FR3075616A1 - PROCESS FOR TREATING KERATINOUS FIBERS USING DIRECT OXAZONE OR PHENAZINE HALOCHROME COLOR, DEVELOPER THEN ERASER - Google Patents

Abstract

The subject of the present invention is a process for the treatment of particularly human keratinous fibers such as the hair using i) at least one oxazone or phenazine direct dye of formula (I), (I '), (II) or (II') ) as defined below, then ii) a developer and then iii) an eraser. The subject of the invention is also a composition comprising at least one oxazone or phenazine direct dye of formula (I), (I '), (II) or (II') as defined below and at least one thickener and / or or at least one hydrotrope solvent, and a multi-compartment kit comprising in separate compartments i), ii) and iii). The present invention makes it possible in particular to obtain a coloration of the keratinous fibers with intense and stubborn reflections that can be modified, erased and reformed several times without loss of color.

Description

PROCESS FOR THE TREATMENT OF KERATINIC FIBERS USING A DIRECT OXAZONE OR HALOCHROME PHENAZINE DYE, A DEVELOPER THEN AN ERASER

The subject of the present invention is a process for treating keratin fibers, in particular human fibers such as the hair, using i) at least one direct dye chosen from oxazones and phenazine of formula (I), (I '), (II) or (II ′) as defined below, then ii) a developer, then iii) an eraser. The subject of the invention is also a composition comprising at least one direct dye chosen from the oxazone and phenazine of formula (I), (I '), (II) or (II') as defined below and at least one thickener and / or at least one hydrotropic solvent, and a kit with several compartments comprising in 3 separate compartments i), ii) and iii).

It is known to dye keratin fibers, and in particular human keratin fibers such as the hair, with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines. , ortho- or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.

It is also known that the shades obtained with these oxidation bases can be varied by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta- diphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.

The so-called permanent coloring obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and rubbing.

The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its tip and its root.

It is also known to dye keratin fibers, and in particular human keratin fibers such as the hair, with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibers. They are applied to the keratin fibers for a time necessary to obtain the desired coloration, then rinsed off.

The conventional dyes which are used are in particular dyes of the nitro benzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine, triarylmethane, nitro benzene type or natural dyes.

The colorings obtained are temporary or semi-permanent, because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their bad resistant to washing, bad weather, or perspiration. These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair.

It is also sought by users to be able to color the keratin fibers as they wish by making the color of the fibers appear with a developer (“switch on”) then erasing or extinguishing the color with a color eraser (“switch off”). ») And if necessary repeat these switch on switch off cycles, with very little loss of color after repeating the switch on cycle. It is also sought that even after several shampoos this color can be revealed or extinguished without damaging the keratin fibers.

However, the processes of the prior art do not describe successive coloring steps "switch on - switch off - switch on - switch off". In addition, the dyes are not always sufficiently tenacious, and / or there is a reduction in Colonial properties of the color revealed in terms of color increase, intensity, chromaticity, tenacity, in particular with respect to successive shampoos, and / or selectivity of the root and tip color. In addition, in the pH ranges close to neutral these dyes are not always interchangeable in “switch off-switch on” or “switch on switch off”. Another problem encountered is to obtain a rapid or clear color development or color erasure without a strong residual color persisting after the "sweetch off" color erasure step. Finally there is a diffusion problem when we want to make artistic coloring by revealing only one part of the color or by erasing only one part of the color. The rendering of the color or of the erasure is not always satisfactory (in particular with the use of stencil because of the diffusion of the erasure or of the revelation on the keratin fibers (smearing). In addition it is sought a coloring system which could change color "switch on", "switch off" with a "switch on" which would be in natural colors called basic colors such as chestnut, brown or even black.

Thus the object of the invention is to provide coloring of keratin fibers with intense colors, and a good rise in color which can permute according to the pH ideally close to neutrality even after several cycles, with a rapid effect. and frank about the color change "switch off - switch on" or "switch on - switch off", with structured effects (geometric, graphic effect ...), without color transfer from one wick to another (by eg possibility on braid comprising three dyes of different colors not to diffuse the color from one wick to another even after several cycles of pH developers), allow the development or erasure of the color without smearing and avoid denaturation keratin fibers. Another goal is to be able to obtain a coloring in the fundamental colors which can be erased or change color in a frank, visible and quickly manner.

These aims are achieved with the present invention which relates to a process for treating keratin fibers, in particular human fibers such as the hair, using:

i) a step of applying a composition (A) comprising one or more compounds chosen from the oxazone and phenazine of formula (I), (I '), (II) or (II') as well as its (their) optical, geometric, tautomeric isomers, as well as its solvates such as hydrates:

(II) (II ’)

Formulas (I) to (II ’) in which:

X and X ′, which may be identical or different, represent an oxygen or sulfur atom or an N (R _a ) group with R _a representing a hydrogen atom or a (Ci-C6alkyl, aryl such as phenyl group), or aryl (Ci-C6) alkyl such as benzyl, in particular R _a represents a hydrogen atom or a (Ci-C4) alkyl group such as methyl;

- R, and R ', identical or different, represent a hydrogen atom or a group chosen from (Ci-C6alkyl, (Ci-C6alkoxy, (di) (CiC6) (alkyl) amino, preferably hydrogen or (Ci- Côjalkyle;

- R ”, and R '”, identical or different, represent a hydrogen atom, or a group (Ci-C6alkyl, aryl such as phenyl, or aryl (Ci-C6) alkyl such as benzyl ,, preferably hydrogen or (Ci-Côjalkyle;

- G represents a nitrogen atom, a group: N (O) or: N ⁺ -O '

- M represents an alkali metal, alkaline earth metal, or an ammonium group;

- An 'represents an anionic counter ion;

Then:

When the composition (A) comprises one or more compounds of formula (I), the application of the composition (A) is followed by ii) a development step ("switch on") consisting in applying to said fibers a composition (C) at acidic pH; followed by iii) a step of switching off or erasing the color (“switch off”) consisting in applying to said fibers a composition (B) at basic pH;

When the composition (A) comprises one or more compounds of formula (I ′), the application of the composition (A) is followed by ii) a step of dyeing the color consisting in applying to said fibers a composition (B) at basic pH, followed by iii) a development step consisting in applying to said fibers a composition (C) at acidic pH;

When the composition (A) comprises one or more compounds of formula (II), the application of the composition (A) is followed by ii) a development step (“switch on”) consisting in applying to said fibers a composition (B) at basic pH; followed by iii) a step of dyeing or erasing the color ("switch off") consisting in applying to said fibers a composition (C) at acidic pH; and • When the composition (A) comprises one or more compounds of formula (II ′), the application of the composition (A) is followed by ii) a step of quenching the color consisting in applying to said fibers a composition (C) at acid pH, followed iii) by a development step consisting in applying to said fibers a composition (B) at basic pH;

it being understood that steps ii) and iii) can be repeated several times.

Another subject of the invention is a composition (Ai) comprising a) one or more oxazone compounds of formula (I), (I '), (II) and / or (II') as defined above and optionally b) one or more thickeners, in particular polymeric, and / or one or more hydrotropic solvents, in particular aromatic.

Another subject of the invention is a kit with several compartments which comprises: i) in a first compartment the compounds chosen from the oxazones and phenazines of formula (I), (I '), (II) and / or (II' ) as defined above, ii) in a second compartment: a composition (B) at basic pH; and iii) in a third compartment a composition (C) at acidic pH.

i) The dyes fl), fl ’), (II) and fine

The process for treating keratin fibers of the invention implements in the first step a step of applying a composition (A) comprising one or more compounds of formula (I), (I '), (II) and / or (II ′) as defined above, or an application step (Ai) as defined above.

Preferably, the oxazone or phenazine compounds of formula (I), (I '), (II) and / or (II') are dyes which have a color-changing zone at the pH inclusive between 4.5 and 8 .

In the context of the present invention, the term “alkyl” is intended to mean a saturated, linear or branched hydrocarbon-based radical comprising from 1 to 6 carbon atoms, preferably comprising from 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl or ter-butyl.

An "alkoxy" radical is an alk-O- radical with the alkyl radical being as defined above.

An “aryl” radical is an aromatic unsaturated hydrocarbon cyclic radical comprising from 5 to 20, preferably between 6 and 10 members, in particular the aryl radical represents a phenyl group;

An “anionic counterion” is an anion or an anionic group derived from an organic or mineral acid salt counterbalancing the cationic charge of the dye; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including Ci-C6 alkylsulfonates: Alk-S (O) 2O 'such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 2O 'such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-OS (O) O 'such as methysulphate and ethyl sulphate; x) arylsulfates: Ar-OS (O) O 'such as benzenesulfate and toluenesulfate; xi) alkoxysulfates: Alk-OS (O) 2O 'such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS (O) 2O ', xiii) phosphates O = P (OH) ₂ -O; O = P (O) ₂ -OH O = P (O) ₃ , HO- [P (O) (O-)] _w -P (O) (O-) ₂ with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate disulfate (O =) 2S (O ') 2 or SO4 ² ' and monosulfate HSO4 ';

the anionic counter ion, derived from organic or mineral acid salt, ensures the electroneutrality of the molecule.

It is understood for the salified forms of (I) and (II) which are respectively (I ') and (II') the compounds (I ') and (II') can be in forms of salts other than those previously written, for example:

According to an advantageous embodiment of the invention the colorant (s) O), (! '), (II) and (II') are chosen from the compounds of formula (la), (a), (lia) and (ll'a) following:

as well as their optical, geometric, tautomeric isomers, as well as their solvates such as hydrates Formulas (la) to (ll’a) in which:

- X and X ’, as defined above, in particular X’ represents an oxygen atom, preferably X and X ’represent an oxygen atom;

- R, and R ’, as defined above, in particular R and R’ represent a hydrogen or (Ci-C4) alkyl atom; such as methyl, preferably R represents a hydrogen atom and R ’represents a (Ci-C4) alkyl group; such as methyl;

- R ”, and R’ ”, as defined above, in particular represent a hydrogen atom, or a group (Ci-C6alkyl, preferably hydrogen or (Ci-C4) alkyl such as methyl;

- R _a as defined above, in particular represents a hydrogen atom or a (Ci-C4) alkyl group such as methyl

- G represents a nitrogen atom, a group: N (O) or: N ⁺ -O '

- M represents an alkali metal, alkaline earth metal, or an ammonium group, preferably alkaline such as sodium; and

- An 'represents an anionic counter ion.

As examples of compounds of formula (I), (I '), (II) and (II') or (la), (a), (a) and (ll'a) there may be mentioned the following compounds (1) to (3 '):

Ο

Resazurin salt (2 ’)

Resofurin (3)

Resofurin salt (3 ’)

With An ^_ as defined above, preferably halide such as Cl, and M as defined above, preferably an alkali metal such as sodium. Preferably the compounds of formula (1), (T), (2), or (2 ').

The compounds chosen from the compounds of formula (I), (I '), (II) and / or (II') or (la), (a), (Ha) and / or (ll'a) such as defined above preferably represent from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of the composition (A), or (Ai), (A2) or (A3) as defined above after.

According to a particular embodiment of the invention, the composition (Ai) comprises one or more compounds of formula (I), (I '), (II) and / or (II') or (la), (a ), (a) and / or (ll'a) as defined above in an amount between 0.001 to 10% by weight, preferably between 0.005 to 5% by weight relative to the total weight of the composition (Ai).

According to a particular embodiment of the invention, the composition (A2) comprises one or more compounds of formula (I), and / or (I '), or (la) and / or (a), as defined previously in an amount between 0.001 to 10% by weight, preferably between 0.005 to 5% by weight relative to the total weight of the composition (A2).

According to a particular embodiment of the invention, the composition (A3) comprises one or more compounds of formula (II), and / or (II '), or (11a) and / or (11a), as defined previously in an amount between 0.001 to 10% by weight, preferably between 0.005 to 5% by weight relative to the total weight of the composition (A3).

In general, the addition salts of organic or inorganic bases of the compounds of formula (IIa) corresponding to the compounds of formula (IIa) in the context of the invention are in particular chosen from the addition salts with a base chosen from alkaline agents as defined below, in particular chosen from soda, potash, ammonia, and alkanolamines.

Optional dyes:

The compositions (A) and (Ai) as defined above may also comprise one or more direct dyes different from the compounds of formula (I) and / or (I ') as defined above which can in particular be chosen from nitro dyes of the benzene series, azo direct dyes, methine direct dyes and natural dyes. These direct dyes can be of nonionic, anionic or cationic nature. These dyes can be halochromic.

The compositions (A), (Ai), (A2), and (A3) as defined above can also comprise one or more direct dyes different from the compounds of formula (I), (I '), (II) and / or (II ') or (la), (a), (lia) and / or (ll'a) as defined above, which can in particular be chosen from nitro dyes of the benzene series, azo direct dyes, direct methine dyes and natural dyes. These direct dyes can be of nonionic, anionic or cationic nature.

These dyes can be halochromes different from the oxazones and phenazine of formula (I), (I ’), (II) or (II’) as defined above.

In the presence of additional direct dyes in the composition according to the invention, these represent in particular from 0.001 to 20% by weight relative to the total weight of the composition (A), (Ai), (A2), or (A3 ) preferably from 0.01 to 10%.

The compositions (A), (Ai), (A2), and (A3) can also comprise one or more oxidation dyes chosen from oxidation bases and couplers conventionally used in oxidation coloring.

Preferably the oxidation dyes in composition (A), (Ai), (A2), and (A3) represent in particular from 0.001 to 20%, preferably from 0.01 to 10% by weight relative to the total weight of composition (A), (Ai), (A2), or (A3).

ii) The revelation stage

The method of the invention implements after the step of applying the composition (A), (Ai), (A2), (A3), as defined above, and a step of revealing using a composition (B) or (C) for revealing or revealing depending on whether said compositions (A), (Ai), (A2), (A3), comprise a compound (I), (I '), (II), (II '), (la), (a), (Ha) or (ll'a).

For the compounds of formula (II) or (IIa) as defined above, the composition revealing the color on the keratin fibers is composition (B). The revealing composition (B) has a basic pH, ie is an aqueous composition having a pH greater than 7, preferably between 7.5 and 12.5, particularly between 8.5 and 12, more particularly between 9 and 11, 5.

Composition (B) contains one or more alkaline agent (s), which can be any agent which makes it possible to increase the pH of the composition in which it is found. The alkaline agent (s) are chosen from BronstedLowry or Lewis bases. It (s) can (be) mineral (aux) or organic (s).

In particular, the alkaline agent (s) are chosen from:

a) ammonia,

b) alkanolamines, in particular mono-, di- or tri- (CiCojalkanolamines such as mono-, di- and triethanolamines, isopropanolamine, 2-amino-2-methyl-1-propanol (AMP), 2 -amino2-methyl-1,3-propanediol (AMPD) and, 2-amino 1,3-propanediol and their derivatives,

c) (Ci-C6) oxyethylenated and / or oxypropylenated alkylenediamines,

d) mineral or organic hydroxides,

e) basic amino acids such as arginine, lysine, ornithine, citrulin and histidine,

f) silicates or metasilicates of alkali or alkaline-earth metals such as sodium metasilicates,

g) carbonates and bicarbonates, particularly of primary, secondary or tertiary amine, of alkali or alkaline-earth metal, or of ammonium, and

h) the compounds of formula (III) below:

^x \ / NWN

R

R.

(III)

Formula (III) wherein W represents an alkylene divalent radical Ci-C _{6 alkyl} optionally substituted with a hydroxyl group or an alkyl radical Ci-alkyl; Rx, R _y , Rz and Rt, identical or different, represent a hydrogen atom, or a C1-C6 alkyl, C1-C6 hydroxyalkyl, or C1-C6 aminoalkyl group.

Examples of such compounds of formula (III) that may be mentioned include 1,3diaminopropane, 1,3-diamino-2-propanol, spermine, spermidine.

The mineral or organic hydroxides are preferably chosen from the hydroxides of an alkali metal, the hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, the hydroxides of a transition metal, such as hydroxides of metals in groups III, IV, V and VI of the periodic table, lanthanide or actinide hydroxides, quaternary ammonium hydroxides, and guanidinium hydroxide.

The hydroxide can be formed in situ, for example guanidine hydroxide, formed by the reaction of calcium hydroxide and guanidine carbonate.

The preferred alkaline agents are chosen from ammonia, carbonates or bicarbonates such as ammonium or sodium carbonate, ammonium or sodium bicarbonate, basic amino acids such as arginine, alkanolamines such as monoethanolamine (MEA), 2-amino-2methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD) and, 2amino 1,3-propanediol preferably alkanolamines such as the MEA.

The alkaline agent (s) as defined above can represent, for example, from 0.1 to 20% by weight, and preferably from 1 to 15% by weight, relative to the total weight of the composition (B ).

For the compounds of formula (I) or (la) as defined above, the composition revealing the color on the keratin fibers is composition (C). The revealing composition (C) is at acidic pH ie is an aqueous composition having a pH of less than 7, preferably less than 6, and ranging up to 0.5 inclusive, particularly at a pH inclusive between 1 and 5, of preferably between 1.3 and 3.

Particularly the composition (C) comprises one or more organic or mineral acids preferably chosen from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) phosphoric or orthophosphoric acid H3PO4, iv) (Ci-C6) alkylsulfonic acids: Alk-S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzene sulfonic acid and toluene sulfonic acid; vi) carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids. succinic acid vii) of (Ci-C6) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; viii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4.

By “carboxylic acid” is meant a compound comprising at least one carboxylic acid group -C (O) -OH, preferably of formula (I) as defined above, preferably comprising between 1 and 4 carboxylic acid groups such as 1 or 2; or chosen from: i) (Ci-C6) alkyl- [C (O) -OH] _n and ii) heter- [C (O) -OH] _n , with n an integer inclusive between 1 and 4, preferably between 1 and 2, heter representing a heterocyclic group such as pyrrolidone, the alkyl or heter group possibly being optionally substituted by one or more groups chosen from OH, and (di) (Ci-C4) (alkyl) amino.

More preferably, the acids used in the quenching composition (C) of the invention are chosen from orthophosphoric acid, and the carboxylic acids such as acetic acid, tartaric acid, citric acid, or acid. lactic acid, more particularly chosen from orthophosphoric acid and carboxylic acid such as acetic acid.

The acid (s) as defined above can represent for example from 0.1 to 20% by weight, and preferably from 1 to 15% by weight, relative to the total weight of the composition (C).

iii) The shutdown step

The method of the invention implements after the step of applying the composition (A), (Ai), (A2), (A3), as defined above, a step of quenching using a composition (C) or (B) for revealing or revealing depending on whether said compositions comprise compounds (I), (I '), (II), (II'), (la), (a), ( lia) or (ll'a).

For the compounds of formula (II) or (IIa) as defined above, the composition for quenching the color on the keratin fibers is the composition (C) as defined above.

For the compounds of formula (I) or (la) as defined above, the composition for quenching the color on the keratin fibers is composition (B) as defined above.

The supports of the compositions

The compositions (A), (Ai), (A2), (A3), (B) and (C) of the invention are found in a cosmetic medium, ie suitable for dyeing keratin fibers, in particular human fibers such as the hair, also called a dye carrier, which generally comprises water or at least one organic solvent or a mixture of water and at least one organic solvent.

iv) Hydrotropic liquid organic compounds

According to one embodiment of the invention, at least one of the compositions (A), (Ai), (A2), (A3), (B) or (C) comprises one or more liquid organic compounds having a solubility parameter en of Hansen greater than 0 and less than 16 MPa ^1/2 . More particularly composition (A), (Ai), (A2), or (A3), comprising the compound or compounds of formula ((I), (I '), (II), (II'), (la) , (a), (lla) or (ll'a) further comprises one or more liquid organic compounds having a Hansen solubility parameter δΗ greater than 0 and less than 16 MPa ^1/2 . present invention, such a liquid organic compound is also called a hydrotropic compound.

By "hydrotropic compound" is meant in the sense of the present invention a compound capable of increasing the solubility of hydrophobic compounds in the aqueous phases.

Said liquid compounds more preferably have a Hansen 5H solubility parameter of between 5 and 15.8 MPa ^1/2 , even more preferably between 8 and 15.8 MPa ^1/2 , and better still between 8 and 15 MPa ^1/2 .

These compounds are liquid at a temperature of 25 ° C and at atmospheric pressure (760 mm Hg, or 1.013.105 Pa).

The compound or compounds exhibiting a value of the Hansen solubility parameter 5H, as defined above, are for example described in the reference work "Hansen solubility parameters A user's handbook, Charles M. HANSEN", CRC Press, 2000, pages 167 to 185, or in the book “Handbook of Solubility Parameters and other cohesion parameters”, CRC, Press, pages 95 to 121 and pages 177 to 185.

This value of the 5H solubility parameter is linked to the formation of hydrogen bonds. It may be recalled that there are three major types of interactions in organic compounds, non-polar interactions, permanent dipole dipole interactions and hydrogen bond type interactions, the latter being the subject of the parameter defining the hydrotropic compound present in the composition used in accordance with the invention.

In particular, the book “Handbook of Solubility Parameters and other cohesion parameters”, CRC Press, pages 95 to 121 and pages 177 to 185, gives the equation ÔH = (£ -zUh / V) 1/2 where, zUh ( in J. mol-1) describes the contributions of the functional group considered in the parameters of solubility linked to hydrogen bonds (values in table 14, page 183), this parameter zUh being also described in the book “The relation between surface tension and solubility parameter in liquids ”, Bagda, E, Farbe Lack, 84, 212, 1978; and V is the volume of the molecule.

It should be noted that the value of the solubility parameter ôH is usually given for a temperature of 25 ° C and at atmospheric pressure (760 mm Hg, or 1.013.105 Pa).

In particular, the liquid organic compounds having a value of the Hansen solubility parameter ôH greater than 0 and less than 16 MPa%, are nonionic compounds.

Preferably, the said liquid organic compound (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa% are chosen from alcohol ethers, aliphatic esters, aliphatic ethers, aromatic ethers, aryl-substituted alkanols, lactones, sulfones and mixtures thereof.

The said liquid organic compound (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa ^1/2 can be chosen from:

• alcohol ethers, in particular C1-C4 ethers of C5-C30 alcohols, preferably saturated, linear or branched, possibly interrupted by one or more non-adjacent ether functions;

• aliphatic esters of C1-C4 carboxylic acids and of C3-C10 mono or poly-hydroxylated alcohols, interrupted by one or more non-adjacent ether functions;

• the aromatic ethers, in particular in C6-Cio, of C1-C6 alkyl possibly carrying a hydroxyl group, • the ethers (C6-Cio) aryl (Ci-C6) alkyl of C1-C6 alkyl optionally carrying a hydroxyl group, • alkanols with aryl substituents, preferably for which the aryl part is C 6 -C 10, advantageously C 6, and the alkyl part of the C 1 -C 4 alkanol, this alkyl part being able to be terminated or interrupted by a heteroatom, preferably oxygen or a hydroxyl group, preferably such as benzyl alcohol;

• the lactones preferably of formula (iii), as well as their mixtures, with:

Formula (iii) in which R 'represents a hydrogen, a linear or branched C1-Cs alkyl, a linear or branched C1-C4 hydroxyalkyl, n is 1, 2 or 3 and preferably, R' represents a hydrogen, a linear or branched C1-C6 alkyl, linear or branched C1-C2 hydroxyalkyl • especially cyclic sulfones in particular sulfolanes. preferably substituted by one or more (Ci-C4) alkyl groups such as 3-methyl sulfolane.

As particularly advantageous examples of lactones, mention may be made of γ-butyrolactone.

Mention may also be made of certain liquid alkanols, for example 1pentanol.

Even more preferably, said liquid organic compound compound (s) according to the invention are chosen from dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol mono n-butyl ether (whose INCI name is PPG-2 BUTYL ETHER) , tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, 3-phenyl-1-propanol, 2-phenyl1-propanol , benzyl alcohol, benzyloxyethanol, phenoxyethanol, and mixtures of these compounds.

In particular, the organic compound Iiquide (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa% is preferably chosen from i) alcohol ethers, ii) aliphatic esters, iii ) aromatic ethers, iv) alkanols with aryl substituents, preferably for which the aryl part is C 6 -C 10, advantageously C 6, and the alkyl part of the C 1 -C 4 alkanol, this alkyl part being able to be terminated or interrupted by a heteroatom, advantageously oxygen or a hydroxyl group, preferably such as benzyl alcohol and phenoxyethanol, v) cyclic sulfones comprising from 5 to 7 members and optionally substituted by one or more (Ci-C4) alkyl groups such as 3-methyl sulfolane, and mixtures thereof.

According to a particular embodiment of the invention, the liquid organic compound (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa% is (are) chosen (s) selected from aromatic alcohols, and mixtures thereof; even more preferably chosen from alkanols with aryl substituents and even more preferably benzyl alcohol and phenoxyethanol. In particular, benzyl alcohol is present in an amount between 1 and 10% such as 5% by weight relative to the total weight of the composition (A), (Ai), (A2), (A3), (B) or (C), more particularly composition (A), (Ai), (A2), or (A3); and phenoxyethanol in an amount between 0.5 and 3% such as 1% by weight relative to the total weight of the composition (A), (Ai), (A2), (A3), (B) or (C) , more particularly the composition (A), (Ai), (A2), or (A3).

According to another particular embodiment of the invention the liquid organic compound (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa% is (are) chosen (s) chosen from cyclic sulfones comprising from 5 to 7 members and optionally substituted by one or more (Ci-C4) alkyl groups such as 3-methyl sulfolane.

When it (s) is (are) present, the liquid organic compound (s) having a value of the Hansen 5H solubility parameter greater than 0 and less than 16 MPa% represent preferably a total content varying from 0.05 to 35% by weight, preferably from 1 to 20% by weight, better still from 2 to 10% by weight, in particular between 5 and 7% such as 6% by weight relative the total weight of the composition (A), (Ai), (A2), (A3), (B) or (C), more particularly the composition (A), (Ai), (A2), or (A3) .

v) Non-hydrotropic organic solvents

According to one embodiment of the invention, at least one of the compositions of the process of the invention comprises one or more additional organic solvents (different from the liquid organic compound (s) having a value of the parameter Hansen 5H solubility greater than 0 and less than 16 MPa%). More particularly, composition (A), (Ai), (A2), (A3), or (Ai) comprises one or more additional organic solvents (different from the liquid organic compound (s) having a value of the Hansen solubility parameter 5H greater than 0 and less than 16 MPa%), As additional organic solvent, there may be mentioned in particular the lower alkanols in C-iC4, such as ethanol and isopropanol; polyols and polyol ethers.

Preferably, at least one of the compositions of the process according to the invention comprises one or more lower C1-C4 alkanols, such as ethanol and isopropanol.

More particularly preferably, the composition (A), (Ai), (A2), (A3), (B) or (C), more particularly the composition (A), (Ai), (A2), or ( A3), comprising the compound or compounds of formula (I), (Γ), (II), (II '), (la), (a), (lia) or (Il'a) comprises one or more C1-C4 lower alkanols, such as ethanol and isopropanol.

Preferably, at least one of the compositions of the process according to the invention, more preferably the composition (A), (Ai), (A2), or (A3), comprising the compound or compounds of formula (I), (Γ ), (II), (II '), (la), (a), (lia) or (Il'a) includes ethanol.

The additional organic solvents (different from the liquid organic compound (s) having a Hansen 5H solubility parameter value greater than 0 and less than 16 MPa%) may be present in a total content preferably between 1 and 40% by weight, and even more preferably between 5 and 30% by weight approximately relative to the total weight of the composition which contains them in particular relative to the total weight of the composition (A), (Ai), (A2), or (A3).

vi) Thickeners

According to one embodiment of the invention, at least one of the compositions (A), (Ai), (A2), (A3), (B) or (C), further comprises one or more thickeners, preferably polymeric. More particularly, composition (A) or (A-i) further comprises one or more thickeners preferably chosen from cationic, nonionic, anionic or zwitterionic, associative or nonassociative organic polymers, of natural or synthetic origin,

Mention may be made, as thickening polymers, of non-associative thickening polymers with sugar units.

By “sugar unit” is meant within the meaning of the present invention a unit originating from a carbohydrate of formula Cn (H2O) _n -i or (CH2O) _{n which} can be optionally modified by sustitution, and / or by oxidation and / or dehydration.

The sugar units of the thickening polymers of the invention are preferably derived from the following sugars:

glucose;

galactose;

arabinose;

rhamnose;

mannose;

xylose;

fucose;

anhydrogalactose;

galacturonic acid;

glucuronic acid;

mannuronic acid;

galactose sulfate;

anhydrogalactose sulfate and fructose.

Mention may in particular be made, as thickening polymers of the invention, of native gums such as:

a) exudates from trees or shrubs of which:

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

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

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

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

b) gums derived from algae, of which:

agar (polymer derived from galactose and anhydrogalactose);

alginates (polymers of mannuronic acid and glucuronic acid);

carrageenans and furcelleranes (polymers of galactose sulfate and anhydrogalactose sulfate);

c) gums from seeds or tubers of which:

guar gum (polymer of mannose and galactose);

carob gum (polymer of mannose and galactose);

fenugreek gum (polymer of mannose and galactose);

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

konjac gum (glucose polymer and mannose);

d) microbial gums, of which:

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

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

scleroglucan gum (glucose polymer);

e) plant extracts including:

cellulose (glucose polymer);

starch (glucose polymer) and inulin.

These polymers can be modified physically or chemically. By way of physical treatment, mention may especially be made of temperature.

As chemical treatments, mention may be made of esterification, etherification, amidation, oxidation reactions. These treatments make it possible to lead to polymers which can in particular be nonionic, anionic or amphoteric.

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

The nonionic guar gums which can be used according to the invention can be modified by Ci-C6 (poly) hydroxylakyl groups.

Among the C1-C6 (poly) hydroxyalkyl groups that may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the state of the art and can for example be prepared by reacting oxides of corresponding alkenes such as for example propylene oxides with guar gum so as to obtain a guar gum modified by hydroxypropyl groups.

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

Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.

The starch molecules used in the present invention can have, as botanical origin, cereals or tubers. Thus, the starches are for example chosen from starches of corn, rice, cassava, barley, potato, wheat, sorghum, peas.

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

Diamidon phosphates or compounds rich in diamidon phosphate will preferably be used, such as the product proposed under the references PREJEL VA-70-T AGGL (phosphate of hydroxypropylated cassava gelatinized) or PREJEL TK1 (phosphate of diamidon of cassava gelatinized) or PREJEL 200 (acetylated cassava diamidon phosphate gelatinized) by the company AVEBE or NATIONAL STARCH STRUCTURE ZEA (diamatin phosphate cornified gelatinized).

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

The starch molecules can come from all vegetable sources of starch such as in particular corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above. The starch is preferably obtained from the potato.

The non-associative thickening polymers of the invention can be cellulosic polymers that do not contain a C10-C30 fatty chain in their structure.

The term “cellulosic” polymer is understood to mean, according to the invention, any polysaccharide compound having in its structure sequences of glucose residues united by β-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives can be anionic, cationic, amphoteric or nonionic;

Thus, the cellulosic polymers of the invention can be chosen from unsubstituted celluloses including in microcrystalline form and cellulose ethers.

Among these cellulose polymers, there are the cellulose ethers, the cellulose esters and the cellulose ether esters.

Among the cellulose esters, there are inorganic cellulose esters (nitrates, sulfates or cellulose phosphates, etc.), organic cellulose esters (monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates of cellulose ...) and mixed organic / inorganic esters of cellulose such as acetate butyratesulfates and acetate propionatesulfates of cellulose. Among the cellulose ether esters, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulftates.

Among non-ionic cellulose ethers without fatty chain in C10-C30

i.e. “non-associative”, mention may be made of (Ci-C4) alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel standard 100 Premium from DOW CHEMICAL); (poly) hydroxy (C-i-C4) alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR proposed by AOUALON) and hydroxypropylcelluloses (for example Klucel EF from AOUALON); mixed (poly) hydroxy celluloses (C-iC4) alkyl- (Ci-C4) alkylcelluloses such as hydroxypropyl-methylcelluloses (for example Methocel E4M from DOW CHEMICAL), hydroxyethylmethylcelluloses, hydroxyethyl-ethylcelluloses (for example Bermocoll E 481 FO AKZO NOBEL) and hydroxybutyl-methylcelluloses.

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

Among the cationic cellulose ethers without a fatty chain, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such that (poly) hydroxy (Ci-C4) alkyl celluloses, such as hydroxymethyl-, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, dimethyl-diallylammonium. The products sold meeting this definition are more particularly the products sold under the name Celquat® L 200 and Celquat® H 100 by the National Starch Company.

Among the non-associative thickening polymers without sugar units which can be used, mention may be made of crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked homopolymers of 2-acrylamido-2methylpropane sulfonic acid and their crosslinked acrylamide copolymers, homopolymers d 'ammonium acrylate or copolymers of ammonium acrylate and acrylamide alone or in mixtures.

A first family of suitable non-associative thickening polymers is represented by crosslinked acrylic acid homopolymers.

Among homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, such as for example the products sold under the names CARBOPOLS 980, 981, 954, 2984 and 5984 by the company NOVEON or products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3 VSA.

The non-associative thickening polymers can also be crosslinked (meth) acrylic acid copolymers such as the polymer sold under the name AQUA SF1 by the company NOVEON.

The non-associative thickening polymers can be chosen from crosslinked homopolymers of 2-acrylamido-2-methylpropane sulfonic acid and their crosslinked acrylamide copolymers.

Among the crosslinked copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and of partially or fully neutralized acrylamide, mention may be made in particular of the product described in example 1 of document EP 503 853 and it may be refer to this document for these polymers.

The composition may likewise comprise, as non-associative thickening polymers, homopolymers of ammonium acrylate or copolymers of ammonium acrylate and of acrylamide.

As examples of ammonium acrylate homopolymers, mention may be made of the product sold under the name MICROSAP PAS 5193 by the company HOECHST. Among the copolymers of ammonium acrylate and of acrylamide, mention may be made of the product sold under the name BOZEPOL C NEW or the product PAS 5193 sold by the company HOECHST. Reference may in particular be made to documents FR 2 416 723, US 2798053 and US 2923692 with regard to the description and preparation of such compounds.

Among the thickening polymers of the aqueous phases, mention may also be made of non-cellulosic associative polymers well known to those skilled in the art and in particular of a nonionic, anionic, cationic or amphoteric nature.

It is recalled that the "associative polymers" are polymers 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.

By "hydrophobic group" is meant a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms. carbon and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a monofunctional compound. For example, the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.

Among the associative polymers of anionic type, there may be mentioned:

- (a) those comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an anionic ethylenically unsaturated monomer, more particularly still by a vinyl carboxylic acid and most particularly with an acrylic acid or a methacrylic acid or mixtures thereof.

Among these anionic associative polymers, particularly preferred according to the invention, the polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of (meth) acrylates lower alkyls, 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 polyethylene unsaturated monomer, such as diallyl phthalate , allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

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

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

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

Anionic polymers of this type are for example described and prepared, according to US Patents 3,915,921 and 4,509,949.

Among this type of anionic associative polymers, use will be made more particularly of those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) , and 0 to 6% by weight of polymerizable crosslinking monomer, or else those consisting of 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 above.

Among said polymers above, very particularly preferred according to the present invention, the products sold by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TR1®, and the product sold by 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) terpolymers of maleic anhydride / C30-C38 α-olefin / alkyl maleate such as the product (copolymer maleic anhydride / C30C38 oc-olefin / isopropyl maleate) sold under the name PERFORMA V 1608 ® by NEWPHASE TECHNOLOGIES.

- (d) acrylic terpolymers comprising:

i) about 20% to 70% by weight of a α, βmonoethylenically unsaturated carboxylic acid [A], ii) about 20 to 80% by weight of a non-surfactant α, βmonoethylenically unsaturated monomer other than [ A], iii) about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in the application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate behenyl ethoxylated alcohol alcohol (40OE) terpolymer in 25% aqueous dispersion.

- (e) copolymers comprising, among their monomers, an α, β-monoethylenically unsaturated carboxylic acid and an ester of α, β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

Preferably, these compounds also comprise, as monomer, an ester of α, β-monoethylenically unsaturated carboxylic acid and of C1-C4 alcohol.

As an example of this type of compound, mention may be made of ACULYN 22® sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer.

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

The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth) acrylamido (Ci-C22) alkylsulfonic acids, / V- (CiC ₂ 2) alkyl (meth) acrylamido acids. - (Ci-C ₂ 2) alkylsulfonic like undecylacrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.

More preferably, use will be made of (meth) acrylamido (Ci-C ₂₂ ) alkylsulfonic acids such as for example acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid, l 2-acrylamido-2-methylpropane-sulfonic acid, methacrylamido-2methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2acrylamido-2,4,4-trimethylpentane-sulfonic acid, l 2-methacrylamidododecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid and their partially or totally neutralized forms.

More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) will be used as well as its partially or totally neutralized forms.

The polymers of this family can in particular be chosen from random amphiphilic polymers of AMPS modified by reaction with a C 6 -C 22 nmonoalkylamine or a di-n-alkylamine, and such as those described in patent application WO 00/31154 ( part of the content of the description). These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their alkyl derivatives substituted in β or their esters 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 hydrophobic ethylenically unsaturated monomer.

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

These copolymers are described in particular in patent application EPA-750899, US patent 5089578 and in the following publications by Yotaro Morishima:

o “Self-assembling amphiphilic polyelectrolytes and their nanostructures Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. "O" Miscelle formation of random copolymers of sodium 2- (acrylamido) -2methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scatteringMacromolecules, Vol. 33, No. 10 (2000), 3694-3704 ";

o “Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: sait effects on rheological behavior - Langmuir,, Vol. 16, No. 12, (2000) 5324-5332 ”;

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

Among these polymers, there may be mentioned:

• crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C8-Ci6) alkyl (meth) acrylamide units or of (C8-Ci6) units ) alkyl (meth) acrylate with respect to the polymer, such as those described in application EP-A 750 899;

• terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n- (C6-C18) alkylacrylamide units, such as those described in patent US5089578.

Mention may also be made of the fully neutralized AMPS and dodecyl methacrylate copolymers as well as the non-crosslinked and crosslinked AMPS and ndodecylmethacrylamide copolymers, such as those described in the articles by Morishima cited above.

Among the cationic associative polymers that may be mentioned:

- (I) Cationic associative polyurethanes;

- (II) The compound marketed by the company NOVEON under the name AQUA CC and which corresponds to the name INCI POLYACRYLATE-1 CROSSPOLYMER.

POLYACRYLATE-1 CROSSPOLYMER is the product of the polymerization of a mixture of monomers comprising:

o a di (C1-C4 alkyl) amino methacrylate (Ο-ι-Οβ alkyl), o one or more C1-C30 alkyl esters and (meth) acrylic acid, o a methacrylate polyethoxylated C10-C30 alkyl (20-25 moles of ethylene oxide unit), o a polyethylene glycol / polypropylene glycol 30/5 allyl ether, o hydroxy methacrylate (C2-C6 alkyl), and o dimethacrylate d ethylene glycol.

- (III) quaternized (poly) hydroxyethylcelluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote the phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized fatty chains of CsC30 alkyl hydroxyethyl celluloses, such as QUATRISOFT LM 200®, QUATRISOFT LM-X 52918-A®, QUATRISOFT LM-X 529-18-B® (C12 alkyl) and QUATRISOFT LM-X 529-8® (Cis alkyl) sold by the company AQUALON, the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (Cis alkyl) sold by the company CRODA and the SOFTCAT SL 100® product sold by AQUALON.

- (IV) Cationic polyvinyllactam polymers.

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

As poly (vinyllactam) polymers according to the invention, particularly using the terpolymers vinylpyrrolidone / tosylate tosylate terpolymers terpolymers dimethylaminopropylmethacrylamide / dodecyldimethylmethacrylamidopropylammonium, vinylpyrrolidone / dimethylaminopropylmethacrylamide cocoyldiméthyl-méthacrylamidopropylammonium, vinylpyrrolidone / dimethylaminopropylmethacrylamide / tosylate or chloride lauryldiméthylméthacrylamido- propyl.

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

Amphoteric associative polymers according to the invention are for example described and prepared in patent application WO 9844012.

Among the amphoteric associative polymers according to the invention, the acrylic acid / (meth) acrylamidopropyl trimethyl ammonium chloride / stearyl methacrylate terpolymers are preferred.

The nonionic type associative polymers which can be used according to the invention are preferably chosen from:

- (a) copolymers of vinyl pyrrolidone and hydrophobic fatty chain monomers, which may be mentioned by way of example:

- ANTARON V216® or GANEX V216® products (vinylpyrrolidone / hexadecene copolymer) sold by the company I.S.P.

- ANTARON V220® or GANEX V220® products (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P.

(b) copolymers of methacrylates or of C1-C6 alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain such as for example the methyl acrylate / oxyethylenated stearyl acrylate sold by the company GOLDSCHMIDT under the name ANTIL 208®.

- (c) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain such as for example the polyethylene glycol methacrylate / lauryl methacrylate copolymer.

- (d) polyether polyurethanes comprising in their chain, both hydrophilic sequences of a nature most often polyoxyethylenated and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.

- (e) polymers with an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX® compounds offered by the company SUD-CHEMIE.

- (f) celluloses or their derivatives, modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups or their mixtures where the alkyl groups are Cs - and in particular:

* nonionic alkylhydroxyethylcelluloses such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (Cw alkyl) sold by the company AQUALON * nonoxynylhydroxyethylcelluloses nonionics such as the product AMERCELL HM-1500 sold by the company AMERCHOL;

* non-ionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL;

- (g) associative guar derivatives such as hydroxypropylguars modified by a fatty chain such as the product ESAFLOR HM 22 (modified by a C22 alkyl chain) sold by the company LAMBERTI; the product MIRACARE XC 95-3 (modified by an alkyl chain in Cu) and the product RE 205-146 (modified by an alkyl chain in C20) sold by RHODIA CHIMIE;

Preferably, the polyether polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains being able to be pendant chains or chains at the end of hydrophilic block. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The polyether polyurethanes can be multiblock in particular in the form of a triblock. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer with hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These same polymers can also be in grafts or in a star.

The nonionic fatty chain polyurethane polyethers can be triblock copolymers whose hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. Nonionic polyether polyurethanes have a urethane bond between hydrophilic blocks, hence the origin of the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those whose hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds.

As examples of non-ionic polyether polyurethanes with a fatty chain which can be used in the invention, it is also possible to use Rheolate 205® with urea function sold by the company RHEOX or also Rhéolates® 208, 204 or 212, as well as Acrysol RM 184®.

Mention may also be made of the product ELFACOS T210® with a C1214 alkyl chain and the product ELFACOS T212® with a C18 alkyl chain from AKZO.

The product DW 1206B® from ROHM & HAAS with a C20 alkyl chain and a urethane bond, available at 20% dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an alcoholic medium. By way of example, such polymers that may be mentioned are RHEOLATE® 255, RHEOLATE® 278 and RHEOLATE® 244 sold by the company RHEOX. One can also use the product DW 1206F and the DW 1206J offered by the company ROHM & HAAS.

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

More particularly still, it is preferred to use a polyurethane polyether capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) alcohol stearyl or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names ACULYN 46® and ACULYN 44® [ACULYN 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, of stearyl alcohol and methylene bis (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 with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39% ) and water (26%)].

Preferably, the polymers of the cosmetic compositions in accordance with the present invention advantageously have in solution or in dispersion, at 1% of active material in water, a viscosity measured by means of the Rheomat RM 180 rheometer, at 25 ° C, greater than 0.1 ps, and more advantageously still greater than 0.2 cp, at a shear rate of 200 s-1.

Preferably the thickener or thickeners are chosen from polysaccharides, in particular cellulosic polymers, and more particularly hydroxy (Ci-4) alkylcelluloses such as hydroxyethylcelluloses (HEC), hydroxypropylmethylcelluloses (HPMC), xanthan gums, guar gums , and polyvinylpyrrolidones (PVP).

According to a particular embodiment of the invention, the organic thickening polymer or polymers are chosen from cellulosic polymers, and more particularly hydroxy (Ci-4) alkylcelluloses such as hydroxyethylcelluloses (HEC), hydroxypropylmethylcelluloses (HPMC)

When it (s) is (are) present, the organic thickening polymer (s) represents (s) a total content ranging from 0.01 to 10% by weight and preferably from 0.1 to 5% by weight relative to the total weight of the composition (A), (Ai), (A ₂ ), (A3), (B) or (C), and preferably (A), (Ai), (A ₂ ), or (A3).

The compositions (A), (Ai), (A ₂ ), (A3), (B) or (C) of the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric, zwitterionic polymers or mixtures thereof different from the thickening polymers described above, antioxidants, penetration agents , sequestering agents, perfumes, dispersing agents, cations, film-forming agents, ceramides, preserving agents, opacifying agents.

When present, the above adjuvants generally represent an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition (A), (Ai), (A ₂ ) , (A3), (B) or (C).

The pH of the compositions (A), (Ai), (A ₂ ), (A3), (B) or (C), can be adjusted to the desired value by means of alkaline agents as defined above in ii) or from acids as defined above in iii) or even using conventional buffer systems.

The compositions according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

The process of the invention notably makes it possible to obtain colors which change or whose color disappears and then reappears (switch off - switch on), or appears and disappears (switch on - switch off) in a pH zone which does not alter keratin fibers and without substantial loss of color, in particular in terms of color intensity or color rise.

In addition, the process of the invention makes it possible to obtain colorations of keratin fibers with intense colors, and a good rise in color which can permute according to the pH even after several cycles, with a rapid and frank effect of the change of color "switch off - switch on", with structured effects (geometric, graphic effect ...), without color transfer from one wick to another (eg possibility on braid comprising three dyes of different colors not do not diffuse the color from one strand to another, without shedding, even after several cycles of pH developers) and avoid denaturing the keratin fibers there.

In the sense of the present invention, the coloring is erased or extinguished when the keratin fibers have regained their color close to that of origin or even identical in particular on dark keratin fibers. The coloring is modified when the coloring obtained is different from that obtained during the previous step. The coloring is reformed when the coloring of the keratin fibers obtained is identical to that which had been obtained during a previous step and which had then been modified. The coloration obtained depends on the compound or compounds of formula (I), (P), (II), (IP), (la), (Pa), (Ha) or (ll'a) which are applied to the keratin fibers. .

According to a particular embodiment, the method of the invention is carried out on clear keratin fibers in particular of pitch (European scale) between 8 and 10.

"Height of tone" is the unit known to professional hairdressers, and published in the book "Science of hair treatments" by Charles ZVIAK 1988, Ed. Masson, p. 215 and 278, the pitch of the tone ranges according to the European scale from 1 (black) to 10 (light light blonde), a unit corresponding to a tone, the higher the number, the lighter the shade;

According to another particular embodiment, the process is carried out on dark keratin fibers, in particular chestnut, with a pitch (European scale) less than or equal to 6, preferably less than or equal to 4.

The “dark” keratin fiber is a keratin fiber which has a luminescence L * encrypted in the system C, IEL * a * b * less than or equal to 45 and preferably less than or equal to 40, knowing moreover that L * = 0 equivalent to black and L * = 100 to white.

On dark keratin fibers treated with compositions (A), (Ai), (A ₂ ), (A3), and after application of the revealing composition (B) or (C) the color appears up to black, with blue green or more natural copper chromatic reflections which disappear after application of the extinguishing composition (C) or (B).

According to a particular embodiment of the invention for treating keratin fibers, and in particular human keratin fibers such as the hair, the method is characterized in that the following steps are carried out:

i) a step of applying a composition (A), (Ai), or (A2) comprising one or more phenazine compounds of formula (I) or (la) as defined above in particular compound (1); preferably at basic or alkaline pH for which the compound is weakly colored or even colorless, then ii) a development step consisting in applying to said fibers a composition (C) at acidic pH;

then iii) a quenching step consisting in applying to said fibers a composition (B) at alkaline pH;

it being understood that steps ii) and iii) can be repeated several times.

According to a particular embodiment of the invention for treating keratin fibers, and in particular human keratin fibers such as the hair, the method is characterized in that the following steps are carried out:

i) a step of applying a composition (A), (Ai) or (A2), comprising one or more phenazine compounds of formula (I ') or (a) in particular of formula (Γ), such as defined above, then ii) a quenching step consisting in applying to said fibers a composition (B) at alkaline pH;

then iii) a revelation step consisting in applying to said fibers a composition (C) at acidic pH.

According to another particular embodiment of the invention for treating keratin fibers, and in particular human keratin fibers such as the hair, the method is characterized in that the following steps are carried out:

i) a step of applying a composition (A), (Ai), or (A3) comprising one or more oxazone compounds of formula (II) or (IIa) as defined above in particular compound (2); preferably at the acid pH for which the compound is weakly colored or even colorless, then ii) a revealing step consisting in applying to said fibers a composition (B) with basic pH;

then iii) a quenching step consisting in applying to said fibers a composition (C) at acidic pH;

it being understood that steps ii) and iii) can be repeated several times.

According to a particular embodiment of the invention for treating keratin fibers, and in particular human keratin fibers such as the hair, the method is characterized in that the following steps are carried out:

i) a step of applying a composition (A), (Ai) or (A3), comprising one or more oxazone compounds of formula (II ') or (ll'a) in particular of formula (2'), as defined above, then ii) a quenching step consisting in applying to said fibers a composition (C) at acidic pH;

then iii) a revelation step consisting in applying to said fibers a composition (B) at basic pH.

The application of composition (A), (Ai), (A2) or (A3), of the process according to the invention may or may not be followed by a rinsing, preferably with a rinsing.

The application of composition (B) of the process of the invention may or may not also be followed by rinsing, preferably without rinsing.

The application of composition (C) of the process of the invention may or may not also be followed by rinsing, preferably with rinsing.

Preferably, the application of composition (A), (Ai), (A ₂ ) or (A3) of the process according to the invention is followed by drying, preferably after rinsing.

The application of composition (B) of the process of the invention may or may not also be followed by drying.

The application of composition (C) of the process of the invention may or may not also be followed by drying.

The drying step can be carried out either in air (natural drying) or by any heating device such as a hair dryer or heating lamps or a heating helmet, associated or not with a smoothing with a brush (brushing) , occurs before the smoothing step using a smoothing iron.

The composition (A), (Ai), (A ₂ ) or (A3) of the invention can be applied to dry or wet keratin fibers, preferably on dry or damp hair, preferably on dry hair.

The bath ratio of the composition (A), (Ai), (A ₂ ) or (A3), applied can vary from 0.1 to 20, more particularly from 0.2 to 15, and preferably between 0.5 and 13, even more preferably from 1 to 12. By bath ratio is meant the ratio between the total weight of the composition applied and the total weight of keratin materials to be treated.

The exposure time of the composition (A), (Ai), (A ₂ ) or (A3) of the invention is preferably between 3 and 120 minutes, preferably between 5 and 60 minutes, even more preferably between 10 and 40 minutes, such as 30 minutes.

The application temperature is generally fixed between room temperature and 80 ° C, preferably between 25 and 55 ° C, more particularly between 28 and 40 ° C.

A device or kit

Another subject of the invention is a device or kit with several compartments which comprises: i) in a first compartment the oxazone or phenazine compounds of formula (I), (I '), (II), (II'), ( la), (a), (lia) or (ll'a) as defined above, ii) in a second compartment: a composition (B) at basic pH; and iii) in a third compartment a composition (C) at acidic pH.

Preferably, the kit with several compartments of the invention comprises: i) in a first compartment a composition (A), (Ai), (A2) or (A3), as defined above, ii) in a second compartment: a composition (B) at basic pH; and iii) in a third compartment a composition (C) at acidic pH.

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

EXAMPLES

The following compositions were prepared, the amounts are given in g per 100 g of composition:

- Composition (A ’) comprising the compounds of formula (I), the amounts are given in g per 100 g of composition

Ingredients Composition (A2) Composition (A3) invention invention Ethanol 15 15 Hydroxyethylcellulose (HEC - Natrosol 250 HHR) 1.5 1.5 Benzyl alcohol BnOH 5 5 phenoxyethanol 1 1 Caprylyl glycol 1 1 Neutral Red (1) 0.5 - Resazurin Sodium (2 ’) - 0.5 Water Qsp 100 Qs 100

- Composition (B ’) at basic pH

ingredients Amount Monoethanol amine (MEA) 5 Water Qsp 100

pH of the composition 11.4 ± 0.5 - Composition (C ’) at acid pH:

ingredients Amount Phosphoric acid 5 Water Qsp 100

pH of the composition 1.4 ± 0.5

Each of the compositions (A2), and (A3) according to the invention is applied to locks according to the same protocol, namely:

- lock of natural hair with 90% white hair (height of tone HT9),

- then leave to stand for 30 minutes, at 31 ° C;

- then rinse with water then dry

Once the keratin fibers are dried, the "SWITCH" treatment is applied:

• To obtain the "SWITCH ON", the composition (C ') is applied to each lock treated with the composition (A2) by vaporizing it, or else the composition (B') is applied to each lock treated with the composition (A3) by vaporizing it, • To obtain the "SWITCH OFF", the composition (B ') is applied to each lock treated with the composition (A2) by vaporizing it, or else the composition is applied to each lock treated with the composition (A3) (C ') by vaporizing it.

Color results:

The color of the locks was evaluated in the CIE L * a * b * system, using a ColorShot MultiSpectral colorimeter (illuminant D65, angle 10 °). In this L * a * b * system, the three parameters respectively designate the color intensity (L *), a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the L *, the more intense the color.

Color rise:

The colorimetric measurements were carried out just after the application of the composition (A2) or (A3), then after each of the “switch” treatments.

The variation in coloration between the strands of untreated hair and of treated hair is defined by (ΔΕ *) according to the following equation:

Δ E * = 7 (1 * -I _o *) ² + (a * - a0 *) ² + (b * - b0 *) ²

In this equation, L *, a * and b * represent the values measured on locks of hair after treatment and Lo *, ao * and bo * represent the values measured on locks of hair before treatment. The greater the value of ΔΕ *, the greater the rise in color.

The variation in coloration between the strands of hair treated and revealed (switch on) and extinct (switch off) is defined by (AE * on-off) according to the following equation:

Δ E * on - off = -J (£ * off -L * on) ² + (a * off - a * cw) ² + (b * OFF - b * cw) ²

In this equation, L * on, a * oN and ô * on represent the values measured on locks of hair after treatment with composition (A2) or (A3), then application of the composition "switch on" and L * off , £ i * off and b * oFF represent the values measured on locks of hair after treatment with the composition (A2) or (A3), then application of the development composition "switch on" then application of the composition for quenching "Switch off". The higher the value of AE * on-off, the greater the variation in color between the application of the developer and the extinction.

\ E switch \ E vs Name Treatment L * a * b * C * on vs. reference switch off Hair no treated 52.3 9.1 25.8 27.4 Composition of invention (A2) Result spontaneous* 30.7 26.2 13.0 29.2 26.4 Composition of invention (A2), SWITCH WE 28.3 19.7 5.5 20.4 15.7 32.0 Composition of the invention (A ₂ ), SWITCH OFF 42.9 22.3 33.9 40.5 56.6 Composition of invention (As), Result spontaneous* 34.0 11.4 1.2 11.5 5.8

Composition of invention (As), SWITCH WE 35.2 22.7 9.9 24.8 23.6 21.4 Composition of invention (As), SWITCH OFF 31.9 7.2 -4.4 8.5 28.4 It appears that the rise of the color o obtained with the compositions of the invention has a

very large amplitude between the "switch on" and the "switch off", and even after several cycles without a significant loss of amplitude. The colors in "switch on" are very intense.

In addition, the process according to the invention allows the successive appearance (s) / disappearance of color in a few seconds, generally upon application of the revealing composition and without having to use a hair dryer. Many ON / OFF cycles can be chained and very good toughness has been observed, which is in the order of 5 to 8 shampoos. In addition, the integrity and feel of the hair are respected.

Claims (3)

1. Process for treating keratin fibers, in particular human fibers such as the hair, using: i) a step of applying a composition (A) comprising one or more compounds of formula (I), (I '), (II) or (II') as well as its (their) optical, geometric, tautomeric isomers , as well as its (their) solvates such as hydrates: (II) (II ’) Formulas (I) to (II ’) in which: X and X ′, which may be identical or different, represent an oxygen or sulfur atom or an N (R _a ) group with R _a representing a hydrogen atom or a (Ci-C6alkyl, aryl such as phenyl group), or aryl (Ci-C6) alkyl such as benzyl, in particular R _a represents a hydrogen atom or a (Ci-C4) alkyl group such as methyl; - R, and R ', identical or different, represent a hydrogen atom or a group chosen from (Ci-C6alkyl, (Ci-C6alkoxy, (di) (CiC6) (alkyl) amino, preferably hydrogen or (Ci- Côjalkyle; - R ”, and R '”, identical or different, represent a hydrogen atom, or a group (Ci-C6alkyl, aryl such as phenyl, or aryl (Ci-C6) alkyl such as benzyl ,, preferably hydrogen or (Ci-Côjalkyle; - G represents a nitrogen atom, a group: N (O) or: N ⁺ -O '; - M represents an alkali metal, alkaline earth metal, or an ammonium group; - An ^- represents an anionic counter ion; Then: When the composition (A) comprises one or more compounds of formula (I), the application of the composition (A) is followed by ii) a development step ("switch on") consisting in applying to said fibers a composition (C) at acidic pH; followed by iii) a step of switching off or erasing the color (“switch off”) consisting in applying to said fibers a composition (B) at basic pH; When the composition (A) comprises one or more compounds of formula (I ′), the application of the composition (A) is followed by ii) a step of dyeing the color consisting in applying to said fibers a composition (B) at basic pH, followed by iii) a development step consisting in applying to said fibers a composition (C) at acidic pH; When the composition (A) comprises one or more compounds of formula (II), the application of the composition (A) is followed by ii) a development step (“switch on”) consisting in applying to said fibers a composition (B) at basic pH; followed by iii) a step of switching off or erasing the color (“switch off”) consisting in applying to said fibers a composition (C) at acid pH; and • When the composition (A) comprises one or more compounds of formula (II ′), the application of the composition (A) is followed by ii) a step of quenching the color consisting in applying to said fibers a composition (C) at acid pH, followed iii) by a development step consisting in applying to said fibers a composition (B) at basic pH; it being understood that steps ii) and iii) can be repeated several times. 2. Method according to any one of the preceding claims, in which the compound or compounds of formula (I), (! ’) ,. (II) or (II ’) are chosen from the following compounds of formula (la) to ~ (ll’a): as well as their optical, geometric, tautomeric isomers, as well as their solvates such as hydrates: Formulas (la) à (ll’a) in which: - X and X ’, as defined above, in particular X’ represents an oxygen atom, preferably X and X ’represent an oxygen atom; - R, and R ’, as defined above, in particular R and R’ represent a hydrogen or (Ci-C4) alkyl atom; such as methyl, preferably R represents a hydrogen atom and R ’represents a (Ci-C4) alkyl group; such as methyl; - R ”, and R’ ”, as defined above, in particular represent a hydrogen atom, or a group (Ci-C6alkyl, preferably hydrogen or (Ci-C4) alkyl such as methyl; - R _a as defined above, in particular represents a hydrogen atom or a (Ci-C4) alkyl group such as methyl - G represents a nitrogen atom, a group: N (O) or: N ⁺ -O ' - M represents an alkali metal, alkaline earth metal, or an ammonium group, preferably alkaline such as sodium; and - An 'represents an anionic counter ion. 3. Method according to any one of the preceding claims, in which the compound or compounds of formula (I), (I '), (II), (II'), (la), (a), (lia) and ( They are chosen from the following compounds (1) to (3 '):