variant, the total content of associative polymer(s) present in the aqueous composition E is between 0.01% and 10% by weight, more preferentially between 0.05% and 5% by weight and even more preferentially between 0.1% and 2% by weight, relative to the total weight of the aqueous composition E.

According to another particular embodiment of the invention, the process for preparing the composition for dyeing keratin fibres may also use one or more solid particles free of dye.

The mixing of the solid particles with the aqueous composition(s) may be performed using a mechanical stirrer, a magnetic stirrer, and/or by hand, for example using a colouring brush.

The ready-to-use composition

The ready-to-use composition, or final composition, is obtained after mixing the solid particles of the type PI to Pn described above with the at least one aqueous composition comprising at least one associative polymer.

Preferably, the water content of said ready-to-use composition is between 30% and 99% by weight, more preferentially between 50% and 99% by weight and better still between 50% and 90% by weight, relative to the total weight of said ready- to-use composition.

Preferably, when said ready-to-use composition comprises one or more alkaline agents, said agents are present in a total content ranging from 0.001% to 30% by weight, more preferentially from 0.05% to 20% by weight, even more preferentially from 0.5% to 10% by weight and better still between 1% and 5% by weight, relative to the total weight of said ready-to-use composition.

Preferably, when said ready-to-use composition comprises arginine, the arginine content of the ready-to-use composition ranges from 0.001% to 20% by weight, more preferentially from 0.05% to 10% by weight, even more preferentially from 0.1% to 5% by weight and better still between 0.5% and 3% by weight, relative to the total weight of said ready-to-use composition.

Preferably, when said ready-to-use composition comprises one or more chemical oxidizing agents, said agents are present in a total content ranging from 0.001% to 30% by weight, more preferentially from 0.05% to 20% by weight, even more preferentially from 0.1% to 15% by weight and better still between 1% and 10% by weight, relative to the total weight of said ready-to-use composition.

Preferably, the associative polymer(s) are present in the ready-to-use composition in a total content ranging from 0.001% to 8% by weight, more preferentially from 0.005% to 4% by weight, and even more preferentially from 0.01% to 1% by weight, relative to the total weight of said ready-to-use composition.

Preferably, the weight ratio of the total mass of the ready-to-use composition, on the one hand, to the total mass of solid particles, on the other hand, is between 1 and 22, more preferentially between 2 and 15; even more preferentially between 5 and 12.

The ready-to-use composition 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 notably human hair.

A subject of the invention is also the use of the composition obtained via the preparation process as described previously, for the dyeing, preferably for the oxidation dyeing, of keratin fibres, in particular of human keratin fibres such as the hair.

More particularly, the invention relates to the use of the composition, obtained via the preparation process comprising the mixing: - of at least two solid particles as described previously; with

- at least one aqueous composition A comprising at least one chemical oxidizing agent, preferably chosen from those described previously, more preferentially from hydrogen peroxide, persalts and mixtures thereof; and

- at least one different aqueous composition B comprising at least one alkaline agent, preferably chosen from those described previously; more preferentially, the alkaline agent is arginine; and

- at least one different aqueous composition C comprising at least one associative polymer, preferably chosen from those described previously, more preferentially from the anionic associative polymers as described previously; for the dyeing, preferably for the oxidation dyeing, of keratin fibres, in particular of human keratin fibres such as the hair.

A subject of the invention is also a process for dyeing the keratin fibers comprising the implementation of a step of applying to said fibers the ready-to-use composition obtained according to the preparation process as described previously, less than two hours, preferably less than an hour, more preferably less than 30 minutes, after obtaining said ready-to-use composition according to said preparation process.

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

Examples

The solid particles and the compositions below according to the present invention were prepared using the ingredients of which the contents, expressed as mass percentages of active material relative to the total weight of the solid particle or of the composition, are indicated in the tables below. Examples of particles

Solid particle without an upper coating layer

[Table 1]

Examples of upper coatins layers [Table 2]

Examples of solid particles with an upper coating layer

[Table 4]

[Table 5]

[Table 61 [Table 7]

[Table 8] Oxidizing composition

[Table 9]

Alkaline composition 1 [Table 101 Alkaline composition 2

[Table 11]

Thickening composition [Table 121 Process for dyeing keratin fibres

A composition (M) for dyeing keratin fibres is prepared in a bowl according to the following steps:

(1) 100 coated solid particles (i.e. 6 g) according to table 4 above, 58 coated solid particles (i.e. 3.48 g) according to table 6 above, 22 coated solid particles (i.e. 1.32 g) according to table 5 above, 21 coated solid particles (i.e. 1.26 g) according to table 7 above, and 14 coated solid particles (i.e. 0.84 g) according to table 8 above, are mixed with 12 g of oxidizing composition according to table 9 above and 36 g of stabilized water adjusted to pH 2.2; and then, after at least 30 seconds (2) the mixture obtained in step (1) is mixed with 24 g of thickening composition according to table 12 above, 28.8 g of alkaline composition 1 according to table 10 above and 19.2 g of alkaline composition 2 according to table 11 above.

A homogeneous aqueous composition (M), in which the coated solid particles are dispersed in the composition, is thus obtained.

Composition (M) obtained is then applied to locks of natural Caucasian hair containing 90% grey hairs (locks of NG hair) in a proportion of 10 g of composition (M) per 1 g of hair. After a leave-in time of 30 minutes at 27°C, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

L, a, b results:

The colorimetric data for each of the locks are then measured in the CIELab system with a Data Color SF600X spectrophotometer (illuminant D65, angle 10° and specular component included). In this L* a* b* system, L* represents the lightness, a* indicates the green/red colour axis and b* indicates the blue/yellow colour axis. The higher the value of L*, the lighter or less intense the colour. Conversely, the lower the value of L*, the darker or more intense the colour. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade. The colour build-up on the hair thus corresponds to the variation in colouring between the locks of dyed NG hair and the locks of undyed (i.e. untreated) NG hair and is measured by the AE according to the following equation:

In this equation, L*, a* and b* represent the values measured after dyeing of the NG hair, and Lo*, ao* and bo* represent the values measured for the untreated NG locks of hair. The higher the DE value, the better the build-up of the colouring.

The results are collated in the table below:

[Table 13]

It is seen from the results of the table that the keratin fibres treated with composition (M) prepared according to the preparation process of the invention are dyed intensely and with a good colour build-up.

It was also found that composition (M) is easy to prepare and to spread on the locks of hair, notably without any running.