FR3083106A1 - METHOD FOR COLORING KERATINIC FIBERS USING A MONOSACCHARIDE, AN AMINE GROUP POLYSACCHARIDE AND A COLORING MATERIAL - Google Patents

Abstract

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers a) of at least one monosaccharide, b) of at least one particular polysaccharide , in salified form or not and c) at least one coloring matter, followed by a heat treatment of the keratin fibers. The present application also relates to a composition at acidic pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), in salified form or not, and c) at least a coloring matter. The present invention also relates to a kit comprising a device with several compartments containing a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), and c) at least one coloring matter and a device for heating keratin fibers.

Description

© PROCESS FOR COLORING KERATINIC FIBERS USING A MONOSACCHARIDE, A POLYSACCHARIDE WITH AMINE GROUPS AND A COLORING MATERIAL.

@) The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers a) of at least one monosaccharide, b) of at least one particular polysaccharide, in salified form or not and c) at least one coloring matter, followed by a heat treatment of the keratin fibers.

The present application also relates to a composition at acid pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), in salified or unsalted form, and c) at least a coloring matter.

The present invention also relates to a kit comprising a device with several compartments containing a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), and c) at least one coloring matter and a device for heating keratin fibers.

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Process for dyeing keratin fibers using a monosaccharide, a polysaccharide with amino groups and a coloring matter

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers a) of at least one monosaccharide, b) of at least one particular polysaccharide , in salified form or not and c) at least one coloring matter, followed by a heat treatment of the keratin fibers.

The present application also relates to a composition at acid pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), in salified or unsalted form, and c) at least a coloring matter.

The present invention also relates to a kit comprising a device with several compartments containing a) at least one monosaccharide, b) at least one polysaccharide with amine group (s), and c) at least one coloring matter and a device for heating keratin fibers.

For a long time, many people have sought to modify the color of their hair in order, for example, to mask their gray hair.

To color keratin materials, and in particular human keratin fibers, two types of color have essentially been developed.

The first type of coloring is the so-called permanent or oxidation coloring, which uses dye compositions containing oxidation dye precursors, generally called oxidation bases. 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 combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.

The second type of coloration is the so-called semipermanent coloration or direct coloration, which consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for said fibers, to let them stand, then to rinse them.

This type of process does not require the use of an oxidizing agent to develop the coloring. However, it is possible to use such an agent, in order to obtain a lightening effect with the coloring. This is called direct or semi-permanent coloring under lightening conditions.

The permanent or semi-permanent coloring processes under lightening conditions therefore require the use, with the dye composition, of an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases.

These conventional staining procedures can damage the integrity of the keratin fibers. Softer solutions, also called makeup solutions and based on weak physico-chemical interactions, make it possible to deposit coloring and / or pearlescent agents on the surface without threatening the integrity of the fibers. Among the coloring agents which can be used in these makeup compositions, the pigments and in particular the nacres, such as the nacres of the mica / iron oxide type, exhibit advantageous coloring properties.

It is currently possible to deposit these coloring agents on the fibers to obtain the desired effect. However, the colorings thus obtained are only of short duration. In fact, given the weak interaction between the coloring agents and the fibers, the colorings tend to fade, or even be eliminated, quickly, vis-à-vis external agents, such as light, sweat, mechanical actions (brushing, styling), and in particular after a few shampoos.

Furthermore, the dyeing power of these compositions may not be entirely satisfactory, or even low, and lead to a restricted range of colors. The colors can also be too selective, that is to say that the discrepancy in color is too great along the same keratin fiber which is differently sensitized between its tip and its root.

It is also interesting to find a way to color the damaged keratin fibers by repairing them, that is to say by improving the cosmetic of the intrinsically damaged keratin fibers, while retaining or even improving the managability (discipline), the anti-frizz and / or the remanence of the styling of said fibers. It is also interesting to prevent breakage of natural keratin fibers, while retaining or even improving the manageability (discipline), anti-frizz and / or the remanence of the styling of said fibers.

Finally, to these drawbacks, there are the risks of dyeing users' hands and clothes when applying these compositions to keratin fibers.

Thus, there is a real need to develop a process for coloring keratin materials, in particular keratin fibers, and in particular human keratin fibers such as the hair, which makes it possible to obtain good coloring properties, in particular in terms of intensity, tenacity and homogeneity, as well as satisfactory cosmetic properties, while preserving the integrity of the keratin fibers. The coloring properties, and in particular the intensity, the tenacity and the homogeneity, must also be persistent in the shampoos.

In addition, there is a real need to propose a process which is easy to implement and which avoids any risk of transfer of the colors to the hands and clothes of the users.

It has been discovered, surprisingly, that the combination of applications on keratin fibers of at least one monosaccharide, at least one particular polysaccharide and at least one particular coloring matter, with a heat treatment of said fibers allows achieve these goals; and in particular to provide colorings having good properties, in particular in terms of intensity, homogeneity and tenacity with regard to external agents, while respecting the integrity of the keratin fibers and avoiding staining the hands and user clothes.

The present application therefore relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising:

(i) a step of applying to said keratin fibers a) one or more monosaccharide (s), (ii) a step of applying to said keratin fibers b) one or more polysaccharide (s) with amino group (s) ( s), salified (s) or not salified (s); and (iii) a step consisting in applying to said keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof;

it being understood that steps (i), (ii) and (iii) can be carried out simultaneously or sequentially, before being followed by iv) a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C, preferably with an iron.

The present invention also relates to an aqueous composition at acid pH (pH <7), also called composition (C), comprising:

a) one or more monosaccharide (s),

b) one or more polysaccharide (s) with amine group (s), salified (s) or not salified,

c) one or more coloring matter (s) chosen from pigments, direct dyes and mixtures thereof, and

d) optionally one or more mineral or organic acid (s).

Another subject of the invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a step of applying to said keratin fibers an aqueous composition (C), as described above , followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C., preferably with an iron.

The association of particular (poly) saccharides with a pigment and / or a direct dye, followed by a heat treatment makes it possible to color the keratin fibers without damaging the fibers, or staining the hands and clothes of the users.

Furthermore, the combination of the particular monosaccharide and the amino polysaccharide makes it possible to form a protective film around the fibers containing the coloring matter. Thus the colorings obtained are more resistant to external agents, and are in particular persistent in shampoos.

The colors and the keratin fibers treated are also resistant to friction and other mechanical attacks such as brushing and combing. It should also be noted that the treated keratin fibers do not transfer the color to the tissues and do not stain the scalp.

The colored fibers with the combination of the particular monosaccharide (s), the amino polysaccharide (s) and the coloring material (s) according to the invention make it possible to color and in addition to improving the cosmetics of intrinsically damaged keratin fibers, while retaining or even improving the manageability (discipline), the anti-frizz and / or the remanence of the styling of said fibers. This association also makes it possible to prevent breakage of natural keratin fibers, while retaining or even improving the managability (discipline), the anti-frizz and / or the remanence of the styling of said fibers.

The colors also have improved coloring properties, in particular in terms of intensity, homogeneity and persistence, in particular with shampoos.

Finally, the present invention relates to a kit comprising:

a device with several compartments comprising a first compartment containing a cosmetic composition (ca) comprising a) one or more monosaccharide (s); a second compartment containing a cosmetic composition (cb) comprising b) one or more polysaccharide (s) with amine group (s) and optionally d) one or more organic or mineral acids; and a third compartment containing a coloring composition (ce) comprising c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof; and

- a device for heating keratin fibers to a temperature of at least 80 ° C.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

In what follows unless stated otherwise:

by “monosaccharides” is meant a mono-osidic sugar comprising at least 5 carbon atoms of formula C _X (H2O) _X , with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusive between 5 and 7, preferably x = 6, they can be of configuration D or L, and of alpha or beta anomer, as well as their salts and their solvates such as hydrates, one or more hydroxyl groups can be replaced by one or more amino groups;

by “polysaccharides” is meant a polysaccharide sugar which is a polymer made up of several oses linked together by O-osidic bonds, said polymers being made up of monosaccharide units as defined above, said monosaccharide units comprising at least 5 atoms of carbon, preferably 6, in particular the mono-osidic units are linked together in 1.4 or 1.6 in an a (alpha) or β (beta) anomer, each osidic unit possibly being of L or D configuration, as well as its salts and its solvates such as the hydrates of said monosaccharides; they are more particularly polymers formed from a certain number of oses (or monosaccharides) having the general formula: - [Cx (H2O) _y )] _n -, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusive between 5 and 7, preferably x = 6, and y is an integer which represents x - 1, and n is an integer greater than or equal to 2, particularly inclusive between 3 and 3000, more particularly between 5 and 2500, preferably between 10 and 2300;

by “with amine group (s)” is meant that the monosaccharide (s) a) or polysaccharide (s) b) are substituted by one or more amino group (s) NR1R2 ie at least one of the groups hydroxy of at least one sugar unit is replaced by a group NR1R2, with Ri and R2, identical or different, representing i) a hydrogen atom, ii) a (Ci-C6) alkyl group optionally substituted, preferably by a or more hydroxy or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl (Ci-C4) alkyl group such as benzyl, v) a (hetero) cyclo (C5-C7) alkyl group such as cyclohexyl, morpholinyl , piperazinyl, piperidinyl, vi) a (hetero) cyclo (C5C7) alkyl (Ci-C4) alkyl group such as cyclohexylmethyl, vii) -C (Y) - (Y ') _P R'i with Y and Y', identical or different, representing an oxygen, sulfur or N (R'2) atom, preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined above, and in particular R'i denoting a (Ci-C6) alkyl group such as methyl. Preferably R1 and R2 represent a hydrogen atom, or a (C1-C4) alkylcarbonyl group such as acetylene;

by "low molecular weight" is meant that the amine group polysaccharide has an average molecular weight of less than 400,000 Da;

by “organic or mineral acid salt” is meant more particularly the organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids Alk-S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2ÛH such as benzene sulfonic acid and toluene sulfonic acid; vi) alkoxysulfinic acids: AlkO-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) H3PO4 phosphoric acid; ix) triflic acid CF3SO3H and x) tetrafluoroboric acid HBF4; xi) organic monocarboxylic acids of formula (I) (I) R-C (O) -OH (I) formula (I) in which:

R representing a (hetero) aryl group such as phenyl, (hetero) aryl (Ci-C4) alkyl such as benzyl, or (Ci-C3o) alkyl or an unsaturated C2-C30 radical (ie comprising at least one ethylenic unsaturation, of preferably ethylenic unsaturation) said unsaturated C2-C30 alkyl group or radical being optionally interrupted and / or optionally substituted preferably with one or more hydroxy groups and unsubstituted by one or more amino radicals, R preferably denoting a group (Ci-C6 ) alkyl optionally interrupted and / or optionally substituted by 1, 2 or 3 hydroxy groups, more preferably R represents a (Ci-C4) alkyl group such as methyl or ethyl; in particular the monocarboxylic organic acids (I) are chosen from acetic acid, glycolic acid, lactic acid and their mixtures, and more particularly from acetic acid and lactic acid; xii) polycarboxylic acids of the following formula (H):

formula (II) in which:

A represents a polyvalent hydrocarbon group comprising from 1 to 30 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms such as oxygen and / or optionally substituted in particular by one or more hydroxy groups and t represents an integer inclusive between 1 and 5; preferably A represents a divalent (Ci-C6) alkylene group optionally substituted in particular by one or more hydroxy groups and unsubstituted by at least one amino radical, and t is 1, 2 or 3, the polycarboxylic acids of formula (II) are preferably chosen from tartaric acid, succinic acid, fumaric acid, citric acid and their mixtures; and xiii) amino acids containing more carboxylic acid radicals than amino groups such as gammacarboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; in particular the salts of monocarboxylic acids other than pyrrolidonecarboxylic acid, ethoxylated stearic acids 100 EO and 500 EO and linoleic acid;

an “alkyl radical” is a linear or branched Ci-Cio hydrocarbon radical, preferably in Ci-Cô and in particular in CiC4 such as methyl or ethyl, unless otherwise indicated;

a (Cx-Cy) alkyl radical is a Cx-Cy hydrocarbon radical, linear or branched;

the expression “optionally interrupted” attributed to the alkyl radical or to the polyvalent hydrocarbon group A as defined above implies that said radical can be interrupted by one or more groups or heteroatoms chosen from O, S, CO or their combinations such as - CO-O- or -O-CO-, preferably interrupted by one or more non-adjacent oxygen atoms;

the expression “optionally substituted” attributed to the alkyl radical or to the polyvalent hydrocarbon group A as defined above implies that said radical may be substituted by one or more radicals chosen from the radicals i) hydroxyl, ii) C1-C4 alkoxy , Hi) carboxy, iv) acylamino, v) amino optionally substituted by one or two alkyl radicals, identical or different, in C1-C4, said alkyl radicals being able to form with the nitrogen atom which carry them a heterocycle comprising of 5 with 7 links, optionally comprising another heteroatom different or not from nitrogen;

an “alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C1-C10 preferably in Ci-Cô and more particularly in CiC4 such as methoxy or ethoxy;

when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical can be substituted by at least one substituent carried by a carbon atom, chosen from an atom or group:

- halogen;

- C1-C6, preferably C1-C4 alkyl, optionally substituted;

- hydroxyl;

- C1-C2 alkoxy;

- (poly) -hydroxyalkoxy C1-C4;

- amino;

- 5 or 6-membered heterocycloalkyl;

- heteroaryl with 5 or 6 members and optionally substituted by a (Ci-C4) alkyl radical, preferably methyl;

- amino substituted by one or two alkyl radicals, identical or different, in C1-C6 optionally substituted:

- acylamino (-NR-C (O) -R ') in which the radical R is a hydrogen atom, an alkyl radical in C1-C4 optionally carrying at least one hydroxyl group and the radical R' is a radical C1-C2 alkyl;

- carbamoyl ((R) 2N-C (O) -) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group;

- alkylsulfonylamino (R'-S (O) 2-N (R) -) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical;

- aminosulfonyl ((R) 2N-S (O) 2-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group,

- cyano;

- nitro or nitroso; and

- polyhaloalkyl, preferably trifluoromethyl; the cyclic or heterocyclic part of a non-aromatic group can be substituted by at least one substituent chosen from groups:

- hydroxyl;

- C1-C4 alkoxy, (poly) hydroxyalkoxy, C2-C4;

- C1-C4 alkyl;

- alkylcarbonylamino (RC (O) -N (R ') -) in which the radical R' is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl group, amino optionally substituted by one or two identical or different C1-C4 alkyl groups themselves optionally bearing at least one hydroxyl group;

- alkylcarbonyloxy (RC (O) -O-) in which the radical R is a C1-C4 alkyl radical, amino group optionally substituted by one or two identical or different C1-C4 alkyl groups themselves optionally bearing at least one hydroxyl group;

- alkoxycarbonyl (RGC (O) -) in which the radical R is a C1-C4 alkoxy radical, G is an oxygen atom, or an amino group optionally substituted by a C1-C4 alkyl group itself optionally carrying at least one hydroxyl group;

a cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also be substituted by one or more oxo groups;

an “aryl” radical represents a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; such as phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl, preferably phenyl;

a “heteroaryl radical” represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably a heteroaryl radical is chosen from acridinyl, (benz) imidazolyle, (benzo) bistriazolyle, (benzo) pyrazolyle, (benzo) pyridazinyle, (benzo) quinolyle, (benzo) thiazolyle, (benzo) triazolyle, (benz) oxazolyle, pyridinyle , tetrazolyl, dihydrothiazolyl, imidazopyridinyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phénooxazolyle, pyrilyle, pyrazoyltriazyle, pyridyl, pyridinoimidazolyle, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolopyridinyl, thiazoylimidazolyle, thiopyrylyle, triazolyl , and xanthylyl;

a “heterocyclic radical” is a radical which may contain one or two unsaturations but not aromatic, mono or polycyclic, condensed or not, containing from 5 to 22 links, comprising from 1 to 6 heteroatoms chosen from the nitrogen atom, oxygen, sulfur and selenium;

a “heterocycloalkyl radical” is a heterocyclic radical comprising at least one saturated ring;

the term “soft” keratin fibers or “soft” hair means that said fibers or hair are elastic, have no corporalisation, do not hold, the hair is flat without volume;

the expression "at least one" is equivalent to "one or more";

the limits of a range of values are included in this range, in particular in the expressions “included between” and “going from ... to ...” and the expression “inclusive” for a range of concentrations means that the limits of the range are part of the defined interval.

Monosaccharides

The dyeing process according to the present invention comprises a step consisting in applying to the keratin fibers a) one or more monosaccharide (s), as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates and their mixtures, also called ingredients a).

The monosaccharide (s) a) which can be used according to the present invention can be with an amine group (s) or not, that is to say that they can be chosen from monosaccharides not comprising amine group, monosaccharides comprising at least one amine group and mixtures thereof.

According to a first variant of the invention, the monosaccharide (s) a) are chosen from monosaccharides not comprising an amine group, as well as their anomers a or β, their optical isomers of L or D configuration and their solvates such as hydrates and their mixtures.

According to a particular form of this variant, the monosaccharide (s) a) denote a mixture of monosaccharide (s) one of which is xylose or its anomers a or β, its optical isomers of configuration L or D and its solvates such as hydrates.

According to another particular form of this variant, the monosaccharide (s) a) denote a single monosaccharide, in particular xylose or its a or β anomers, its optical isomers of L or D configuration and its solvates such as hydrates.

According to a first embodiment, the monosaccharide (s) a) are C? : heptoses, such as aldoheptoses and ketoheptoses as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, and their mixtures.

According to a second preferred embodiment of the invention, the monosaccharide (s) a) is (are) Ce monosaccharides: the hexoses, as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such than hydrates, and mixtures thereof.

More preferably, the monosaccharide (s) a) are chosen from the hexoses of formula (A1) as well as their anomers a or β, their optical isomers of configuration L or D and their solvates such as hydrates, and their mixtures:

formula (A1) in which, R ^a , R ^b , R ^d , R ^e and R ^f , which are identical or different, represent i) a hydroxy group, ii) an (CiC4) alkoxy group in which the alkyl chain may be optionally substituted in particular by one or more hydroxy groups, or iii) a carboxy group, more preferably R ^a , R ^b , R ^d , R ^e and R ^f , represent a hydroxy group.

Preferably, the monosaccharide (s) a) are chosen from the hexoses of formula (Al) of configuration D, or also called D-glucopyranes, and better still from the hexoses of formula (Al) of anomeric configuration β (beta).

Better still, the monosaccharide (s) a) are chosen from the hexoses of formula (A1 ′) as well as their anomers a or β, their optical isomers of configuration L or D, preferably D, and their solvates such as hydrates, and their mixtures:

(Al ') formula (Al') in which, R ^a , R ^b , R ^d , R ^e and R ^f are as defined above for (Al).

The monosaccharide (s) a) are advantageously chosen from aldohexoses and ketohexoses, preferably from glucose, galactose, allose, altrose, mannose, gulose, idose, talose, as well as their anomers alpha or beta their optical isomers of configuration L or D, their solvates such as hydrates and their mixtures, more preferentially among glucose and galactose, better still glucose, and still better glucose of configuration D.

According to yet a third particular embodiment, the monosaccharide (s) a) is (are) C5 monosaccharides: the pentoses, as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates , and mixtures thereof. According to this embodiment, the monosaccharide (s) a) are chosen from the pentoses of formula (A2), as well as their anomers a or β, their optical isomers of configuration L or D, their solvates such as hydrates and their mixtures:

Ri

(A2) formula (A2) in which, Rg, Rh, Ri, and Rj, which are identical or different, represent i) a hydroxy group, or ii) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted, in particular by one or more hydroxy groups.

More preferably, the monosaccharide (s) a) are chosen from the pentoses of formula (A2) of configuration D, and better still, from the pentoses of formula (A2) of anomeric configuration β (beta).

Preferably, the monosaccharide (s) a) are chosen from aldopentoses, ketopentoses and their mixtures, and more preferably xylose, arabinose, lyxose, ribose, ribulose and xylulose as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, and their mixtures.

According to this first variant of the invention, the monosaccharide (s) a) are advantageously chosen from monosaccharides not comprising an amine group, and preferably from xylose, glucose and their mixtures.

According to a second variant of the invention, the monosaccharide (s) a) are chosen from monosaccharides with amine group (s), that is to say monosaccharides comprising at least one amine group, as well as their anomers a or β, their optical isomers of configuration L or D and their solvates such as hydrates and their mixtures.

When the monosaccharide (s) a) is (are) chosen from monosaccharides with amine group (s), it (s) is (are) preferably salified (s) using a mineral acid such as hydrochloric acid.

According to a particular form of this variant, the monosaccharide (s) a) is (are) with amine group (s) and denote (s) a mixture of monosaccharide (s) with amine group (s) ) one of which is glucosamine or its organic or mineral acid salts such as hydrochloric acid, its a or β anomers, its optical isomers of L or D configuration and its solvates such as hydrates.

According to another form of this variant, the monosaccharide (s) a) is (are) with amine group (s) and denote (s) a single monosaccharide with amine group (s), in particular glucosamine or its organic or mineral acid salts or more particularly its mineral acid salts such as its hydrochloric acid salt, its a or β anomers, its optical isomers of L or D configuration and its solvates such as hydrates .

According to a first particular embodiment, the monosaccharide (s) a) is (are) chosen (s) from monosaccharides with amine group (s), in: pentosamines, as well as their a or β anomers, their isomers L or D configuration optics and their solvates such as hydrates and mixtures thereof. According to this particular embodiment, the pentosamines are chosen from aldopentosamines and ketopentosamines such as xylosamine, arabinosamine, lyxosamine, ribosamine, ribulosamine and xylulosamine as well as their organic or mineral acid salts, their oc or β anomers, their isomers L or D configuration optics and their solvates such as hydrates.

According to a second particular embodiment, the monosaccharide (s) a) is (are) chosen from monosaccharides with amine group (s), at C? : heptosamines such as aldoheptosamines and ketoheptosamines as well as their organic or mineral acid salts, as well as their oc or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates.

According to yet a third particular embodiment, the monosaccharide (s) a) is (are) chosen from the Ce monosaccharides: hexosamines as well as their organic or mineral acid salts, their a or β anomers, their optical configuration isomers L or D and their solvates such as hydrates.

Preferably, the monosaccharide (s) a) (is) are chosen from the hexosamines of formula (A3) below as well as their organic or inorganic acid salts such as hydrochloric acid, as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates:

(A3) formula (A3) in which:

-R ^a , R ^b , R ^d , R ^e and R ^f , which are identical or different, represent (1) a hydroxy group, (2) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted in particular by a or several hydroxy groups, (3) a carboxy group, or (4) a NR1R2 group with R1 and R2 identical or different, representing i) a hydrogen atom, ii) an optionally substituted (Ci-C6) alkyl group, of preferably by one or more hydroxy or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl (Ci-C4) alkyl group such as benzyl, v) a (hetero) cyclo (C5-C7) alkyl group such as cyclohexyl, morpholinyl, pyperazinyl, or piperidinyl, vi) a (hetero) cyclo (C5-C7) alkyl (Ci-C4) alkyl group such as cyclohexylmethyl, vii) -C (Y) - (Y ') _P -R' 1 with Y and Y ', identical or different, representing an oxygen, sulfur or N (R' ₂ ) atom, preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined above, and in particular R'i denoting a (CiC6) alkyl group such as methyl;

it being understood that at least one of the radicals R ^a , R ^b , R ^d , R ^e and R ^f represents a group NR1R2 and preferably at least one of the radicals R ^a , R ^b , R ^d , R ^e and R ^f , represents an NR1R2 group and the radicals other than NR1R2 denote a hydroxy group.

Preferably, Ri and R2 are chosen from the hydrogen atom and -C (O) -R’i in which R’i is as defined above; and more preferably Ri and R2 represent i) a hydrogen atom or ii) -C (O) -R’i, with R’i representing a (Ci-C4) alkyl group such as methyl.

Preferably, R ^b represents a NR1R2 group such as NH2 or N (H) -C (O) -R'1 with R'i representing a (Ci-C4) alkyl group such as methyl, and more preferably NH2, and R ^a , R ^d , R ^e and R ^f , represent a hydroxy group.

Preferably, the monosaccharide (s) a) are chosen from the hexosamines of formula (A3) of configuration D or also called D-glucopyranes, and more preferably from the hexosamines of formula (A3) of anomeric configuration β (beta).

Better still, the monosaccharide (s) a) is (are) chosen (s) from the hexosamines of formula (A3 ′) as well as their organic or mineral acid salts, preferably mineral acid such as hydrochloric acid, their anomers a or β, their optical isomers of configuration L or D, preferably D, and their solvates such as

hydrates, and mixtures thereof: R ^f t -0 \ - χαΑΛ / \ / i (A3 ') formula (A3 ') in which R ^a , R ^b , R ^d , R ^e and R ^f are as defined

previously for (A3).

The monosaccharide (s) a) are advantageously chosen from hexosamines, preferably from aldohexosamines, ketohexosamines and their mixtures, more preferably from glucosamine, galactosamine, allosamine, altrosamine, mannosamine, gulosamine, idosamine , lagalactosamine, talosamine, and mixtures thereof.

Preferably the monosaccharide (s) a) are chosen from glucosamine and galactosamine, as well as their organic or mineral acid salts such as hydrochloric acid, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, and mixtures thereof, more preferably the monosaccharide a) is glucosamine, better still glucosamine of configuration D, and even better glucosamine salified with a mineral acid such as hydrochloric acid.

Polysaccharides

The dyeing method according to the present invention further comprises a step consisting in applying to the keratin fibers b) one or more polysaccharide (s) with amine group (s) as well as their organic or mineral acid salts, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, also called ingredients b).

Preferably, the polysaccharide (s) with amine group (s) b) has (have) an average molecular weight (PM) less than or equal to 400 KDa, and more preferably less than 200 KDa.

Advantageously, the polysaccharide (s) with amine group (s) b) have a low average molecular weight PM, that is to say that they have a molecular weight less than 100 KDa, preferably less than 40 KDa , more preferably, they have an average PM of between 1 KDa and 30 KDa, and better still between 3 KDa and 28 KDa.

The polysaccharide (s) with amine group (s) b) is (are) preferably of natural animal, plant origin, or else derived from synthesis, hemisynthesis or biosynthesis.

According to a particular embodiment of the invention, the polysaccharide (s) with amine group (s) b) is (are) chosen from polysaccharide with C5-C7 osidic units with group ( s) amine (s) as well as their organic or mineral acid salts, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, and their mixtures.

More particularly, the polysaccharide (s) with amine group (s) b) is (are) with an osidic unit in Ce with amine group (s), these polysaccharides with amine group (s) ) are then called polyhexosamines.

According to a particular embodiment, the osidic units of the polysaccharide with amine group (s) b) are of anomeric configuration β (beta) and / or of configuration D.

According to a particular embodiment, the osidic units of the polysaccharide with amine group (s) b) are linked together between the carbon atoms 1 of an osidic unit and of carbon 4 of the other osidic unit, denoted ( 1-> 4).

According to this embodiment, the polysaccharide (s) with amine group (s) are preferably chosen from polysaccharides with an osidic unit of formula (B) below, as well as their organic or mineral acid salts, their a or β anomers, their optical isomers of L or D configuration and their solvates such as

(B) formula (B) in which:

-n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300;

-R _a , Rb, and R _c , identical or different for each sugar unit, represent (1) a hydroxy group, (2) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted in particular by one or more hydroxy and / or carboxy groups, (3) a carboxy group, or (4) a NR1R2 group with R1 and R2 identical or different, representing i) a hydrogen atom, ii) an optionally substituted (Ci-C6) alkyl group , preferably by one or more hydroxy or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl (Ci-C4) alkyl group such as benzyl, v) an (hetero) cyclo (C5C?) alkyl group such cyclohexyl, morpholinyl, pyperazinyl, or piperidinyl, vi) a (hetero) cyclo (C5-C7) alkyl (Ci-C4) alkyl group such as cyclohexylmethyl, vii) -C (Y) - (Y ') _P -R' 1 with Y and Y ', identical or different, representing an oxygen, sulfur or N (R'i) atom, preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined above, and in particular R'i denoting a (Ci-C6) alkyl group such as methyl;

it being understood that at least one of the radicals R _a , Rb or R _c of at least one sugar unit represents a group NR1R2 and that at least one of the groups NR1R2 of at least one sugar unit represents a group NH ₂ .

Preferably, Ri and R2 are chosen from the hydrogen atom and -C (O) -R’i in which R’i is as defined above; and more preferably Ri and R2 represent i) a hydrogen atom or ii) -C (O) -R’i, with R’i representing a (Ci-C4) alkyl group such as methyl;

Preferably, R _a of at least one sugar unit represents a group NR1R2 with Ri which represents a hydrogen atom and R2 chosen from i) a hydrogen atom or ii) a group -C (O) -R'i , and Rb and R _c represent a hydroxy group, it being understood that at least one of the NR1R2 groups of at least one osidic unit represents an NH2 group.

More particularly, the polysaccharide (s) with amine group (s) b) is (are) chosen from polysaccharides with osidic units of formula (B1) below, as well as their organic acid salts or mineral, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates, and their mixtures:

formula (B1) in which:

- R 'represents a hydrogen atom or a (CiC4) alkylcarbonyl group such as acetyl CH3-C (O) -;

- R ”represents a hydrogen atom or a (Ci-C4) alkyl group optionally substituted by a carboxy group such as -CH (CO2H) CH ₃ ;

- N is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300;

it being understood that at least one sugar unit carries an amino NH2 group and at least one other sugar unit carries at least one N (H) -R 'group with R' representing a (Ci-C4) alkylcarbonyl group such as acetyl CH3- CO)-.

Preferably, the sugar units of formula (B) or (B1) are of configuration D or also called D-glucopyran.

In particular, the osidic units of formula (B) or (B1) are of anomeric configuration β (beta).

According to a particular embodiment, the polysaccharide (s) b) is (are) chosen (s) from polysaccharides with an osidic unit of formula (B2) as well as their acid, organic or mineral salts, and their solvates such as hydrates, and their mixtures:

(B2) formula (B2) in which:

- R _a , Rb, and R _c , are as defined for (B) above; and, the radicals R _a , Rb, Rc of each osidic unit can be identical or different; and

- N is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300;

it being understood that at least one of the radicals R _a , Rb or R _c of at least one sugar unit represents a group NR1R2, with Ri and R ₂ as defined above for (B), and that at least one of the groups NRiR ₂ of at least one sugar unit represents an NH ₂ group; preferably at least one sugar unit carries a group R _a representing an amino group NH ₂ and at least one other sugar unit carries a group R _a representing a group -N (H) -R 'with R' representing a group (Ci- C4) alkylcarbonyl such as acetyl CH3C (O) -.

Preferably, the polysaccharide (s) with amine group (s) b) is (are) chosen from chitin, chitosan and their derivatives, and more preferably chitosan.

More particularly, the polysaccharide (s) with amine group (s) b) is (are) chosen from polysaccharides with an osidic unit of formula (B3) as well as their organic or mineral acid salts, and their solvates such as hydrates, and their mixtures:

formula (B3) in which,

- Ri and R2 are as defined above in formulas (B), 5 and (B2); and

- N is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300;

it being understood that at least one sugar unit carries an amino group NH2 and that at least one other sugar unit carries an N (H) -R 'group with R' representing a (Ci-C4) alkylcarbonyl group such as acetyl CH ₃ -C (O) -.

More particularly, the polysaccharide (s) with amine group (s) b) is (are) chosen from the chitosans of formula (B4) below as well as their organic or mineral acid salts and their solvates such as hydrates, and mixtures thereof:

(B4) formula (B4) in which:

-R’i representing a (Ci-C4) alkyl group such as methyl; and

-n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300;

-p is greater than 0 and goes up to 0.5, preferably from 0.05 to 0.3, and better still from 0.1 to 0.20 such that 0.15 with m + p being equal to 1;

it being understood that in chitosan at least one osidic unit carries an amino group NH2 and at least one other osidic unit carries an N (H) -R'i group with R'i representing a (CiC4) alkylcarbonyl group such as acetyl CH3- CO)-.

For example, when m = 0.7 and p = 0.3, this means that 70% of the amino groups are free (unsubstituted) and 30% of the amino groups are N-alkyl (C1-C4) carbonylated, in particular N -acetylated, corresponding to the chitosan polymer of formula:

with n as defined above.

Preferably, the polysaccharide (s) with amine group (s) b) is (are) salified, or in salified form, using one or more organic acid (s) or mineral (s), and preferably using one or more organic acid (s).

The organic or mineral acid (s) which can be used correspond to the mineral and organic acids described above in the “organic or mineral acid salt” section.

Preferably, the polysaccharide (s) with amine group (s) b) is (are) salified (s) with the aid of one or more organic acid (s) chosen (s) among the monocarboxylic acids of formula (I):

RC (O) -OH (I) formula (I) in which, R represents a (hetero) aryl radical such as phenyl, a (hetero) aryl (Ci-C4) alkyl radical such as benzyl, a (Ci-C3o) radical ) alkyl or an unsaturated C2-C30 radical (ie comprising at least one ethylenic unsaturation, preferably an ethylenic unsaturation); said unsaturated alkyl or C2-C30 radicals being optionally interrupted and / or optionally substituted preferably by one or more hydroxy groups and unsubstituted by one or more amino radicals; R preferably denoting a (Ci-C6) alkyl group optionally interrupted and / or optionally substituted by 1, 2 or 3 hydroxy groups, preferably R represents a (Ci-C4) alkyl group, such as methyl or ethyl;

- polycarboxylic acids of formula (II):

OH

L HO ° (H) represents an aromatic atom or several heteroatoms such as a polyvalent carbon group, saturated or non-aromatic, formula (II) in which, hydrocarbon comprising unsaturated, cyclic or non-cyclic, optionally interrupted by oxygen and / or optionally substituted in particular by one or more hydroxy groups and t represents an integer inclusive between 1 and 5; preferably A represents a divalent (Ci-C6) alkylene group optionally substituted in particular by one or more hydroxy groups and unsubstituted by at least t amino radicals, and t is 1, 2 or 3; and

- amino acids containing more carboxylic acid radicals than amino groups.

Preferably, the monocarboxylic organic acids of formula (I) are chosen from acetic acid, glycolic acid, lactic acid and their mixtures, and more preferably from acetic acid, lactic acid and their mixtures.

Preferably, the polycarboxylic acids of formula (II) are chosen from tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid and their mixtures.

Preferably, the amino acids comprising more carboxylic acid radicals than amino groups are chosen from gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and their mixtures, and more preferably gammacarboxyglutamic acid

More preferably, the organic acid (s) which can be used is (are) chosen from acetic acid, glycolic acid, lactic acid tartaric acid, succinic acid , fumaric acid, maleic acid, citric acid, gammacarboxyglutamic acid, aspartic acid, glutamic acid and mixtures thereof, and preferably the organic acid is lactic acid.

Particularly, the polysaccharide (s) with amine group (s) b), is (are) chosen (s) from chitosans, salified using organic acid, preferably using monocarboxylic acid of formula (I) as defined above or polycarboxylic acid of formula (II) as defined above, even more preferably salified with the aid of carboxylic acid of formula (I) such as lactic acid.

According to a particular form of the invention, the polysaccharide (s) with amine group (s) b) denote a mixture of polysaccharide (s) with amine group (s), one of which is a chitosan or its organic or mineral acid salts, preferably its organic acid salts such as lactic acid, its a or β anomers, its optical isomers of L or D configuration and its solvates such as hydrates.

According to another particular form of the invention, the polysaccharide (s) with amine group (s) b) denote a single polysaccharide with amine group (s), in particular a mixture of chitosan or their organic or mineral acid salts or more particularly their organic acid salts such as their lactic acid salt, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates.

According to yet another particular form of the invention, the polysaccharide (s) with amine group (s) b) denote a single polysaccharide with amine group (s), in particular a chitosan or its salts of organic or mineral acid or more particularly its organic acid salts such as its lactic acid salt, its a or β anomers, its optical isomers of L or D configuration and its solvates such as hydrates.

Coloring matters

The dyeing method according to the present invention further comprises a step consisting in applying to the keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof, also called ingredients c).

Preferably, the coloring material (s) are chosen from pigments.

By “pigment” is meant a solid, white or colored particle, naturally insoluble in the hydrophilic and lipophilic liquid phases usually used in cosmetics or rendered insoluble by formulation in the form of a lacquer, if necessary. More particularly, the pigment is little or not soluble in hydroalcoholic media.

As pigment, mention may be made of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a20 371 and ibid, Pigments , Inorganic, 1. General ”2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 143 56007.a20_243.pub3.

Mention may in particular be made of azo pigments which contain one or more azo groups AN = NB with A representing an optionally substituted (hetero) aryl, B representing optionally substituted (hetero) aryl or -CH [C (O) -R] -C ( O) -Xi-A ', A' representing an optionally substituted (hetero) aryl and R representing a hydrogen atom or a (Ci-C6) alkyl group, with the groups A, A 'and B (hetero) aryls which do not contain a solubilizing group such as -SO3H, -COOH.

They can be particularly monoazoic including βNaphthols, monoazopyrrolone pigments, Benzimidazolone pigments; diazo pigments such as diazodiarylide pigments and Bis (N-acetoacetarylide), triazo or tetraazo pigments.

Mention may also be made of Azo Pigments with Metal Complexes “azo metal complex pigment”.

Other pigments are also interesting, these are the pigments Isoindolinones and Isoindolines, the pigments Phthalocyanine; Quinacridone pigments; Perinones pigments; Perylene pigments; Anthraquinones pigments such as Hydroxyanthraquinones Pigments; Aminoanthraquinone pigments including Acylaminoanthraquinones and Azoic Anthraquinone pigments; Heterocyclic Anthraquinones; Anthraquinones polycarbocyclic pigments, Pyranthrones Pigments; Anthanthrones pigments; Diketopyrrolopyrroles (DPP) pigments; Thioindigo pigments; Dioxazines pigments; Triphenylmethanes pigments; Quinophthalone pigments; and Fluorescent pigments.

When the dyes comprise one or more solubilizing groups such as -SO3H, -COOH, these dyes are made insoluble and therefore pigments by formation of lacquer ie by salification (eg Na, Ca, St, Ba ...) and mainly divided in β-naphthol pigment and 2-hydroxy-3-naphthoic acid "(GOOD) pigment lakes".

In the context of the present invention, the pigment can be at least partially organic.

According to an embodiment of the invention, the pigment is an organic pigment.

According to another embodiment of the invention, the pigment is a mineral pigment.

The microcapsules according to the invention comprise at most 80% by weight of the pigment relative to the weight of the polymer matrix. In particular, they can comprise from 0.5 to 75% by weight, for example from 1 to 70% by weight, in particular from 20 to 65% by weight, or even from 30 to 60% by weight of the pigment relative to the weight of the polymer matrix.

Of course, the encapsulation rate depends on the modulation of the desired shade and can therefore vary significantly depending on the effect that one wishes to obtain.

By way of illustration of the pigments which can be used in the present invention, mention may be made of carbon black, titanium oxide, chromium oxide, pigments of the D&C, FD&C type and their lacquers, and in particular those known under the names D&C Blue n ° 4, D&C Brown n ° l, FD&C Green n ° 3, D&C Green n ° 5, D&C Green n ° 6, FD&C Green n ° 8, 20 D&C Orange n ° 4, D&C Orange n ° 5, D&C Orange n ° 10, D&C Orange n ° ll, FD&C Red n ° 4, D&C Red n ° 6, D&C Red n ° 7 (CI 15850), D&C Red n ° 17, D&C Red n ° 21, D&C Red n ° 22, D&C Red n ° 27, D&C Red n ° 28, D&C Red n ° 30, D&C Red n ° 31, D&C Red n ° 33, D&C Red n ° 34, D&C Red n ° 36, FD&C Red n ° 40, FD&C Red 40 lake, D&C Violet n ° 2, Ext. D&C Violet n ° 2, FD & C Blue n ° 1, D&C Yellow n ° 6, FD&C Yellow n ° 6, D&C Yellow n ° 7, 25 Ext. D&C Yellow n ° 7, D&C Yellow n ° 8, D&C Yellow n ° 10 or D&C Yellow n ° ll, it being understood that when said pigment is not naturally insoluble in the hydrophilic and lipophilic phases usually used in cosmetics, it is used in the form of a corresponding lacquer as explained above.

As an example of lacquers, mention may in particular be made of lacquers based on barium, strontium, calcium, aluminum, or else diketo pyrrolopyrrole.

As another example of pigments which can be used in the present invention, mention may in particular be made of mineral pigments, optionally surface-treated and / or 14 coated, and in particular titanium dioxide, zirconium or cerium oxides, as well as zinc oxides , iron (black, yellow or red) or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or even metallic powders such as aluminum powder, copper powder, gold powder and silver powder.

Mention may also be made of pigments with an optical effect such as particles comprising an organic or mineral, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being covered or not with metallic substances like aluminum, gold, silver, platinum, copper, bronze, or metallic oxides like titanium dioxide, iron oxide, or chromium oxide.

It can also be pearlescent.

By "nacres" is meant iridescent pigments, in particular produced by certain molluscs in their shell or else synthesized.

The pearlescent pigments can be chosen from mica coated with titanium or bismuth oxychloride, mica titanium coated with iron oxides, mica titanium coated with in particular ferric blue or chromium oxide, mica titanium coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use interference pigments, in particular liquid crystal or multilayer pigments.

It can also be pigments having a structure which can, for example, be of the sericite / brown iron oxide / titanium dioxide / silica type.

It can also be pigments having a structure which can, for example, be of the silica microsphere type containing iron oxide.

By way of examples of pigments which are very particularly suitable for implementing the present invention, mention may in particular be made of D&C Red n ° 7, titanium oxide, chromium oxide, lacquers of pigments of the D&C type. and FD&C cited above, and in particular D&C Red n ° 22 lake, Yellow n ° 6 lake, FD&C Blue n ° l lake.

The pigments according to the invention can be in the form of powder or pigment paste. They can be coated or uncoated.

The pigments in accordance with the invention can, for example, be chosen from white or colored pigments, lacquers, pigments with special effects such as nacres or glitter, and mixtures thereof.

As examples of white or colored mineral pigments, there may be mentioned zirconium or cerium oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.

Examples of white or colored organic pigments that may be mentioned include the nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon blacks such as Black 2, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, pigments blue coded in the Color Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21 108, 47000 , 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, 71105, the red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole derivatives, phenolics ues as they are described in patent FR 2,679,771.

Preferably, carbon blacks such as Black 2 or lacquers such as D&C Red 7.

Pigment pastes of organic pigment can be used such as the products sold by the company HOECHST under the name: -JAUNE COSMENYL IOG: Pigment YELLOW 3 (Cl 11710); - YELLOW COSMENYL G: Pigment YELLOW 1 (Cl 1 1680); -ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105); -ROUGE COSMENYL R: Pigment RED 4 (Cl 12085); -CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490); -VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319); -BLUE COSMENYL A2R: Pigment BLUE 15.1 (Cl 74160); - GREEN COSMENYL GG: GREEN 7 Pigment (Cl 74260); -NOIR COSMENYL R: Pigment BLACK 7 (Cl 77266).

The pigments according to the invention can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising:

- an inorganic nucleus,

- at least one binder ensuring the fixation of organic pigments on the core, and

- at least one organic pigment covering the core at least partially.

By "lacquer" is meant the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, mention may be made of cochineal carmine.

Examples of lacquers that may be mentioned include the products known under the following names: D & C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850: 1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

By "special effect pigments" is meant the pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is non-uniform and changeable according to the conditions of observation (light , temperature, observation angles ...). They are therefore opposed to white or colored pigments which provide a uniform opaque, semi-transparent or transparent classic shade.

As examples of pigments with special effects, mention may be made of white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearly pigments such as mica coated with titanium and iron oxides , mica coated with titanium and in particular with ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above as well as pearlescent pigments based on bismuth oxychloride.

Mention may also be made of pigments with an interference effect that are not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances which fluoresce in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by Quantum Dots Corporation.

Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation having a wavelength between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can be manufactured according to the methods described for example in US 6,225,198 or US 5,990,479, in the publications cited therein, as well as in the following publications: Dabboussi BO et al (CdSe) ZnS core- shell quantum dots synthesis and characterization of a size series of highly luminescent nanocristallites Journal of physical chemistry B, vol 101, 1997, pp 9463-9475. and Peng, Xiaogang et al, Epitaxial Growth of highly Luminescent CdSe / CdS core / shell nanocrystals with photostability and electronic accessibility Journal of the American Chemical Society, vol 119, N ° 30, pp 7019-7029.

The pigments according to the invention are preferably colored pigments.

The variety of pigments involved makes it possible to obtain a rich palette of colors, as well as specific optical effects such as metallic, interference effects.

The size of a pigment other than the nacres in solution is generally between 10 nm and 10 μm, preferably between 50 nm and 5 μm, and even more preferably between 100 nm and 3 μm. The size of a mother-of-pearl in solution is generally between 1 and 200 μm, preferably between 1 and 80 μm, and even more preferably between 1 and 50 μm.

Among the mineral pigments, there may be mentioned, for example, titanium dioxide (rutile or anastase) optionally surface-treated and codified in the Color Index under the reference CI77891; black, yellow red and brown iron oxides, coded under the references CI77499, 77492, 77491; manganese violet (CI77742); ultramarine blue (CI77007); hydrated chromium oxide (CI77289); ferric blue (CI77510).

Among the organic pigments, there may be mentioned, by way of example, the pigment YELLOW 3 sold in particular under the trade name JAUNE COVANOR W 1603 by the company WACKHERR (CI 17710), D & C RED No. 19 (CI 45170), D & C RED n ° 9 (CI 15585), D & C RED n ° 21 (CI 45380), D & C ORANGE n ° 4 (CI 15510), D & C ORANGE n ° 5 (CI 45370 ), D & C RED n ° 27 (CI45410), D & C RED n ° 13 (CI 15630), D & C RED n ° 7 (CI 15850-1), D & C RED n ° 6 (CI 15850-2), the D & C

YELLOW n ° 5 (CI 19140), D & C RED n ° 36 (CI 12085), D & C ORANGE n ° 10 (CI 45425), D & C YELLOW n ° 6 (CI 15985), D & C RED n ° 30 (CI 73360), D & C RED n ° 3 (CI 45430), carbon black (CI 77266), and lacquers based on cochineal carmine (CI 75470).

It is also possible to use pearlescent pigments which can in particular be chosen from white pearlescent pigments such as mica coated with titanium oxide, bismuth oxide; colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the precipitated type, as well as those based on oxychloride of bismuth.

Use is more particularly of organic pigment pigment pastes such as the products sold by the company HOECHST under the name:

- YELLOW COSMENYL 1OG: Pigment YELLOW 3 (CI 11710)

- YELLOW COSMENYL G: Pigment YELLOW 1 (CI 11680)

- ORANGE COSMENYL GR: Pigment ORANGE 43 (CI 71105)

- ROUGE COSMENYL R °: Pigment RED 4 (CI 12085)

- CARMIN COSMENYL FB: Pigment RED 5 (CI 12490)

- VIOLET COSMENYL RL: Pigment VIOLET 23 (CI 51319)

- BLUE COSMENYL A2R: Pigment BLUE 15.1 (CI 74260)

- GREEN COSMENYL GG: Pigment GREEN 7 (CI 74260)

- BLACK COSMENYL R: Pigment BLACK 7 (CI 77266)

The dye (s) is (are) advantageously chosen from pigments, preferably from white organic pigments, colored organic pigments, and mixtures thereof, and more preferably carbon blacks, such than Black 2, lacquers, such as D&C Red 7, and their mixtures.

Preferably, the coloring material (s) are chosen from direct dyes.

By "direct dye" is meant natural and / or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber.

They can be ionic or nonionic, preferably cationic or nonionic, either as the only dyes.

These direct dyes are, for example, chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, quinonic dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct azine dyes , triarylmethane direct dyes, azomethin direct dyes and natural direct dyes.

As examples of suitable direct dyes, mention may be made of azo direct dyes; (poly) methine dyes such as cyanines, hemicyanins, and styryl dyes; carbonyls; azinics; nitro (hetero) aryl; tri (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

Preferably, the direct dye (s) contain at least one quaternized cationic chromophore or at least one chromophore carrying a quaternized or quaternizable cationic group.

According to a particular embodiment of the invention, the direct dyes comprise at least one quaternized cationic chromophore.

As direct dye according to the invention, there may be mentioned acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly) azo, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyranes; benzothiazoles; benzoquinones; bisazines; bis isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahémicyanines, hemicyanines, or tétraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines;

diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones;

indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones;

(poly) methines such as dimethines of stilbene or styryl types; naphthalimides; naphthhanilides; naphtholactams; naphthoquinones; nitro, especially aromatic nitro (hetero); oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine;

polyenes / carotenoids; porphyrins; pyranthrones;

pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones;

squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

For cationic azo dyes, mention may especially be made of cationic dyes described in the Kirk Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19/04/2010.

Among the azo dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

According to a preferred embodiment of the invention, the direct dye (s) are chosen from cationic dyes called "basic dyes".

Mention may be made, among the azo dyes described in the Color Index International 3rd edition, and in particular the following compounds:

- Basic Red 22

- Basic Red 76

- Basic Yellow 57

- Basic Brown 16

- Basic Brown 17.

Among the cationic quinone dyes those mentioned in the abovementioned Color Index International are suitable, and among these, the following dyes may be mentioned, among others:

- Basic Blue 22

- Basic Blue 99.

Among the azine dyes which are suitable, mention may be made of those listed in the International Color Index and for example the following dyes:

- Basic Blue 17

- Basic Red 2.

Among the cationic triarylmethane dyes which can be used according to the invention, there may be mentioned, in addition to those listed in the Color Index, the following dyes:

- Basic Green 1

- Basic Violet 3

- Basic Violet 14

- Basic Blue 7

- Basic Blue 26.

Mention may also be made of cationic dyes in documents US 5888252, EP 1 133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954. We can also cite those listed in the encyclopedia The chemistry of synthetic dye by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia Kirk Othmer Chemical technology, chapter dyes and Dye intermediate, 1993, Wiley and sons, and in various chapter of the encyclopedia ULLMANN's ENCYCLOPEDIA chemistry 7th edition, Wiley and sons.

Preferably, the cationic direct dyes are chosen from those derived from dyes of the azo type, and hydrazono.

According to a particular embodiment, the direct dyes are cationic azo, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122,

DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772,

WO 515144, GB 1 195386, US 3524842, US 5879413, EP 1062940,

EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645,

Acta Histochem. (1978), 61 (1), 48-52; Tsitologiya (1968), 10 (3), 403; Zh. Obshch. Khim. (1970), 40 (1), 195-202; Ann. Chim. (Rome) (1975), 65 (5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45 (1), 209-211; Rev. Roum. Chim. (1988), 33 (4), 377-83; Text. Res. J. (1984), 54 (2), 105-7; Chim. Ind. (Milan) (1974), 56 (9), 600-3; Khim. Tekhnol. (1979), 22 (5), 548-53; Ger. Monatsh. Chem. (1975), 106 (3), 643-8; MRL Bull. Res. Dev. (1992), 6 (2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29 (4), 233-4; Dyes Pigm. (1992), 19 (1), 69-79; Dyes Pigm. (1989), 11 (3), 163-72.

Preferably, the cationic direct dye (s) co-take a quaternary ammonium group, more preferably the cationic charge is endocyclic.

These cationic radicals are for example a cationic radical:

- with exocyclic charge (di / tri) (Ci-C8) alkylammonium, or

- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolidiumidolidolidolidolidolidinidolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidinolidium naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

Mention may be made of the hydrazono cationic dyes of formula (III) and (IV), the azo compounds of formulas (V), and (VI) below:

Hét ⁺ -C (R _a ) = NN (Rb) -Ar, Q '(ΙΠ)

Het ⁺ -N (R _a ) -N = C (Rb) -Ar, Q '(IV)

Hét ⁺ -N = N-Ar, Q '

Ar ⁺ -N = N-Ar ”, Q '(V) (VI) formulas (III) to (VI) in which:

• Hét ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally preferentially substituted by at least one (Ci-Cs) alkyl group such as methyl;

• Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferably ammonium, particularly tri (Ci-C8) alkyl-ammonium such as trimethylammonium;

• Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron donor groups such as i) (Ci-Csjalkyl optionally substituted, ii) (Ci-Csjalcoxy optionally substituted, iii) (di) (Ci-C8) (alkyl) amino optionally substituted on the alkyl group or groups by a hydroxyl group, iv) aryl (Ci-C8) alkylamino, v) N- (Ci-C8) alkyl-N-aryl (Ci-C8) alkylamino optionally substituted or then Ar represents a julolidine group;

• Ar ”represents a group (hetero) aryl optionally substituted such as phenyl or pyrazolyl optionally substituted, preferably by one or more groups (Ci-Csjalkyle, hydroxyle, (di) (Ci-C8) (alkyl) amino, (Ci-Csjalcoxy or phenyl;

• R _a and Rb, identical or different, representing a hydrogen atom or a group (Ci-Csjalkyle optionally substituted, preferably by a hydroxyl group;

• or the substituent R _a with a substituent of Het ⁺ and / or Rb with a substituent of Ar form together with the atoms which carry them a (hetero) cycloalkyl; particularly R _a and Rb, representing a hydrogen atom or a (C 1 -C 4) alkyl group optionally substituted by a hydroxyl group;

• Q represents an organic or mineral anionic counterion such as a halide or an alkyl sulphate.

In particular, mention may be made of direct dyes with azo and hydrazono endocyclic cationic charges of formula (III) to (VI) as defined above. More particularly the cationic direct dyes of formula (III) to (VI) with endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably, the following direct dyes:

(V-l) formulas (III-1) and (V-l) in which:

- R ¹ represents a group (Ci-C4) alkyl such as methyl;

- R ² and R ³ , identical or different, represent a hydrogen atom or a (Ci-C4) alkyl group such as methyl; and

- R ⁴ represents a hydrogen atom or an electron donor group such as (Ci-Cs) optionally substituted alkyl, (CiCs) optionally substituted alkoxy, (di) (Ci-C8) (alkyl) amino optionally substituted on the group or groups alkyl with a hydroxyl group; particularly R ⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferably CH,

- Q is an anionic counter ion as defined above, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (HI-1) and (V-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives:

Basic Red 51 Basic Orange 31 Basic Yellow with Q ’an anionic counterion as defined above, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say that they contain at least one fluorescent chromophore as defined above.

As fluorescent dyes, mention may be made of the radicals derived from acridine dyes, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro {2 - [(2H-pyrrol-2ylidene-kN) methyl] - IH-pyrrolato-kN] bores (BODIPY®), dikétopyrrolo-pyrroles, fluorindines, (poly) methines (in particular cyanines and styryles / hemicyanines), naphthalimides, naphthhanilides, naphthylamine (like dansyles), oxadiazoles, perinones, , perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

Mention may also be made of the fluorescent dyes described in documents EP 1 133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia The chemistry of synthetic dye by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the Kirk Othmer Chemical technology encyclopedia, chapter dyes and Dye intermediate, 1993,

Wiley and sons, and in various chapters of ULLMANN's ENCYCLOPEDIA encyclopedia of Industrial chemistry 7th edition, Wiley and sons, in The Handbook - A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes / Invitrogen Oregon 2005 published on the Internet or in previous printed editions.

According to a preferred variant of the invention, the fluorescent dye (s) are cationic and comprise at least one quaternary ammonium radical such as those of formula (VII) below:

W ⁺ - [C (Rc) = C (R _d )] m'-Ar, Q '(VH) formula (VII) in which:

• W ⁺ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more alkyl groups (CiCs) optionally substituted in particular by one or more hydroxyl groups;

• Ar representing an aryl group such as phenyl or naphthyl, optionally preferably substituted by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-Cs) alkyl groups, preferably C1-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cs) alkoxy groups such as methoxy; v) one or more hydroxy (Ci-Cs) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (CiCsjalkylamino) groups, preferably with the C1-C4 alkyl part optionally substituted by one or more hydroxyl such as (di) hydroxyethylamino, vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, pyperidinyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl;

• m 'represents an integer inclusive between 1 and 4, particularly m is 1 or 2; more preferably 1;

• R _c , Ra, identical or different, represent a hydrogen atom or an optionally substituted (Ci-Cs) alkyl group, preferably C1-C4, or else R _c contiguous to W ⁺ and / or Ra contiguous to Ar form with the atoms which carry them a (hetero) cycloalkyl, particularly R _c is contiguous with W ⁺ and form a (hetero) cycloalkyl such as cyclohexyl;

• Q is an organic or mineral anionic counterion as defined above.

Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the poultices or extracts based on henna.

The essays

The present invention also relates to an aqueous composition (C), at acidic pH comprising:

a) one or more monosaccharide (s) as defined above,

b) one or more polysaccharide (s) with amine group (s), salified (s) or non-salified (s), as defined above,

c) one or more coloring matters, as defined above, and

d) optionally one or more mineral or organic acid (s), preferably different from the following acids: aspartic acid.

According to a particular embodiment of the invention, the ingredients a), b) and c) as defined above are applied sequentially and are preferably included in three separate compositions (ca), (cb) and (ce). In other words, the composition (ca) comprises a) one or more monosaccharide (s) as defined above, the composition (cb) comprises b) one or more polysaccharide (s) with amine group (s) , salified (s) or non-salified (s), as defined above and optionally c) one or more mineral (s) or organic acid (s), and the composition (cc) comprises one or more material (s) ) coloring (s) as defined above.

The mineral or organic acid (s) that can be used in the compositions (C) and (cb) of the invention correspond to the mineral and organic acids described above in the “salt of 'organic or mineral acid'.

The content of the monosaccharide (s) present in the compositions (C) and (ca) preferably ranges from 0.01 to 20% by weight, more preferably from 0.05 to 10% by weight, and better still from 0.1 to 5% by weight, relative to the total weight of the composition (s) comprising it.

The content of the polysaccharide (s) containing an amino group (s) present in the compositions (C) and (cb) preferably ranges from 0.01 to 20% by weight, more preferably from 0.05 to 10% by weight, and better still from 0.1 to 5% by weight, relative to the total weight of the composition comprising it (s).

The weight ratio between the amount of the monosaccharide (s) and the amount of the polysaccharide (s) with amino group (s) present in composition (C) of the invention ranges from preferably from 0.5 to 10.

The content of the coloring matter (s), chosen from pigments, direct dyes and mixtures thereof, present in compositions (C) and (cc), preferably ranges from 0, 05 to 30% by weight, and more preferably from 0.5 to 10% by weight, relative to the total weight of the composition (s) comprising it.

Composition (C) and composition (s) (ca), (cb) and / or (cc) are cosmetic compositions, ie they contain a physiologically acceptable medium, that is to say a medium compatible with keratin materials human beings such as skin (body, face, eye area, scalp), hair, eyelashes, eyebrows, body hair, nails, lips.

The cosmetically acceptable medium of the compositions (C), (ca), (cb) and / or (ce) is advantageously aqueous. It can for example consist of water or a mixture of water and at least one cosmetically acceptable organic solvent.

Mention may be made, as organic solvent, of lower C2-C4 alcohols, such as ethanol and isopropanol; polyols, and in particular those having from 2 to 6 carbon atoms such as glycerin, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether; and their mixtures.

Preferably, the cosmetic composition (s) (C), (ca), (cb) and / or (ce) each comprise from 50 to 99.8% by weight of water, relative to the weight of each composition.

The pHs of the compositions (C), (ca), (cb) and (ce) of the invention can be adjusted by an organic or mineral acid, or by an alkaline agent chosen from mineral, organic or hybrid alkaline agents or their mixtures.

The pHs can be adjusted with d) one or more organic or mineral acids as defined above in "organic or mineral acid salt".

Preferably, the composition (ca) which comprises a) one or more monosaccharides as defined above, and in particular glucose or xylose, is at an acidic pH, ie less than 7, and in particular less than or equal to 6. More particularly, the pH of the composition (ca) is between 2 and 6, preferably between 2.5 and 5.5, and more preferably between 3.5 and 5 such as 4.5.

Preferably, the monosaccharide (s) a), present in the composition (ca) are found in the presence of one or more mineral acid (s), and more particularly hydrochloric acid.

Preferably, the composition (cb) which comprises b) one or more polysaccharide (s) with amine group (s) as defined above, and in particular a polysaccharide with osidic units of formula ( B), (Bl), (B2), (B3) or (B4) as defined above as chitosan, is found at an acidic pH, ie less than 7, and in particular less than or equal to 6. More particularly, the pH of the composition (cb) is between 2 and 6, preferably between 2.5 and 5.5, and more preferably between 3.5 and 5 such as 4.5.

Preferably, the polysaccharide (s) with amine group (s)

b), present in composition (cb), are in the presence of one or more organic acid (s), preferably chosen from monocarboxylic acids of formula (I) or polycarboxylic acids of formula (II) such as defined above, and even more preferably among the carboxylic acids of formula (I) such as lactic acid.

According to a first particular embodiment of the invention, the composition (C) comprises:

a) one or more monosaccharides as defined above, preferably glucose or xylose, in the presence of one or more mineral acid (s), preferably hydrochloric acid, and

b) one or more polysaccharide (s) with amine group (s) as defined above, preferably a polysaccharide with osidic units of formula (B), (B1), (B2), (B3) or (B4) as defined above, more preferably chitosan, and better still chitosan of average molecular weight less than or equal to 400KDa, in the presence of one or more mineral acid (s), preferably lactic acid,

c) one or more coloring matter (s) as defined above, and

d) optionally one or more mineral or organic acid (s);

the pH of said composition (C) is acidic, ie less than 7, preferably less than or equal to 6, more preferably between 2 and 6, better still between 2.5 and 5.5, and even more preferably between 3, 5 and 5 such as 4.5.

According to a second particular embodiment of the invention, the composition (C) comprises:

a) one or more monosaccharides as defined above, preferably glucose or xylose, in the absence of organic or mineral acid (s), and

b) one or more polysaccharide (s) with amine group (s) as defined above, preferably a polysaccharide with osidic units of formula (B), (B1), (B2), (B3) or (B4) as defined above, more preferably chitosan, in the presence of one or more mineral acid (s), preferably lactic acid,

c) one or more coloring matter (s) as defined above, and

d) optionally one or more mineral or organic acid (s);

the pH of said composition (C) is acidic, ie less than 7, preferably less than or equal to 6, more preferably between 2 and 6, better still between 2.5 and 5.5, and even more preferably between 3, 5 and 5 such as 4.5.

According to a third particular embodiment of the invention, the composition (C) comprises:

a) one or more monosaccharides as defined above, preferably glucose or xylose, in the presence of one or more mineral acid (s), preferably hydrochloric acid, and

b) one or more polysaccharide (s) with amine group (s) as defined above, preferably a polysaccharide with osidic units of formula (B), (B1), (B2), (B3) or (B4) as defined above, more preferably chitosan, and better still chitosan with an average molecular weight less than or equal to 400 KDa, in the absence of organic or mineral acid (s) ( ux)

c) one or more coloring matter (s) as defined above, and

d) optionally one or more mineral or organic acid (s);

the pH of said composition (C) is acidic, ie less than 7, preferably less than or equal to 6, more preferably between 2 and 6, better still between 2.5 and 5.5, and even more preferably between 3, 5 and 5 such as 4.5.

According to a fourth particular embodiment of the invention, the composition (C) comprises:

a) one or more monosaccharides as defined above, preferably glucose or xylose, in the absence of mineral acid (s),

b) one or more polysaccharide (s) with amine group (s) as defined above, preferably a polysaccharide with osidic units of formula (B), (B1), (B2), (B3) or (B4) as defined above, more preferably chitosan, and better still chitosan with an average molecular weight less than or equal to 400 KDa, in the absence of organic or mineral acid (s) ( ux), and

c) one or more coloring matter (s) as defined above, and

d) one or more mineral or organic acid (s), said acid c) being preferably chosen from hydrochloric acid, the monocarboxylic organic acids of formula (I) as defined above, the polycarboxylic acids of formula (II) as defined above, and more preferably from hydrochloric acid, lactic acid, citric acid, fumaric acid, maleic acid and their mixtures;

the pH of said composition (C) is acidic, ie less than 7, preferably less than or equal to 6, more preferably between 2 and 6, better still between 2.5 and 5.5, and even more preferably between 3, 5 and 5 such as 4.5.

According to a fifth particular embodiment of the invention, the composition (C) comprises one or more monosaccharide (s) a) chosen from monosaccharides with an amine group as defined above.

The pHs of the compositions (C), (ca), (cb) and / or (ce) can be adjusted with one or more mineral alkaline agents which are preferably chosen from ammonia, alkali carbonates or bicarbonates such as carbonates of sodium or potassium and sodium or potassium bicarbonates, sodium or potassium hydroxides or mixtures thereof.

The pHs can also be adjusted with one or more organic alkaline agents which are organic amines i.e. they contain at least one substituted or unsubstituted amino group. The organic alkaline agent (s) are more preferably chosen from organic amines whose pKb at 25 ° C is less than 12, and preferably less than 10, even more advantageously less than 6. It should be noted that these are pKb corresponding to the highest basicity function.

The pHs can also be adjusted with one or more hybrid compounds. Mention may be made, as hybrid compounds, of the salts of the amines mentioned above with acids such as carbonic acid or hydrochloric acid.

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

^R \ z ^RZ

N-W-N

R ^y (HIV) formula (VIII) in which:

- W is a divalent C1-C6 alkylene radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as oxygen or NR ^U ;

- R ^x , R ^y , R ^z R 'and R ^u , identical or different, represent a hydrogen atom, a C 1 -C 6 alkyl radical, a C 1 -C 6 hydroxyalkyl radical, or a C 1 -C 6 aminoalkyl radical .

The polysaccharide (s) with amine group (s), present (s) in composition (C) of the invention, can (can) not be salified (s) or not salified (s)

According to a first variant of the invention, the composition (C) corresponds to the composition (C ’) at acidic pH and comprises:

a) one or more monosaccharide (s) as defined above,

b) one or more polysaccharide (s) with salified amine group (s) as defined above, preferably having an average molecular weight less than or equal to 400 KDa,

c) one or more coloring matter (s) as defined above, and

d) optionally one or more mineral or organic acid (s).

According to another variant of the invention, the composition (C) corresponds to the composition (C ”) at acid pH and comprises:

a) one or more monosaccharide (s) as defined above,

b) one or more polysaccharide (s) with non-salified amino group (s) as defined above, preferably having an average molecular weight less than or equal to 400 KDa,

c) one or more coloring matter (s) as defined above, and

d) optionally one or more mineral or organic acid (s).

The compositions (C) and / or (ce) can optionally also comprise one or more additional direct dyes different from the direct dyes mentioned above.

These direct dyes are for example chosen from those conventionally used in direct dyeing, and among which mention may be made of all the aromatic and / or non-aromatic dyes of common use such as neutral, nitrous, acid or cationic direct dyes, direct dyes azo neutral, acidic or cationic, natural direct dyes other than pigments and / or one or more direct dyes sparingly or not soluble in hydro-alcoholic solvents, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes direct azines, triarylmethanics, indoamines, methines, styriles, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes.

Among the natural direct dyes, mention may be made of lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the poultices or extracts based on henna.

The compositions (C), (ca), (cb) and / or (ce) may optionally further comprise one or more additives, different from the compounds of the invention and among which mention may be made of cationic, anionic and ionic, amphoteric or zwitterionic, cationic, anionic, non-ionic, amphoteric polymers or their mixtures different from the polysaccharides of the invention, anti-dandruff agents, antiseborrheic agents, anti-hair loss and / or hair regrowth agents, vitamins and provitamins including panthenol, sunscreens, sequestering agents, plasticizing agents, solubilizing agents, silicones, oils, mineral or organic thickening agents, in particular polymeric thickening agents, antioxidant agents, hydroxy acids, perfumes, preservatives, and ceramides.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the compositions according to the invention are not, or not substantially, altered by the addition or additions envisaged.

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

Process for coloring keratin fibers

The process for dyeing keratin fibers, in particular human keratin fibers such as the hair, according to the present invention comprises:

(i) a step of applying to said keratin fibers a) one or more monosaccharide (s), (ii) a step of applying to said keratin fibers b) one or more polysaccharide (s) with amino group (s) ( s), salified (s) or not salified (s); and (iii) a step consisting in applying to said keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof;

it being understood that steps (i), (ii) and (iii) can be carried out simultaneously or sequentially, before being followed by iv) a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C, preferably with an iron.

The dyeing process according to the present invention can optionally further comprise a step of drying the keratin fibers. When present, this keratin fiber drying step follows steps (i), (ii) and (iii) and precedes the heat treatment step (iv).

According to a first particular embodiment of the method of the invention, steps (i), (ii) and (iii) are carried out simultaneously, that is to say together. In other words, a) the monosaccharide (s) as defined above, b) the polysaccharide (s) with salified or non-salified amine group (s) ), as defined above, and c) the coloring material (s) chosen from pigments, direct dyes and mixtures thereof, as defined above, are applied together or the method of the invention comprises a first step of application to the keratin fibers of an aqueous composition (C) as defined above.

Preferably, the method of the invention comprises a first step consisting in applying to the keratin fibers the composition (C) as defined above, optionally followed by a step of drying said keratin fibers, followed by a step of heat treatment said keratin fibers at a temperature above 80 ° C, preferably between 100 ° C and 250 ° C, and preferably with an iron.

According to a first advantageous variant of the invention, the composition (C) is the composition (C ’) as defined above.

According to another advantageous variant of the invention, the composition (C) represents a composition (C ”) as defined above.

In other words, according to a first variant of this embodiment, the method of the invention comprises:

a step consisting in applying simultaneously to the keratin fibers a) the monosaccharide (s), as defined above, b) the polysaccharide (s) with amine group (s), such ( s) as defined previously, and c) the coloring material (s) chosen from pigments, direct dyes and mixtures thereof, as defined above, followed an exposure time between 1 and 60 minutes,

- optionally followed by a step of drying said keratin fibers,

- followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C, preferably between 100 ° C and 250 ° C.

According to a second variant of this embodiment, the method of the invention comprises:

a step consisting in applying to the keratin fibers a composition (C), (C ’) or (C”) as defined above, followed by an exposure time of between 1 and 60 minutes,

- optionally followed by a step of drying said keratin fibers,

- followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C, preferably between 100 ° C and 250 ° C.

According to a second embodiment of the invention, steps (i) and (ii) can be carried out simultaneously, before or after step (iii). In other words, according to a first variant of this embodiment, the method can include:

a step consisting in applying to said keratin fibers a) one or more monosaccharide (s), as defined above, and b) one or more polysaccharide (s) with amino group (s) , salified (s) or unsalted (s), as defined above,

- optionally followed by a step of drying the keratin fibers,

- followed by a step consisting in applying to said keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof, as defined previously,

- optionally followed by a step of drying the keratin fibers, followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C., preferably with an iron.

According to a second variant of this embodiment, the method can include:

a step consisting in applying to said keratin fibers the mixture of compositions (ca) and (cb), as defined above, followed by an exposure time of between 1 and 30 minutes,

- optionally followed by a step of drying the keratin fibers,

- followed by a step consisting in applying to said keratin fibers the composition (cc) as defined above, followed by an exposure time of between 1 and 30 minutes,

- optionally followed by a step of drying the keratin fibers, followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C., preferably with an iron.

According to a third variant of this embodiment, the method can comprise:

a step consisting in applying to said keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof, as defined above,

- optionally followed by a step of drying the keratin fibers,

- followed by a step consisting in applying to said keratin fibers a) one or more monosaccharide (s), as defined above, and b) one or more polysaccharide (s) with amino group (s) (s), salified (s) or non-salified (s), as defined above,

- optionally followed by a step of drying the keratin fibers, followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C., preferably with an iron.

According to a fourth variant of this embodiment, the method can include:

a step consisting in applying to said keratin fibers the composition (cc) as defined above, followed by an exposure time of between 1 and 30 minutes,

- optionally followed by a step of drying the keratin fibers,

- followed by a step consisting in applying to said keratin fibers the mixture of compositions (ca) and (cb), as defined above, followed by an exposure time of between 1 and 30 minutes,

- optionally followed by a step of drying the keratin fibers, followed by a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C., preferably with an iron.

According to a particular variant of the invention, the process of the invention does not use an oxidized polysaccharide, more generally the process of the invention does not use a compound comprising at least one aldehyde group.

According to a preferred embodiment of the invention, the composition (s) (cb), (C), (C '), or (C ”), as defined above does not contain ( nent) no oxidized polysaccharide and more generally the composition (s) (cb), (C), (C '), or (C ”) does not contain (nen) t any compound comprising at least one aldehyde group.

The method according to the invention can also comprise an additional step of drying the keratin fibers after the application a) of the monosaccharide (s) as defined above, b) of the polysaccharide (s) with amine group (s) as defined above and / or c) of the coloring material (s) as defined above or after application of the composition (s) (C), (C '), (C ”), (ca), (cb) and / or (cc) containing it and before the heat treatment step (iv) of the keratin fibers carried out at a temperature of at least 80 ° C.

Preferably, the method of the invention implements a step of drying keratin fibers, in particular human keratin fibers such as the hair, before step (iv) of heat treatment.

This drying step is carried out in particular by means of a hair dryer, a helmet or even with a towel, an absorbent, or by free air drying. This drying step is advantageously carried out at a temperature ranging from 20 to 70 ° C.

Step (iv) of heat treatment of keratin fibers of the process of the invention is preferably carried out at a temperature between 80 ° C and 250 ° C, it being understood that the temperature is that of the heating means, in particular the iron, not the temperature of the keratin fibers.

According to a preferred form of the invention, the heat treatment step (iv) is carried out on dry keratin fibers.

Preferably, step (iv) of heat treatment of keratin fibers is carried out at a temperature of at least 100 ° C, in particular at a temperature inclusive between 100 ° C and 250 ° C.

Advantageously, step (iv) of heat treatment of keratin fibers is carried out at a temperature ranging from 150 ° C to 220 ° C, preferably ranging from 160 ° C to 220 ° C, more preferably ranging from 160 ° C to 200 ° C, and better still ranging from 130 ° C to 190 ° C.

It is understood that the heat treatment temperatures correspond to the temperatures of the heating means, in particular iron when it is iron, and not the temperature of the keratin fibers.

This step (iv) of heat treatment is advantageously carried out using an iron.

By "iron" is meant, within the meaning of the present invention, a device for heating keratin fibers bringing said fibers into contact with the heating device.

Within the meaning of the present invention, iron is different from a heating comb.

The tip of the iron coming into contact with the keratin fibers generally has two surfaces. These two surfaces can be metallic or ceramic. In particular, these two surfaces can be smooth or notched or curved.

The heat treatment step can be carried out using a straightening iron, a curling iron, a crimping iron or a steam iron such as Steampod. Preferably, the heat treatment step is carried out using a straightening iron.

By “steam irons” is meant, within the meaning of the present invention, irons which comprise a device which emits water vapor and which apply this water vapor before, during or after straightening / straightening.

By way of example of irons which can be used in the process according to the invention, mention may be made of all types of flat iron, and in particular, without limitation, those described in US Patents 5,957,140 and US 5,046,516.

The application of iron can be carried out by successive separate touches of a few seconds, or by progressive displacement or sliding along the keratin fibers, in particular along human keratin fibers such as the hair.

Preferably, the application of iron in the process according to the invention is carried out in continuous movement from the root to the tip of the keratin fibers, in particular human keratin fibers, such as the hair, in one or more passages, in particular in one to twenty passages. The duration of each pass of the iron can range from 2 seconds to 1 minute for a length of the treated keratin fibers of 30 cm +/- 3 cm.

Step (iv) of heat treatment of keratin fibers is carried out for a period which can advantageously range from 100 milliseconds to 30 minutes, preferably from 1 second to 15 minutes, more preferably from 2 seconds to 10 minutes, better still from 3 seconds to 5 minutes, and even better from 4 seconds to 1 minute.

The bath ratio of the composition (s) applied before the heat treatment step of the process preferably varies from 0.1 to 10, and more preferably from 0.2 to 5. With respect to bath, for the purposes of the present invention, the ratio between the total weight of the composition applied and the total weight of keratin fibers to be treated is understood.

After the heat treatment step (iv) of the process, the keratin fibers can optionally be rinsed with water or washed with a shampoo. The keratin fibers are then optionally dried using a hair dryer or a helmet or left to dry in the open air.

According to a particular embodiment of the invention, the coloring process is carried out one or more times, spaced or not by one or more cosmetic treatments, preferably spaced by one or more shampoos, and this to treat the keratin fibers which will have regrown, will have undergone other treatments likely to cause changes in coloring or to obtain the desired intensity of coloring.

According to one embodiment of the invention, the method is implemented on keratin fibers, in particular human keratin fibers such as hair, in particular natural hair, in particular natural hair.

The kit

The invention also relates to a kit comprising:

- a device with several compartments comprising a first compartment containing a cosmetic composition (ca) comprising one or more monosaccharide (s) as defined above; a second compartment containing a cosmetic composition (cb) comprising one or more poly saccharide (s) with amine group (s) as defined above and optionally one or more organic or mineral acids as defined previously; and a third compartment containing a coloring composition (ce) comprising one or more coloring material (s) as defined above; and

- A device for heating keratin fibers to a temperature greater than or equal to 80 ° C, preferably between 100 and 250 ° C.

The contents of each compartment of the kit can be released either sequentially or simultaneously.

The packaging assembly for the compositions, that is to say the device with several compartments, is in known manner any packaging suitable for storing cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).

Such a kit makes it possible to implement the process for coloring keratin fibers according to the invention.

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

EXAMPLES

Example 1

1) Preparation of the compositions

The compositions (A) and dye (B) according to the present invention were prepared from the ingredients mentioned in the tables below, and the contents of which are expressed as a percentage by weight relative to the total weight of the composition comprising them.

ingredients Composition (A) chitosan 1 glucosamine hydrochloride 1 Lactic acid Qs pH 4 Water Qsp 100

ingredients Coloring composition (B) Black 2 (CI 77266) 20 Propylene glycol 10 polyvinylpyrrolidone 1.5 methylparaben 1 phenoxyethanol 0.8 Water Qsp 100

2) Protocol

The compositions (A) and dye (B) obtained below are applied according to the following methods 1 to 9:

Processes 1 and 2 (comparative)

At the time of use, the coloring composition (B) is diluted to 10% in water.

The solution thus obtained is applied to two strands of sensitized hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Methods 3 and 4 (invention)

At the time of use, the coloring composition (B) is diluted to 10% in the composition (A).

The mixture thus obtained is applied to two strands of sensitized hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Methods 5 and 6 (invention)

At the time of use, the coloring composition (B) is diluted to 10% in water.

The solution thus obtained is applied to two strands of sensitized hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet.

Composition (A) is then applied to the two locks of hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Methods 7, 8 and 9 (invention)

At the time of use, the coloring composition (B) is diluted to 10% in water.

The solution thus obtained is applied to two strands of sensitized hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet.

Composition (A) is then applied to the two locks of hair at the rate of 0.5 g of composition per gram of hair. After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passages of 7 seconds of a straightening iron at a temperature of 190 ° C.

The application of composition (A) followed by the exposure time, drying with a helmet and the 5 successive passes with a straightening iron were repeated three times.

At the end of each of the processes mentioned above, the locks of hair of processes 2, 4, 6 and 8 are washed with a shampoo according to the following protocol:

The locks are thoroughly rinsed with water at 37 ° C for 15 seconds. Then, they are washed with a DOP shampoo at the rate of 0.4 g of shampoo per gram of hair. The locks are then rinsed under water for 15 seconds before being wrung, combed and dried.

This protocol is repeated five times for the wick of method 9.

3) Qualitative results

The color of the locks and the color transfer to the fingers are assessed visually. The results are given in the table below.

Unwashed wick with shampoo Wick washed with shampoo Method 1 (comparison) Black coloring Transfer to fingers - Method 2 (comparison) - Total loss of color Method 3 (invention) Black coloring No transfer to -

fingers Method 4 (invention) - Black coloring No transfer to fingers Method 5 (invention) Black coloring No transfer to fingers - Method 6 (invention) - Black coloring No transfer to fingers Method 7 (invention) Black coloring No transfer to fingers - Method 8 (invention) - Black coloring No transfer to fingers Method 9 (invention) - Black coloring No transfer to fingers

The results obtained above show that the process of the invention confers a black coloration on the hair which is remanent to shampoos, and this up to five shampoos (process 9), unlike the comparative processes using no monosaccharide, nor any polysaccharide with amine group (s).

Furthermore, the coloration obtained by the process of the invention does not transfer to the user's fingers.

4) Quantitative results

The color of the locks is then evaluated by colorimetry in the CIE L * a * b * system using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10 °, specular component included).

In this system L * a * b *; L * represents the clarity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the value of L *, the darker, more powerful the coloration.

The lower the value of a * and the greener the color, the higher the value of a * the more the color is red.

The lower the value of b * and the more blue the color, the higher the value of b * the more yellow the color.

The rise in color corresponds to the variation in coloring between the locks of hair, before and after treatment or coloring is defined by (ΔΕ *) according to the following equation:

ΔΕ * = * -L ₀ *) ² + (a * - a0 *) ² + (b * - b0 *) ²

In this equation, L *, a * and b * represent the values measured on locks of hair after shampooing, namely the locks of hair of methods 2, 4, 6, 8 and 9 mentioned above, and LO *, aO * and bO * represent the values measured on the respective locks of hair not washed with shampoo, namely the locks of hair of methods 1, 3, 5 and 7 mentioned above.

In other words, the value of ΔΕ * for process 2 was calculated with L *, a * and b * representing the values obtained for process 2, and Lo *, ao * and bo * representing the values obtained for process 1.

The lower the value of ΔΕ *, the greater the resistance to shampooing of the colorings.

The colorimetric values obtained after coloring the locks with methods 1 to 9 are given in the table below.

L * at* b * ΔΕ * Method 1 (comparison) 15.49 0.29 1.41 - Method 2 (comparison) 52.17 2.46 19.43 40.92

Method 3 (invention) 22.41 0.19 2.87 - Method 4 (invention) 27.3 0.49 5.9 5.76 Method 5 (invention) 19.8 0.32 1.82 - Method 6 (invention) 26 0.26 4.55 6.77 Method 7 (invention) 22.68 0.33 2.65 - Method 8 (invention) 20.76 0.3 2.14 1.99 Method 9 (invention) 21.64 0.34 2.84 1.1

The results obtained above show that the coloring obtained by the process of the invention, using a monosaccharide, a polysaccharide with amine group (s) and a coloring matter, is resistant to shampoos, unlike coloring. obtained with the comparative process not using a monosaccharide or a polysaccharide containing an amine group (s).

The coloration obtained with the process of the invention is moreover persistent with at least five shampoos (process 9).

Example 2

1) Preparation of the compositions

The compositions (A '), (A ”) and coloring (B') according to the present invention were prepared from the ingredients mentioned in the tables below, and the contents of which are expressed as a percentage by weight relative to the weight total of the composition including them.

Composition (A ’) Composition (AT") chitosan 5 3 glucosamine hydrochloride 1.5 - Xylose - 1 Lactic acid Qs pH 3.5 Qs pH 3.5 Water Qsp 100 Qsp 100

Coloring composition (B ’) D&C Red 7 (CI 15850) 15 Butylene glycol 5 Ceteth-40 3 Polysorbate 60 1.5 phenoxyethanol 0.5 Water Qsp 100

2) Protocol

The compositions (A ’) and coloring (B’) obtained above are applied according to methods 11 and 13 below. The comparisons are carried out by replacing the composition (A ’) with water according to methods 10 and 12 below.

The compositions (A ”) and dye (B ') obtained above are applied according to methods 15 and 17 below and the comparisons are carried out by replacing the composition (A”) with water according to methods 14 and 16 below.

Method 10 (comparison)

The coloring composition (B ’) is applied to two strands of white natural hair at the rate of 1 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two strands of hair at the rate of 3 g of water per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passages of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 11 (invention)

The coloring composition (B ’) is applied to two strands of white natural hair at the rate of 1 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet. The composition (A ’) is then applied to the two strands of hair at the rate of 3 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passages of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 12 (comparison)

The coloring composition (B ’) is applied to two strands of white natural hair at the rate of 2 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two strands of hair at the rate of 10 g of water per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passages of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 13 (invention)

The coloring composition (B ’) is applied to two strands of white natural hair at the rate of 2 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet. The composition (A ’) is then applied to the two strands of hair at the rate of 10 g of composition per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet before each undergoing 5 successive passages of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 14 (comparison)

At the time of use, 20g of coloring composition (B ’) are diluted in 50g of water, adjusted to pH 3.5 with lactic acid.

The mixture thus obtained is applied to two locks of white natural hair at the rate of 5 g of mixture per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 15 (invention)

At the time of use, 20g of coloring composition (B ’) are diluted in 50g of composition (A”).

The mixture thus obtained is applied to two locks of white natural hair at the rate of 5 g of mixture per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 16 (comparison)

At the time of use, 10g of coloring composition (B ’) are diluted in 50g of water, adjusted to pH 3.5 with lactic acid.

The mixture thus obtained is applied to two locks of white natural hair at the rate of 3 g of mixture per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

Method 17 (invention)

At the time of use, 10g of coloring composition (B ’) are diluted in 50g of composition (A”).

The mixture thus obtained is applied to two locks of white natural hair at the rate of 3 g of mixture per gram of hair.

After an exposure time of 5 minutes at 33 ° C, the locks are dried with a helmet, before each undergoing 5 successive passes of 7 seconds of a straightening iron at a temperature of 190 ° C.

At the end of each of the processes mentioned above, a lock of hair from each process was washed with a shampoo according to the following protocol:

The locks are thoroughly rinsed with water at 37 ° C for 15 seconds. Then, they are washed with a DOP shampoo at the rate of 0.4 g of shampoo per gram of hair. The locks are then rinsed under water for 15 seconds before being wrung, combed and dried.

3) Qualitative results

The color of the locks and the transfer of color to a cotton fabric are assessed visually.

The fabric is pulled along the length of the wick using constant finger pressure and the final color of the fabric evaluated.

The results are given in the table below.

Unwashed wick with shampoo Wick washed with shampoo Method 10 (comparison) Red coloring Transfer to fabric - Method 10 (comparison) - Total loss of color Method 11 (invention) Light red color transfer to -

tissue Method 11 (invention) - Red coloring No transfer to tissue Method 12 (comparison) Red coloring Transfer to fabric - Method 12 (comparison) - Total loss of color Method 13 (invention) Light red coloring transfer to fabric - Method 13 (invention) - Red coloring No transfer to tissue Method 14 (comparison) Red coloring Transfer to fabric - Method 14 (comparison) - Total loss of color Method 15 (invention) Light red coloring transfer to fabric - Method 15 (invention) - Red coloring No transfer to tissue Method 16 (comparison) Red coloring Transfer to fabric - Method 16 (comparison) - Total loss of color Method 17 (invention) Light red coloring transfer to fabric - Method 17 (invention) - Red coloring No transfer to tissue

The results obtained above show that the process of the invention gives a red coloring to the hair which is remanent to shampoos, unlike the comparative processes using no monosaccharide, nor any polysaccharide with amine group (s).

Furthermore, the coloration obtained using the process of the invention does not transfer to the fabric.

4) Quantitative results

The colorimetric values obtained after coloring and shampooing the locks with methods 10 to 17 are given in the table below.

L * at* at* ΔΕ Method 10 (comparison) 50.17 13.8 10.87 28.19 Method 11 (invention) 40,41 29.95 11.96 12.89 Method 12 (comparison) 52.21 7.84 10.54 30.32 Method 13 (invention) 35.55 34.32 20,89 8.53 Method 14 (comparison) 49.87 16 11.37 26.88 Method 15 (invention) 39.36 34.93 16.58 13.35 Method 16 (comparison) 45.74 14,07 7.52 28.52 Method 17 (invention) 38.1 31.17 14.76 10.71

The results obtained above show that the coloration obtained using the process of the invention, using a monosaccharide, a polysaccharide with amine group (s) and a coloring material, is resistant to shampoos, unlike the coloration obtained with the comparative process not using a monosaccharide or a polysaccharide containing an amine group (s).

Claims (25)

1. Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising: (i) a step of applying to said keratin fibers a) one or more monosaccharide (s), (ii) a step of applying to said keratin fibers b) one or more polysaccharide (s) with amino group (s) ( s), salified (s) or not salified (s); and (iii) a step consisting in applying to said keratin fibers c) one or more coloring material (s) chosen from pigments, direct dyes and mixtures thereof; it being understood that steps (i), (ii) and (iii) can be carried out simultaneously or sequentially, before being followed by iv) a step of heat treatment of said keratin fibers at a temperature greater than or equal to 80 ° C, preferably with an iron. 2. Method according to claim 1, characterized in that the monosaccharide (s) a) is (are) chosen (s) from hexoses as well as their a or β anomers, their optical isomers of L or D configuration, their solvates such as hydrates and mixtures thereof; and preferably among the hexoses of formula (A1) as well as their a or β anomers, their optical isomers of L or D configuration, their solvates such as hydrates and their mixtures: formula (A1) in which: - R ^a , R ^b , R ^d , R ^e and R ^f , identical or different, represent i) a hydroxy group, ii) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted in particular by one or more hydroxy groups or iii) a carboxy group; preferably R ^a , R ^b , R ^d , R ^e and R ^f , represent a hydroxy group; and more preferably, (Al) represents (Al '): (Al ') formula (Al') in which R ^a , R ^b , R ^d , R ^e and R ^f are as defined above for (Al). 3. Method according to claim 1 or 2, characterized in that the monosaccharide (s) a) is (are) chosen (s) from aldohexoses, ketohexoses and their mixtures, preferably from glucose, galactose, allose , altrose, mannose, gulose, idose, galactose, talose and their mixtures, more preferably among glucose and galactose, as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates and mixtures thereof; better still the monosaccharide a) is glucose, and even better the glucose of configuration D. 4. Method according to claim 1, characterized in that the monosaccharide (s) a) is (are) chosen (s) from monosaccharides with amine group (s), as well as their organic acid salts or mineral, their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates; preferably among the monosaccharides containing amine group (s) salified with the aid of a mineral acid such as hydrochloric acid. 5. Method according to the preceding claim, characterized in that the monosaccharide (s) a) is (are) chosen (s) from the hexosamines of formula (A3) below as well as their organic or mineral acid salts such as hydrochloric acid, as well as their a or β anomers, their optical isomers of L or D configuration and their solvates such as hydrates: (A3) formula (A3) in which: -R ^a , R ^b , R ^d , R ^e and R ^f , which are identical or different, represent (1) a hydroxy group, (2) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted in particular by a or several hydroxy groups, (3) a carboxy group, or (4) a NR1R2 group with R1 and R2 identical or different, representing i) a hydrogen atom, ii) an optionally substituted (Ci-C6) alkyl group, of preferably by one or more hydroxy or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl (Ci-C4) alkyl group such as benzyl, v) a (hetero) cyclo (C5-C7) alkyl group such as cyclohexyl, morpholinyl, pyperazinyl, or piperidinyl, vi) a (hetero) cyclo (C5-C7) alkyl (Ci-C4) alkyl group such as cyclohexylmethyl, vii) -C (Y) - (Y ') _P -R'1 with Y and Y ', identical or different, representing an oxygen, sulfur or N (RU) atom, preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined above, and in particular R'i denoting a (CiC6) alkyl group such as methyl; it being understood that at least one of the radicals R ^a , R ^b , R ^d , R ^e and R ^f represents a group NR1R2 and preferably at least one of the radicals R ^a , R ^b , R ^d , R ^e and R ^f , represents a group NR1R2 and the radicals other than NR1R2 denote a hydroxy group, and more preferably (A3) represents (A3 ′): R ^f H (A3 ') formula (A3 ') in which R ^a , R ^b , R ^d , R ^e and R ^f are as defined previously for (A3). 6. Method according to claim 4 or 5 above, characterized in that the monosaccharide (s) a) is (are) chosen (s) from aldohexosamines, ketohexosamines and their mixtures, preferably from glucosamine, galactosamine, allosamine, altrosamine, mannosamine, gulosamine, idosamine, galactosamine, talosamine and their mixtures, more preferably among glucosamine, and galactosamine, as well as their organic or inorganic acid salts such as hydrochloric acid, their a or β anomers, their optical isomers of configuration L or D and their solvates such as hydrates and their mixtures, better still the monosaccharide a) is glucosamine, even better glucosamine of configuration D, and even more particularly glucosamine salified with a mineral acid such as hydrochloric acid. 7. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) is (are) with osidic units in Ce with amine group (s) ( s); preferably the osidic units of the polysaccharide with amine group (s) are of anomeric configuration β (beta) and / or of configuration D; and more preferably the osidic units of the polysaccharide with amine group (s) are linked together in (1—> 4). 8. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) is (are) chosen (s) from the polysaccharide (s) with units osidics of formula (B), as well as their organic or mineral acid salts, their a or β anomers, their optical isomers of L or D configuration, their solvates such as hydrates and their mixtures: (B) formula (B) in which: - N is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300; - R _a , Rb, and R _c , identical or different for each osidic unit, represent (1) a hydroxy group, (2) a (Ci-C4) alkoxy group in which the alkyl chain may be optionally substituted in particular by one or more hydroxy and / or carboxy groups, (3) a carboxy group, or (4) a group NR1R2 with R1 and R2, identical or different, representing i) a hydrogen atom, ii) an optionally (Ci-C6) alkyl group substituted, preferably by one or more hydroxy or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl (Ci-C4) alkyl group such as benzyl, v) an (hetero) cyclo (C5C?) alkyl group such as cyclohexyl, morpholinyl, piperazinyl, pyperidinyl, vi) a (hetero) cyclo (C5-C7) alkyl (Ci-C4) alkyl group such as cyclohexylmethyl, vii) a group -C (Y) - (Y ') _P - R'1 with Y and Y ', identical or different, representing an oxygen, sulfur or N (R' ₂ ) atom, p is equal to 0 or 1, and R'i and R'2 representing i) to vi) of Ri and R2 defined s previously, it being understood that at least one of the radicals R _a , Rb or R _c of at least one sugar unit represents a group NR1R2 and that at least one of the NR1R2 groups of at least one sugar unit represents a group NH ₂ . 9. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) is (are) chosen from polysaccharides with osidic units of formula (B1) ), as well as their organic or mineral acid salts, their a or β anomers, their optical isomers of L or D configuration, their solvates such as hydrates and their mixtures: formula (B1) in which: (i) R ′ represents a hydrogen atom or a (CiC4) alkylcarbonyl group such as acetylene CH3-C (O) -; (ii) R ”represents a hydrogen atom or a (Ci-C4) alkyl group optionally substituted by a carboxy group such as CH (CO ₂ H) -CH ₃ ; and (iii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300; it being understood that at least one sugar unit carries an amino group NH2 and at least one other sugar unit carries an N (H) -R 'group with R' representing a (Ci-C4) alkylcarbonyl group such as acetyy CH ₃ -C (O) -. 10. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) is (are) chosen from polysaccharides with osidic units of formula (B3), as well as their organic or mineral acid salts, their solvates such as hydrates, and their mixtures: (B3) formula (B3) wherein, (i) Ri and R2 are as defined in claim 8; and (ii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300; it being understood that at least one sugar unit carries an amino group NH2 and at least one other sugar unit carries an N (H) -R 'group with R' representing a (Ci-C4) alkylcarbonyl group such as acetyl CH ₃ -C (O) -. 11. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) is (are) chosen (s) from the chitosans of formula (B4) as well as their organic or mineral acid salts, their solvates such as hydrates, and their mixtures: (B4) formula (B4) in which: (i) R’i representing a (Ci-C4) alkyl group such as methyl; and (ii) p is greater than 0 and goes up to 0.5, preferably from 0.05 to 0.3, and more preferably from 0.1 to 0.20 such that 0.15 with m + p being equal to 1; (iii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferably between 5 and 2500, and better still between 10 and 2300; it being understood that at least one sugar unit carries an amino NH2 group and at least one other sugar unit carries an N (H) -R'i group with R'i representing a (Ci-C4) alkylcarbonyl group such as acetyl CH ₃ -CO)-. 12. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) is (are) salified (s) using one or more several organic acid (s), preferably chosen from: - the monocarboxylic acids of formula (I): RC (O) -OH (I) formula (I) in which R represents a (hetero) aryl radical such as phenyl, a (hetero) aryl (Ci-C4) alkyl radical such as benzyl, a (Ci-C3o) radical alkyl or an unsaturated C2-C30 radical, said unsaturated alkyl or C2-C30 radicals being optionally interrupted and / or optionally substituted preferably by one or more hydroxy groups and unsubstituted by one or more amino radicals; - polycarboxylic acids of formula (II): OH L HO Jt O (H) formula (II) in which A represents a polyvalent hydrocarbon group comprising from 1 to 30 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms such as oxygen and / or optionally substituted in particular by one or more hydroxy groups and t represents an integer inclusive between 1 and 5; and - amino acids containing more carboxylic acid radicals than amino groups. 13. Method according to the preceding claim, characterized in that the organic acid (s) are chosen from acetic acid, glycolic acid, lactic acid tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, gamma-carboxyglutamic acid, aspartic acid, glutamic acid and mixtures thereof, and preferably the organic acid is the acid lactic. 14. Method according to any one of the preceding claims, characterized in that the polysaccharide (s) with amine group (s) b) has (have) an average molecular weight PM less than or equal to 400 KDa, preferably less than 200 KDa, more preferably less than 100 KDa, better still less than 40 KDa, even better still between 1 KDa and 30 KDa, even more preferably between 3 KDa and 28 KDa. 15. Method according to any one of the preceding claims, characterized in that the coloring material (s) is (are) chosen from pigments, preferably from white organic pigments, organic pigments colored, and their mixtures, and more preferably carbon blacks such as Black 2, lacquers such as D&C Red 7, and their mixtures. 16. Method according to any one of the preceding claims, characterized in that steps (i), (ii) and (iii) are carried out simultaneously or by applying to the keratin fibers an aqueous composition (C) at acid pH comprising a ) one or more monosaccharide (s), b) one or more polysaccharide (s) with amine group (s), salified (s) or unsalified (c), one or more coloring matter (s) ( s) chosen from pigments, direct dyes and mixtures thereof, and optionally d) one or more organic or inorganic acid (s). 17. Method according to any one of claims 1 to 15, characterized in that steps (i) and (ii) are carried out simultaneously, before or after step (iii). 18. Method according to any one of claims 1 to 15, characterized in that steps (i), (ii) and (iii) are applied sequentially. 19. Method according to the preceding claim, characterized in that the monosaccharide (s), the polysaccharide (s) with amine group (s) and the dye (s) or material (s) are respectively included in three separate compositions (ca), (cb) and (ce). 20. Method according to claim 16 or 19, characterized in that the content of the monosaccharide (s), present (s) in the composition (C) or the composition (ca), ranges from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition comprising it. 21. Method according to any one of claims 16, 19 or 20, characterized in that the content of the polysaccharide (s) with amine group (s), present (s) in composition (C) or the composition (cb) ranges from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition including them. 22. Method according to any one of the preceding claims, characterized in that step (iv) of heat treatment of the keratin fibers is carried out at a temperature of at least 100 ° C, preferably at a temperature ranging from 100 to 250 ° C; more preferably from 150 to 220 ° C, better still from 160 to 220 ° C, even better from 160 to 200 ° C, and even more preferably from 130 to 190 ° C. 23. Method according to any one of the preceding claims, characterized in that it comprises a step of drying the keratin fibers before step (iv) of heat treatment, said drying step being carried out by means of a dryer. hair, a helmet or even with a towel, an absorbent, or by free drying, the drying step is preferably carried out at a temperature ranging from 20 to 70 ° C. 24. Cosmetic composition (C), at acidic pH, comprising: a) one or more monosaccharide (s) as defined in any one of claims 1 to 6 and 20, b) one or more polysaccharide (s) with amine group (s), salified (s) or non-salified (s), as defined in any one of claims 1, 7 to 11 and 21, c) one or more coloring material (s) as defined in any one of claims 1 and 15, and d) optionally one or more mineral or organic acid (s), as defined in any one of claims 12 or 13. 5 25. Kit including: - a device with several compartments comprising a first compartment containing a cosmetic composition (ca) comprising a) one or more monosaccharide (s) as defined in any one of claims 1 to 6 and 20; a second compartment 10 containing a cosmetic composition (cb) comprising b) one or more polysaccharide (s) with amine group (s) as defined in any one of claims 1, 7 to 11 and 21 , and optionally c) one or more organic or inorganic acids as defined in any one of claims 12 and 13; and a third compartment containing a coloring composition (ce) comprising one or more coloring material (s) as defined in any one of claims 1, and 15; and - a device for heating keratin fibers to a temperature of at least 80 ° C.