A process for coloring keratin fibers comprising applying to the keratin fibers at least one protease, an acetoacetate compound, a coloring agent, and a (poly)amine compound

Abstract

The present invention relates to a process for coloring keratin fibers comprising: - at least one application step P on said keratin fibers of a composition comprising at least one protease-type enzyme, then - the application on said keratin fibers, in one or more steps, of the following ingredients, included in one or more separate compositions: i) at least one compound with particular acetoacetate functions, ii) at least one coloring agent selected from pigments, direct dyes, and mixtures thereof, and iii) at least one (poly)amine compound.

Description

Title of the invention: A method for coloring keratin fibers comprising applying to the keratin fibers at least one protease, an acetoacetate compound, a coloring agent, and a (poly)amine compound

[0001] The present invention relates to a method for coloring keratin fibers comprising a step of applying to said keratin fibers a pretreatment composition comprising at least one protease-type enzyme, then applying to said keratin fibers, in one or more steps, at least one particular acetoacetate compound, at least one coloring agent and at least one (poly)amine compound.

[0002] Cosmetic products for the temporary coloring of keratin fibers may classically employ one or more film-forming polymers in order to obtain a quality deposit of these products on the keratin fibers, and in particular giving satisfaction to the expectations detailed below.

[0003] Furthermore, in the hair care sector, a new range of products known as hair makeup, or "Hair Make-up," has recently been developed. These products guarantee temporary hair coloring that lasts after one to three shampoos. They constitute a particularly attractive alternative for consumers to permanent hair coloring, provided, of course, that the color effect is effectively maintained upon contact with water and a few shampoos. This requirement is also met, in particular, through the use of effective film-forming agents. Thus, for example, document FR 2 741 530 proposes, for this purpose, for the temporary coloring of keratin fibers, the use of a dispersion of film-forming polymer particles comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.The colors obtained using this coloring method are not always satisfactory in terms of permanence, particularly after shampooing. In fact, generally speaking, these polymers do not always allow for the deposition of pigments on the keratin fibers that fully meets all the aforementioned requirements, namely excellent water resistance, especially with hair shampoos, the ability to adjust shine or invisibility, and, in the case of hair application, very satisfactory hold during styling.

[0004] US patent 2006 / 0079599 describes a medical polymer-based tissue adhesive in which certain ACAC (acetoacetate) group polymers are associated with polyamines in the form of a hydrogel.

[0005] Document EP 3 250 177 A1 describes the use of acetoacetylated compounds in the field of keratin fibers. Keratin fibers treated with said acetoacetylated compounds do not always give satisfactory results, particularly in terms of resistance to water and shampoos.

[0006] There therefore remains a need to make available processes for coloring keratin fibers which allow for intense, chromatic colorings with good color rise, as well as good resistance to water and shampoos, in order to guarantee color retention over time, particularly in terms of intensity and / or chromaticity.

[0007] Furthermore, the formulation of environmentally friendly cosmetic products, that is to say whose design and development take into account environmental issues, is becoming a major concern in order to help meet global challenges.

[0008] It is therefore essential to propose more sustainable compositions and / or preparation processes and / or ingredients, thus enabling us to meet these environmental challenges.

[0009] In this context, it is important to develop processes for preparing cosmetic products and / or cosmetic ingredients with a better carbon footprint capable of reducing the generation of carbon dioxide throughout the product life and / or low cost in energy and water and / or using greener solvents and / or with fewer synthesis steps and / or with good atom economy.

[0010] The present invention is specifically aimed at meeting all or part of these needs.

[0011] The present invention relates in particular to a method for coloring keratin fibers comprising:

[0012] - at least one application step P on said keratin fibers of a composition (CP) comprising at least one protease-type enzyme, then

[0013] - the application to said keratin fibers, in one or more steps, of the following ingredients (i), (ii) and (iii), which are included in one or more separate compositions:

[0014] i) at least one compound with acetoacetate functions of the following formula (I):

[0015] in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or their combinations, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (CrC4)alkyl group; - X is a heteroatom or group chosen from O, S, N(R') or , -S-CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-; - n denotes an integer ranging from 2 to 10, particularly from 3 to 9; and

[0016] ii) at least one coloring agent selected from pigments, direct colorants, and mixtures thereof; and

[0017] iii) at least one (poly)amine compound.

[0018] It has been observed that the process according to the invention makes it possible to obtain an intense, chromatic coloration of the keratin fibers with a good rise in color.

[0019] It has also been observed that the colouring obtained by the process according to the invention is particularly resistant to water and shampoos.

[0020] The invention also relates to a device containing: - a first compartment comprising a composition (CP) containing at least one protease-type enzyme; - a second separate compartment containing at least one ingredient i) and possibly at least one ingredient ii); preferably not containing ingredient iü); - a third separate compartment containing at least one ingredient (iii) and possibly at least one ingredient (ii); preferably not containing ingredient (i); and - possibly at least one fourth compartment containing at least one ingredient ii); provided that at least one of the compartments contains at least one ingredient ii).

[0021] Other objects, features, aspects and advantages of the invention will become even clearer upon reading the description and example that follows.

[0022] For the purposes of the present invention, and unless otherwise indicated: - the expression "at least one" is equivalent to the expression "one or more" and can be substituted for it. - the expression "between... and..." is equivalent to the expression "ranging from... to..." and can be substituted for it, and implies that the limits are included. - By the expression "greater than" and respectively the expression "less than" in the meaning of the present invention, we mean an open interval that is strictly greater than, respectively strictly less than, and therefore that the bounds are not included. - For the purposes of this application, "keratin fibers" refers particularly to human keratin fibers such as hair, eyelashes, eyebrows, and body hair, preferably hair, eyebrows and eyelashes, and even more preferably hair. - For the purposes of this invention, "hair" means the hair on the head. This term does not include body hair, eyebrows, or eyelashes. - "Residual color after shampooing" means, for the purposes of this invention, that the color obtained persists after at least one shampoo, particularly after at least three shampoos, preferably at least five shampoos.

[0023] - an "aryl" radical represents a mono- or polycyclic hydrocarbon group, condensed or not, comprising from 6 to 14 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

[0024] - a "heteroaryl" radical represents a mono- or polycyclic group, condensed or not, comprising 5 to 14 links, 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring is aromatic; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl;

[0025] - By "(hetero)aryl" we mean the aryl or heteroaryl groups;

[0026] - By "(hetero)cycloalkyl" we mean cycloalkyl or heterocycloalkyl groups;

[0027] - The "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radicals can be substituted by at least one substituent attached to a carbon atom, chosen from: • an alkyl radical in Ci-C6, preferably in C1-C4; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxy group; • a C1-C2 alkoxy radical; a C2-C4 (poly)-hydroxyalkoxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, in Ci-C6, Ci-C6, preferably in CrC4; • an acylamino radical (-N(R)-C(O)-R') in which the radical R is a hydrogen atom, • an alkyl radical in Ci-C4 and the radical R' is an alkyl radical in Ci-C4; a carbamoyl radical (R2N-C(O)-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in CrC4; • an alkylsulfonylamino radical (R'S(O)2-N(R)-) in which the radical R represents a hydrogen atom, an alkyl radical in CrC4 and the radical R' represents an alkyl radical in Ci-C4, a phenyl radical; • an aminosulfonyl radical (R2N-S(O)2-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in Ci-C4; • a carboxylic radical in acidic or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); • a cyano group (CN); • a polyhalogeno(Ci-C4)alkyl group, preferably trifluoromethyl (CF3);

[0028] - the cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent attached to a carbon atom chosen from the following groups: • hydroxy, • CrC4 alkoxy, C2-C4 (poly)hydroxyalkoxy, • alkylcarbonylamino (RC(O)-NR'-) in which the radical R' is a hydrogen atom, an alkyl radical in CrC4 and the radical R is an alkyl radical in CrC4, amino substituted by one or two identical or different alkyl groups in CrC4; • alkylcarbonyloxy (RC(O)-O-) in which the radical R is a C1-C4 alkyl radical, amino substituted by one or two identical or different C1-C4 alkyl groups; • alkoxycarbonyl (RO-C(O)-) in which the radical R is an alkyl radical in CrC4,;

[0029] - a cyclic radical, heterocyclic radical, or a non-aromatic part of an aryl radical or heteroaryl, can also be substituted by one or more oxo groups;

[0030] - a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; preferably one or more double bonds;

[0031] - a "cyclic" or "cycloalkyl" radical is a non-cyclic hydrocarbon radical aromatic, mono or polycyclic, condensed or non-condensed, containing from 5 to 14 carbon atoms, which may have from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group;

[0032] - a "heterocyclic" or "heterocycloalkyl" radical is a non-cyclic radical aromatic mono or polycyclic, condensed or non-condensed, containing 3 to 9 links, comprising 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl, or dithiolane;

[0033] - an "alkyl" radical is a saturated hydrocarbon radical, linear or branched, in particularly in C1-C6, preferably in C1-C4;

[0034] - an "alkoxy" radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Ci-C6 preferably in Ci-C4;

[0035] - a "(poly)(hydroxy)alkyl" radical designates a Ci-C6 alkyl radical, of preferably in C1-C4 possibly substituted by one or more hydroxy radicals, preferably substituted by 1 to 4 hydroxy groups, more particularly between 1 and 3;

[0036] - a "sugar" radical is a monosaccharide or disaccharide radical. Examples include: as sugar radical: sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, or lactose;

[0037] - by “monosaccharide” is meant a monosaccharide sugar comprising at 5 carbon atoms, in particular of formula CX(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 inclusively between 5 and 7, preferably x = 6, they may be of D or L configuration, and of alpha or beta anomer, as well as their salts and solvates such as hydrates;

[0038] - by “disaccharide”, we mean a di-osidic sugar which is a compound made up of of two sugars linked together by O-glycosidic bonds, said compounds being consisting of two monosaccharides (also called mono-osidics) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the mono-osidic units are linked together in 1,4 or 1,6 in anomer a (alpha) or [3 (beta), each osidic unit being able to be of L or D configuration, as well as its salts and solvates such as the hydrates of said monosaccharides; these are more particularly compounds formed of two oses (or monosaccharides) having the general formula: -[Cx(H2O)y)] 2- or -[(CH2O)X]2-, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x = 6, and y an integer which represents x - 1;

[0039] - by “polysaccharide” we mean a polysaccharide sugar which is a polymer consisting of at least 3 sugars linked together by O-glycosidic bonds, said polymers being made up of monosaccharide units (also called mono-glycosidic units) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the monosaccharide units are linked together in 1,4 or 1,6 in anomer a (alpha) or [3 (beta), each glycosidic unit being able to be of L or D configuration, as well as its salts and solvates such as the hydrates of said monosaccharides;more specifically, these are polymers formed from a certain number of sugars (or monosaccharides) having the general formula: -[Cx(H2O)y)]w- or -[(CH2O)X]W-, with x an integer greater than or equal to 5, preferably x greater than or equal to 6, in particular x is between 5 and 7 inclusive, preferably x = 6, and y an integer representing x - 1, and w is an integer greater than or equal to 2, particularly between 3 and 3000 inclusive, more particularly between 5 and 2500, preferably between 10 and 2300, particularly between 15 and 1000 inclusive, more particularly between 20 and 500, preferably between 25 and 200; ;

[0040] - by "salt of organic or mineral acid", more particularly means a) the addition salts with a particular organic or mineral acid selected 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)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid H3PO4; ix) triflic acid CF3SO3H and x) tetrafluoroboric acid HBF4; xi) organic carboxylic acids R°-C(O)-OH (l'z) formula (Fz) in which R ° represents a (hetero)aryl group such as phenyl, (hetero)aryl(Ci-C4)alkyl such as benzyl, or (Ci-Cio)alkyl, said alkyl group being optionally substituted preferably by one or more hydroxy groups, amino radicals, or carboxy groups, R ° preferably designating a (Ci-C6)alkyl group optionally substituted by 1, 2 or 3 hydroxy groups, or more preferably monocarboxylic acids of formula (l'z) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid; and polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof; and xii) amino acids containing more carboxylic acid radicals than amino groups such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid;or b) addition salts with an organic or mineral base such as hydroxides of alkali metals, alkaline earth metals, carbonates of alkali metals or alkaline earth metals, bicarbonates of alkali metals or alkaline earth metals, addition salts with so-called basic amino acids such as arginine, lysine, addition salts with amines possibly hydroxylated;

[0041] - an "anionic counterion" is an anion or anionic group associated to the cationic charge; more particularly the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including the Ci-C6 alkylsulfonates: Alk-S(O)2O such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-OS(O)O such as benzene sulfate and toluene sulfate; xi) alkoxysulfates: Alk-OS(O)2O such as methoxysulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS(O)2 O, xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

[0042] - The "solvates" represent the hydrates as well as the association with alcohols linear or branched in linear or branched Ci-C4 such as ethanol, isopropanol, n-propanol;

[0043] - By "anhydrous" is meant a quantity of less than 5% by weight of water, preferably less than 3% by weight of water, better less than 1% by weight of water, relative to the total weight of the composition in question, even more preferably the composition in question is free of water.

[0044] - The terms "coloring agent" and "coloring matter" are equivalent;

[0045] Unless otherwise indicated, the quantities shown are expressed as mass percentages. Application step P Protease-type enzyme

[0046] According to the process of the invention, during the application step P, a composition (CP) comprising at least one protease-type enzyme is applied to the keratin fibers.

[0047] Protease-type enzymes are also called “proteases”, “proteolytic enzymes” or “peptidases” (or even “proteinases” in English).

[0048] The protease-type enzymes that can be used in the composition (CP) of the invention include those belonging to class EC 3.4 according to the nomenclature of the Enzyme Commission.

[0049] Among the commercially available protease enzymes, examples include the one sold by Sigma Aldrich under the name "Proteinase K", those sold by Novozymes under the names Protamax®, Protana® Prime, Flavourzyme®, Neutrase®, Alcalase®, Savinase®, Esperase®, or Durazym®, the one sold by IFF Health & Biosciences under the trade name FoodPro®, the one sold by Takabio under the trade name Sumizyme®, the one sold by DKSH under the trade name Collupolin®, or the one sold by Genencor under the trade name Prionzyme®.

[0050] Preferably, the protease-type enzyme(s) in the composition (CP) are chosen from aminopeptidases, dipeptidases, dipeptidyl-peptidases, tripeptidyl-peptidases, peptidyl-peptidases, serine-type carboxypeptidases, metallocarboxypeptidases, cysteine-type carboxypeptidases, omega peptidases, serine endopeptidases, cysteine ​​endopeptidases, aspartic endopeptidases, metalloendopeptidases, threonine endopeptidases, and mixtures thereof.

[0051] More preferably, the protease-type enzyme(s) in the composition (CP) are chosen from serine endopeptidases, cysteine ​​endopeptidases, aspartic endopeptidases, aminopeptidases, and mixtures thereof.

[0052] More preferably still, the protease-type enzyme(s) in the composition (CP) are chosen from among the keratinases.

[0053] Keratinases are described in particular in the article "Microbial Keratinases: Enzymes with Promising Biotechnological Applications, Food Technology and Biotechnology, Vol. 56, Issue 3".

[0054] Preferably, the total content of protease-type enzyme(s) in the composition (CP) is in the range of 0.0001% to 20% by weight, preferably from 0.0005% to 10% by weight, more preferably from 0.001% to 5% by weight, even more preferably from 0.005% to 2% by weight, better from 0.01% to 1% by weight, even better from 0.05% to 1% by weight, relative to the total weight of the composition (CP).

[0055] Preferably, the total content of serine endopeptidase(s) in the composition (CP) is in the range of 0.0001% to 20% by weight, preferably 0.0005% to 10% by weight, more preferably 0.001% to 5% by weight, even more preferably 0.005% to 2% by weight, better 0.01% to 1% by weight, even better 0.05% to 1% by weight, relative to the total weight of the composition (CP).

[0056] Preferably, the total content of keratinase(s) in the composition (CP) is in the range of 0.0001% to 20% by weight, preferably 0.0005% to 10% by weight, more preferably 0.001% to 5% by weight, even more preferably 0.005% to 2% by weight, better 0.01% to 1% by weight, even better 0.05% to 1% by weight, relative to the total weight of the composition (CP).

[0057] The composition (CP) of the invention preferably comprises water.

[0058] Preferably, the total water content in the composition (CP) is in the range of 50% to 99.9999% by weight, more preferably 60% to 99.95% by weight, more preferably 70% to 99.90% by weight, and even better 80% to 99.90% by weight, relative to the total weight of the composition (CP).

[0059] Preferably, when the composition (CP) of the invention includes water, the pH of the composition (CP) is between 5 and 12, more preferably between 5 and 9, more preferably still between 6 and 8, better between 6.5 and 7.5.

[0060] The pH can be adjusted to the desired value by means of alkalizing agents or acidifying agents commonly used.

[0061] Among the acidifying agents, examples include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

[0062] Among the alkalizing agents, ammonia, mineral or organic hydroxides may be mentioned.

[0063] The composition (CP) may further contain additives commonly used in cosmetics, such as antifoaming agents, thickening agents, moisturizing agents, clays, mineral fillers, UV filters, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, vitamins, preservatives, silicones, waxes, and mixtures thereof. These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition (CP).

[0064] A person skilled in the art will take care to choose these possible additives and their quantities so that they do not impair the properties of the compositions of the present invention.

[0065] The use of the composition (CP) can be done on wet or dry keratin fibers, in rinsed or unrinsed mode.

[0066] Preferably, the use of the composition (CP) is on wet or dry keratin fibers, in rinsed mode, that is to say that after the application of the composition (CP), the keratin fibers are rinsed with water and may possibly undergo one or more shampoos.

[0067] More preferably, the keratin fibers are rinsed with water after the application of the composition (CP) and undergo at least two shampooings. Compound of formula (I)

[0068] According to the process of the invention, after step P, at least one compound of the following formula (I) is applied to the keratin fibers: in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or their combinations, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (CrCJalkyl; - X is a heteroatom or group chosen from O, S, N(R') or , -S-CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-; - n denotes an integer ranging from 2 to 10, particularly from 3 to 9.

[0069] Preferably, the compound of formula (I) is chosen from those of the following formula (la). Formula (la) encompasses optical isomers, geometric isomers, salts, and solvates such as the hydrates of the compound. rpoi -X < (there)

[0070] in which:

[0071] - R1 is such as defined above, in particular represents a radical versatile hydrocarbon in C2 to CM, preferably in C3 to C[2, preferably in C4 to C10, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further:

[0072] a) possibly substituted by one or more hydroxyl groups OH, and / or

[0073] b) optionally interrupted by one or more heteroatoms or groups chosen from O, S, -N(R'), preferably interrupted by one or more oxygen atoms, in which R' is as defined in formula (I);

[0074] - R2 is as defined above, preferably R2 represents a group (Ci-C 6)alkyl, linear or branched, preferably a (CrC4)alkyl group, particularly methyl or tert-butyl such as methyl; and

[0075] - n being such as defined in formula (I), preferably n denotes an integer ranging from 2 to 9.

[0076] The compounds of formula (I) and (la) may be such that R1 represents a C6 to C8 C6-C ...

[0077] The compounds of formula (I) and (la) may also be such that R1 represents a C5 to C2 saturated monocyclic or bicyclic hydrocarbon polyvalent radical, optionally interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), in which R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, preferably interrupted by one or more oxygen atoms. Preferably R1 represents a monosaccharide or polysaccharide motif, in particular a disaccharide on which n hydroxy groups have been substituted by n -OC(O)-CH2-C(O)-R2 groups with R2 as defined previously and n as defined previously.

[0078] Suitable monosaccharides according to the invention include, but are not limited to, ribose, glucose, mannose, galactose, fructose, sorbose and inositol.

[0079] Advantageously, the disaccharides are selected from cellobiose, maltose, lactose, raffinose, sucrose, trehalose, melibiulose, melibiose, mannobiose, kojibiose, nigerose, isomaltose, rutinose, rutinulose, xylobiose, preferably sucrose.

[0080] The compounds of formula (I) and (la) may also be such that R1 represents a C2 to Ci2 acyclic, preferably C3-C10, linear or branched, saturated or unsaturated, more preferably saturated, acyclic hydrocarbon polyvalent radical.

[0081] Preferably, the compounds of formula (I) and (la) are such that R1 represents a versatile acyclic hydrocarbon radical selected from the radicals mannitol, xylitol, sorbitol, trimethylolpropane, di(trimethylolpropane), 2-methyl-l,3-propanediol, 2-hydroxymethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, erythritol, pentaerythritol or dipentaerythritol, more preferably mannitol, xylitol, sorbitol, trimethylolpropane, di(trimethylolpropane), 2-methyl-l,3-propanediol, 2-hydroxymethyl-l,3-propanediol, erythritol, pentaerythritol or dipentaerythritol.

[0082] Preferably, the compounds of formula (I) and (la) are such that n denotes an integer from 2 to 9, more particularly n denotes an integer from 3 to 9, more particularly from 4 to 9, such as 6 or 8. The compounds of formula (I) may be such that n equals 2. The compounds of formula (I) may be such that n equals 3. The compounds of formula (I) may be such that n equals 4. The compounds of formula (I) may be such that n equals 5. The compounds of formula (I) may be such that n equals 6. The compounds of formula (I) may be such that n equals 7. The compounds of formula (I) may be such that n equals 8. The compounds of formula (I) may be such that n equals 9. The compounds of formula (I) may be such that n equals 10.

[0083] More particularly, the compound(s) of formula (I) and (la) are chosen from the following compounds, as well as their optical isomers, their salts, and solvates such as hydrates: (Compound) X CAS (1) 700865-73-2 Chemical name 3-oxo-l,T-(1,7-heptanediyi) acid ester J Chemical structure Ü A 0. A ......x AA XX- •'.v- xv •'çy- ü O c (4) 174498-06-7 3-oxo-l,r-(l,3-propanediyl) butanpic acid 1 I 1 1 VQ-" x- (5) 160187-52-0 3-oxo-1,2-dimethyl- 1,2-ethanediyl butanoic acid ester 9 9 ix""Xs. .“'"'s, - yyy * 0 0 (6) 145020-19-5 3-oxo-2-butyl-2-ethyl-1,3-propanediyl butanoic acid ester .-X, / .AA x' (7) 87530-36-7 3-oxo-1,1,2,2-tetramethyl-1,2-ethanediyl butaeolic acid ester O i Y .o, "o'- V / \ / \ ■ 5 o (8) 58213-75-5 3-oxo-1,1'-(1-methyl-1,3-propanediyl) butaeolic acid ester A > ■'x •A (9) 58213-74-4 3-oxo-1,1'-[2,2-dimethyl-1-phenylethyl,3-propanediyl] butaeolic acid ester Q > 0 0 M (10) 39564-28-8 3-oxo-1,1-(1,5-pentanediyl) butaeolic acid ester 0 c . Â XX J Xx- \Z XZ '«y 1 (H) 14276-67-6 3-oxo-1,1-(2,2-dimethyl-1,3-propanediyl) butanoic acid ester 0 < Z \ / X (12) 13018-41-2 3-oxo-1,4-butanediyl butanoic acid ester 1 .XX, XX X'X ô (13) 6079-90-9 3-oxo-1-methyl-1,2-ethanediyl butanoic acid ester (14) 5459-04-1 3-oxo-1,2-ethanediyl butanoic acid ester Q (15) 2388-18-3 3-oxo-l,r~(l,6~ hexanediyl) tanoic acid ester d ' 3-oxo-1,6-hexanediyl butanoic acid ester (9CI) Y^-x, X x''S'8 x-1 X-3 v'3-1'-6 s( 3 -oxobutanoate ) of l,r-[2,2-Bis[(l,3-dioxobutoxy )methyl]-1,3-propanediyl] O \\ OA— VY OG / A Jkzx / ^ Y z°\ x ? z ■ ir ZY ° c / X \\ u 'G (17) 51980-20-2 bis( 3-oxobutanoate ) of l,r-[22-Bis(lwdro^^ 1,3-pî'opanediyl] 0 0 LA / ........* x ''o'^ / XXVL xx HO-------------,z ! \ (20) 139264-86-1 3-oxo-1,2,4-benzenetriyl butanoic acid ester (21) 22208-25 Triacetoacetate of .SX-.--.SX' .---SX' .■•-SX-.■-•w-» trimethylolpropane K-FLEX 7301 (22) 2360524-48- 5 (23) 66229-33-2 3-oxo-2-butyI-2-[( djqxobj^^ 1,3-propanediyl bytanoic acid ester (24) 1579231-50- 4,4-dimethyl-3-oxo-, lr-[252-bis[[(4.4-dimethyl-1,3-dioxopenhd)oxy]meth yl]-l,3-propanediyl] acid ester pentanoic. (25) 6079-98-7 tris(3-oxobutanoa te) of IJUAUJ-propanetriyl) 0 0 OOAAAA ' ' 0 A 0 ï 0 ô ô (26) tetra-acetoacetate of meso-erythritol A o' c; / -o -o—zyr ■ - . X (A AyA'' C; i (27) 169533-29-3 aD-Glucopyranose, 1,2,3,4,6-pentaxis(3-oxobutanoate) T . "vx Q 0 riyoo 'S"'' xo' ix â - A . * XT-50 t “AOO (A) x24. 7 5-amino-2-[[2,3,4-tris-O-(l,3-dioxobuty!)-D-xy lopyranosy l]oxy ] -d'benzoic acid AGOM AA 9 p *À"" "A <5 (29) 1236300-10- 9 2,3,4,6-tetrakis(3-oxobutanoate) de aD-GJucopyr^^ 1,3,4,6-tetrakis-O-(1,3 -dioxo A butvl}: o ^-D-fhictofuranosvl.v'" x':-•v.w „1 ,I„1 J AA........ -> ■ x A £ l TJ * l.^ (30) 96481-26-4 D-GIucopyranose, pentax(3-oxobutanoate) V. 1J 0 VY"" ü^' a (31) 94-47,D3-12 1,4:3,6-diaiihydro-, 2,5-bis(3-oxobutanoate) / 7 o ff A / "A y 4 hi / y--ù o / / d (32) 2254710-49- 9 ? ? Al.) 0 A A- ? ï 0 J ,-A;. xfx A .9 (33) hexa-aeetoacetate of sorbitol o : ' 9 9 ooc>-;5X'o .11 .K. .... XX o - .- .... .. .0.. ... ,... .. y .. .--. .0 0. zO Q 0 WX"' G ô ... x G (34) 216756-89-7 D-Glucitol, 4-O-fl-D-galactopyranosyl-. polyacetoacetate m / 0 0 RI fft-— 0--- / }---0 O \ \ / \ / \ - RI / \ - RI ) \ RI 0 R"! \ R! with RI chosen among -C(O)-CH2-C(O)-CH3,H with at least two radicals RI represent -C(Ô)-C Hï-CO-C H3 (35) 101655-52-1 Sucrose, polyacetoacetate rî q—-Ri 0 / R' / ricy V — Ric \ — \ — Ric \ — with RI chosen among -C(O)-CH2-C(O)-CHs, H with, at least two RI radicals represent -C(O)-CH2-C(O)-CH3 (36) Glucose. RI / „„ 0 RI \ ^O. À R1 0 B» 6' o R1Z RI (37) Mannose pcdyaxé^ R1 / RI °\ % A R1--0 B»— / O 0 OR RI (38) Xylitol pplyac^ O \ V^io o *"\ £ o Jol (39) Sor cebit go^aceto^cetate RI R1 oz RI. 0 jT XR1 _o R1^ RI of preference 6 RI radicals represent -C(O)-CH2-C(O)-CH3 (40) ri RI ""'O ox I = RI RI / X xr ''y ^0 0 (41) 1471-94-9 OOQO (42) 2552-36-5 1 1 XX A xx XXXT XX x, XX (43) 139614-56-5 0 OOO 1 A YA / \x' \ HH (44) 96169-30-1 $D (45) Q-0159 AA Ak _x-- " vxrt I (46) polya^ RI X C--- Rt ,—4^» / / | R s 0 > .•X kX preferably 5 or 6 RI radicals, more preferably 6 RI radicals represent -C(O)-CH2-C(O)-CH

[0084]

[0085] in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent a -C(O)-CH2-C(O)-CH3 group, preferably at least three RI radicals represent a -C(O)-CH2-C(O)-CH3 group. Preferably, the compounds of formula (I) and (la) are chosen from compounds (16), (18), (21), (35), (36), (37), (38), (39), (40), (46), and their mixtures; more preferably from compounds (16), (21), (35), (38), (39), (46), and their mixtures mixtures; even more preferentially among compounds (21), (35), (46), and their mixtures.

[0086] According to one embodiment of the invention, a single compound of formula (I) and / or (la) is applied to the keratin fibers in one or more distinct compositions, after the application step P.

[0087] According to another embodiment of the invention, several compounds of formula (I) and / or (la) are applied to the keratin fibers in one or more distinct compositions, after the application step P.

[0088] The compound(s) of formula (I) can be obtained by (poly)condensation(s) of n equivalents of dicarbonyl reagent with a nucleophilic reagent R'(XH)n comprising n equivalents of -XH nucleophilic functions according to the following scheme:

[0089] in which:

[0090] - R1, R2, Ra, Rb and n are such as defined for the compound of formula (I) and ;

[0091] - R3 represents a hydrogen atom, a (Ci-C4)alkyl group such as methyl, ethyl, isobutyl, t-butyl, or an electrofuge group such as CHal3, or Hal3C-SO2-like triflate, with Hal, identical or different, representing a halogen atom;

[0092] - X' represents an oxygen atom, or sulfur, preferably O.

[0093] These (poly)condensation methods are known to those skilled in the art; one can cite for example “From rigid and flexible foams to elastomers via Michael addition chemistry”, Polymer, 106, 128-139, (2016), “Dynamic Curing Agents for Amine-Hardened Epoxy Vitrimers with Short (Re)processing Times”, Macromolecules, 53(7), 2485-2495 (2020), “Super photo-base initiated organic-inorganic hybrid coatings by plural-cure mechanisms”, Progress in Organic Coatings, 127, 222-230 (2019) or patent application PL159100: Method for manufacturing acetylacetate esters.

[0094] The compound R'(XH)n can be selected from the acyclic polyols R'(OH)n, in particular from glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, trimethylolethane, pentamethylene glycol, trimethylpentanediol, pentyl glycol, isosorbide, pentaerythritol, dipentaerythritol, hexamethylene glycol, hexylene glycol, hexandediol, neopentyl glycol, 1,2-propanediol; 1,3-propanediol; 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol; 2,4-butanediol, 3,4- butanediol; 1,4-Pentanediol; 1,5-pentanediol, 2,2,4-Trimethyl-l,3-pentanediol, 1,6-hexanediol, 1,2 octanediol, 1,8 octane diol, 1,10-decanediol, 2-methyl-l,3-propane diol, hexylene glycol, isoprene glycol.

[0095] The compound R'(XH)n can also be chosen from among the cyclic polyols R'(OH)n in particular chosen from among the monosaccharides and disaccharides, as defined above, alone or in mixture.

[0096] Preferably, R'(XH)n is selected from polyols R'(OH)n alone or in mixtures of mannitol, xylitol, sorbitol, glycerol, glucose, trimethylolethane, trimethylolpropane, di(trimethylolpropane), 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1'-erythritol, pentaerythritol, dipentaerythritol, and mixtures thereof, more particularly from trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, glycerol, glucose, sucrose, and sorbitol, and mixtures thereof. Furthermore, compound R'(XH)n may be selected from diamines R'(NH2)2 including hydroxyalkylated aliphatic diamines such as ro,o'-bis(diethanolaminomethyl)-p-nonylphenol, N,N,N,N'-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, available from BASF) and N,N,N,N-tetra(2-hydroxyethyl)ethylenediamine, and mixtures thereof.

[0097] Advantageously, the compound(s) of formula (I) are obtained by (poly)condensation(s) of n equivalents of propylenedioxy carbonyl reagent with a polyamine nucleophilic reagent R'(NH2)n comprising n equivalents of -NH2 nucleophilic functions according to the following scheme:

[0098] in which:

[0099] - R1, R2, R“, and n are such as defined for the compound of formula (I)

[0100] - R'-NH2 is in particular selected from ethylenediamine, 1,3-diaminopropane, cadaverine, hexamethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, phenylenediamine; and

[0101] - Rb and Rc', whether identical or different, represent a hydrogen atom, a group (CrC4)alkyl.

[0102] This type of synthesis process is known to those skilled in the art; for example, one can cite "Acetoacetylation with 2,2,6-trimethyl-4H-l,3-dioxin-4-one: a convenient alternative to diketene", Journal of Organic Chemistry, 50(14), 2431-5, (1985) or “Synthesis of new Biginelli polycondensates: renewable materials with tunable high glass transition temperatures”, Polymer International, 70(5), 506-513 (2021).

[0103] Preferably, the compound(s) of formula (I) are obtained by (poly)condensation(s) of n equivalents of diketene reagent with a nucleophilic reagent R*(X)n comprising n equivalents of -XH nucleophilic functions according to the following scheme:

[0104] in which:

[0105] - R1, and n are such as defined for the compound of formula (I)

[0106] - X' represents an oxygen atom, or sulfur atom, or N(R') with R'=H

[0107] This type of process is known to those skilled in the art. For example, one can cite "Acetoacetamides, 2-hydroximinoacetoacetamides, and 2,3-bis(hydroximino)-butyramides", Journal für Praktische Chemie (Leipzig), 323(2), 337-44, (1981) or Angewandte Makromolekulare Chemie, 9, 96-105, (1969).

[0108] Preferably, the total content of compound(s) of formula (I) present in a composition is in the range of 0.1% to 40% by weight, preferably 0.5% to 30% by weight, more preferably 1% to 25%, even more preferably 2% to 20% by weight, relative to the total weight of the composition containing it / them.

[0109] Preferably, the total content of compound(s) of formula (la) present in a composition is in the range of 0.1% to 40% by weight, preferably 0.5% to 30% by weight, more preferably 1% to 25%, even more preferably 2% to 20% by weight, relative to the total weight of the composition containing it / them.

[0110] Preferably, the total content of compound(s) (1) to (46) present in a composition is in the range of 0.1% to 40% by weight, preferably 0.5% to 30% by weight, more preferably 1% to 25%, even more preferably 2% to 20% by weight, relative to the total weight of the composition containing it / them. Coloring agent

[0111] According to the process of the invention, after step P, ii) at least one coloring agent chosen from pigments, direct dyes, and their mixtures is applied to the keratin fibers. Pigments

[0112] Preferably, the colouring agent(s) are chosen from pigments.

[0113] The term "pigment" means all pigments that impart color to keratinous materials. Their solubility in water at 25 °C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01% (in g / L of water).

[0114] The pigments that can be used are in particular chosen from among the organic and / or mineral pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0115] They may be natural, of natural origin, or not.

[0116] These pigments may be in the form of a powder or pigment paste. They may be coated or uncoated.

[0117] Pigments can, for example, be chosen from mineral pigments, organic pigments, lacquers, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0118] The pigment may be a mineral pigment. By mineral pigment, we mean any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium dioxide.

[0119] The pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition in the Ullmann encyclopedia in the chapter on organic pigment.

[0120] The organic pigment may in particular be selected from the following compounds: nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0121] In particular, the white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments coded in the Color Index under references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments coded in the Color Index under references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under reference Cl 61565, 61570, 74260, the orange pigments coded in the Color Index under references CI 11725, 45370, 71105, the red pigments coded in the Color Index under references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole and phenolic derivatives as described in the patent FR 2 679 771.

[0122] By way of example, one can also cite organic pigment pastes such as the products sold by the company HOECHST under the name:

[0123] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0124] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0125] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0126] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0127] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0128] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0129] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0130] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0131] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0132] 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 core, at least one binder ensuring the fixation of organic pigments on the core, and at least one organic pigment covering at least partially the core.

[0133] The organic pigment can also be a lacquer. By lacquer, we mean colorants adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0134] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0135] Among the colorants, carminic acid can be mentioned. We can also mention the colorants 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 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).

[0136] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850 :1).

[0137] The pigment can also be a special effects pigment. Special effects pigments are defined as pigments that generally create an appearance colored (characterized by a certain shade, a certain vividness and a certain clarity) non-uniform and changing according to the conditions of observation (light, temperature, angles of observation...). They are thus opposed to colored pigments which provide a uniform opaque, semi-transparent or classic transparent tint.

[0138] There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as mother-of-pearl, interference pigments or glitter.

[0139] Examples of special effect pigments include pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent pigments such as titanium-coated mica with iron oxides, iron oxide-coated mica, titanium-coated mica, particularly with ferric blue or chromium oxide, titanium-coated mica with an organic pigment as defined above, and bismuth oxychloride-based pearlescent pigments. Examples of pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO2-lacquer), Prestige pearlescent pigments marketed by Eckart (Mica-TiO2), Prestige Bronze pearlescent pigments marketed by Eckart (Mica-Fe2O3), and Colorona pearlescent pigments marketed by Merck (Mica-TiO2-Fe2O3).

[0140] We can also mention gold-colored mother-of-pearl, notably marketed by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze mother-of-pearl, notably marketed by MERCK under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange mother-of-pearl, notably marketed by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-tinted mother-of-pearl, notably marketed by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-tinted mother-of-pearl, notably marketed by BASF under the name Copper 340A (Timica);red-tinted mother-of-pearl, notably marketed by MERCK under the name Sienna Fine (17386) (Colorona); yellow-tinted mother-of-pearl, notably marketed by BASF under the name Yellow (4502) (Chromalite); red-tinted mother-of-pearl with a gold sheen, notably marketed by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl, notably marketed by BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen, notably marketed by BASF under the name Nu; antique bronze 240 AB (Timica), blue mother-of-pearls notably marketed by the MERCK company under the name Matte Blue (17433) (Microna), white mother-of-pearls with a silvery sheen notably marketed by the MERCK company under the name Xirona Silver and orange-pink-green-gold mother-of-pearls notably marketed by the MERCK company under the name Indian Summer (Xirona) and their mixtures.

[0141] As further examples of nacres, one can also cite particles comprising a borosilicate substrate coated with titanium oxide.

[0142] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0143] Finally, examples of mother-of-pearl include polyethylene terephthalate flakes, particularly those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

[0144] Special effect pigments may also be selected from reflective particles, that is to say, in particular, particles whose size, structure, including the thickness of the layer(s) that constitute them and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create, on the surface of the composition or mixture, when applied to the makeup support, highlights visible to the naked eye, that is to say, brighter points that contrast with their surroundings by appearing to shine.

[0145] The reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them, and more particularly so as to optimize this effect in terms of color rendering. They can, in particular, have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection.

[0146] These particles can have various shapes, including being platelet-shaped or globular, particularly spherical.

[0147] Reflective particles, whatever their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

[0148] When reflective particles do not have a multilayer structure, they can be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

[0149] When reflective particles have a multilayer structure, they may, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated by at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate may be monomaterial, multimaterial, organic and / or inorganic.

[0150] More particularly, it may be selected from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being exhaustive.

[0151] The reflective material may include a layer of metal or a metallic material.

[0152] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0153] As further examples of reflective particles comprising a mineral substrate coated with a layer of metal, one can also mention particles comprising a borosilicate substrate coated with silver.

[0154] Silver-coated glass substrate particles in the form of wafers are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Nickel / chromium / molybdenum alloy-coated glass substrate particles are sold under the names CRYSTAL STAR GF 550, GF 2525 by the same company.

[0155] Particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium may also be used, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0156] An example can be cited as aluminium, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0157] Other examples include non-substrate interference pigments such as liquid crystals (Wacker's Helicones HC) and interference holographic glitter (Spectratek's Geometry Pigments or Spectra f / x). Special effect pigments also include fluorescent pigments, whether daylight fluorescent or ultraviolet fluorescent, phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, marketed, for example, by Quantum Dots Corporation.

[0158] The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic, interference effects.

[0159] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 µm, preferably between 20 nm and 80 µm, and more preferably between 30 nm and 50 µm.

[0160] The pigments can be dispersed within the composition by means of a dispersing agent.

[0161] The dispersing agent serves to protect the dispersed particles from agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer, or a mixture of several of these, possessing one or more functionalities with a strong affinity for the surface of the particles to be dispersed. In particular, they may adhere physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible with or soluble in the continuous medium.In particular, esters of 12-hydroxystearic acid are used, especially C8 to C20 fatty acids and polyols such as glycerol and diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750g / mol, such as that sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by Henkel, or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by Uniqema and their mixtures.

[0162] As another dispersant that can be used in the compositions of the invention, we can mention quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by Avecia, poly dimethylsiloxane / oxypropylene mixtures such as those sold by Dow Corning under the references DC2-5185, DC2-5225 C.

[0163] The pigments used in the invention can be surface treated with an organic agent.

[0164] Thus, the surface-treated pigments useful within the scope of the invention are pigments that have undergone, wholly or partially, a surface treatment of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, before being dispersed in the composition according to the invention. These organic agents may, for example, be chosen from waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc, or aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate motifs; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

[0165] The surface-treated pigments useful in the invention may also have been treated by a mixture of these compounds and / or have undergone several surface treatments.

[0166] The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or found as such in the commercial market.

[0167] Preferably, the surface-treated pigments are covered by an organic layer.

[0168] The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

[0169] Surface treatment can thus be achieved, for example, by a chemical reaction of a surfactant with the surface of the pigments and the creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.

[0170] Preferably, an organic agent covalently linked to the pigments will be used.

[0171] The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the pigment treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight of the total weight of the pigment treated on the surface.

[0172] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0173] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0174] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0175] - a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;

[0176] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0177] - a Magnesium Myristate treatment such as MM surface treatment marketed by LCW;

[0178] - an Aluminium Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;

[0179] - a Perfluoropolymethylisopropyl ether treatment as a surface treatment FHC marketed by LCW;

[0180] - an Isostearyl Sebacate treatment such as the commercially available HS surface treatment by Miyoshi;

[0181] - a Perfluoroalkyl Phosphate treatment as a PF surface treatment marketed by Daito;

[0182] - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;

[0183] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0184] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0185] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0186] - an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;

[0187] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0188] Preferably, the dispersing agent is present with organic or inorganic pigments in submicron-sized particulate form.

[0189] By "sub-micronic" or in English "sub-micronic" is meant pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

[0190] Preferably, the dispersing agent and the pigment(s) are present in quantity (dispersing agent: pigment), according to a weight ratio, between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better between 1.75:3 and 3:1.

[0191] The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0192] - amino-silicones i.e. silicones comprising one or more amino groups such than those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee Polymers,

[0193] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0194] - polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X- 22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

[0195] Preferably, the dispersing agent(s) are of the amino-silicone type and are cationic.

[0196] Preferably, the pigment(s) is / are chosen from mineral, mixed mineral-organic or organic pigments.

[0197] In one embodiment of the invention, the pigment(s) are organic pigments, preferably organic pigments surface-treated with an organic agent selected from silicone compounds. In another embodiment of the invention, the pigment(s) are mineral pigments.

[0198] Preferably, the pigment(s) are chosen from zirconium oxides, zinc oxides, cerium oxides, iron oxides, titanium oxides, chromium oxides, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof; more preferably from titanium oxides such as titanium dioxide, iron oxides, chromium oxides in particular green chromium oxide, and mixtures thereof.

[0199] More preferably, the pigment(s) are chosen from iron oxides, in particular red, brown or black, especially red. Direct dyes

[0200] By "direct dye," we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes that diffuse superficially onto the fiber. They can be ionic, for example cationic or anionic, or non-ionic.

[0201] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in mixtures.

[0202] Direct dyes can be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkali substances. Anionic direct dyes are understood to mean any direct dye having in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom or a cation from a metal or an amine, or an ammonium ion. The dyes Anionic dyes can be chosen from acidic nitro direct dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes.

[0203] A titre d’exemple de colorants acides on peut citer : Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 ; Food yellow 3 ou sunset yellow; Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0204] A titre d’exemple de colorants azo anioniques pyrazolones on peut citer : Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76Acid Yellow 17 ;

[0205] As an example of anthraquinone dyes, we can cite: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple No. 2;: Acid Black 48;

[0206] Examples of nitrate dyes include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (XXII') include: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, 4-[3-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C yellow 7;

[0207] Examples of triarylmethane dyes include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

[0208] Examples of xanthenic dyes include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

[0209] Examples of indole dyes include: Acid Blue 74;

[0210] Examples of quinoline dyes include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0211] Among the natural direct dyes that can be used according to the invention, the following may be mentioned: lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orceins. Extracts or decoctions may also be used. containing these natural dyes and in particular poultices or extracts based on henna.

[0212] Preferably, the total content of colouring agent(s) in a composition is in the range of 0.001% to 20% by weight, more preferably 0.005% to 15% by weight, relative to the total weight of the composition comprising it / them.

[0213] Preferably, the total pigment content in a composition is within the range of 0.05% to 20% by weight, more preferably from 0.1% to 15% by weight, better from 0.5% to 14% by weight, relative to the total weight of the composition comprising it / them.

[0214] Advantageously, the total content of direct colorant(s) in a composition is in the range of 0.001% to 10% by weight, more preferably 0.005% to 5% by weight, relative to the total weight of the composition containing it / them. (Poly)amine compound

[0215] According to the process of the invention, after step P, at least one (poly)amine compound is applied to the keratin fibers.

[0216] The (poly)amine compounds iii) of the invention are different from the compounds i) of formula (I) and the coloring agents ii) previously described.

[0217] The (poly)amine compound may in particular be chosen from among monoamine compounds, polyamine compounds having several primary and / or secondary amine groups or from among amino alkoxysilanes, and more particularly from among amino alkoxysilane compounds, polyamine compounds such as chitosan compounds or polylysines, diamine compounds, triamine compounds, and mixtures thereof.

[0218] The (poly)amine compound may be a compound comprising from 2 to 20 carbon atoms, in particular a non-polymeric compound, it may be acyclic, or cyclic, linear or branched, saturated or unsaturated, conjugated or non-conjugated, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms selected from O, S, Si(R')2, N(R”) preferably O, Si(R')2, or their combinations such as -Si(R')2 -O- or -O-Si(R')2 -, with R' identical or different, represents a (Ci-C4)alkyl group such as methyl, and R” represents a hydrogen atom or a (Ci-C4)alkyl group, preferably hydrogen.

[0219] By "non-polymer compound" is meant a compound that is not directly obtained by a polymerization reaction of monomers.

[0220] Examples of (poly)amine compounds include N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, and methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylene triamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, polylysine, cystamine, xylenediamine, tris(2-aminoethyl)amine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, diaminopropanol such as 1,3-diamino-2-propane-1-ol, 4,7,10-Trioxa-1,13-tridecanediamine, spermidine, lysinol, and C36-alkylenediamines (respectively Priamine™ 1071, 1073, 1074, 1075 marketed by CRODA), preferably 1,3-diamino-2-propane-l-ol, polylysine, spermidine and mixtures thereof.

[0221] The (poly)amine compound(s) may be monoamine, i.e., contain a single primary and / or secondary amine group, preferably primary (NH2).

[0222] The (poly)amine compound(s) may be diaminized, i.e., contain two primary and / or secondary amine groups, preferably primary (NH2). An example of a diaminized compound is 1,3-diamino-2-propane-l ol.

[0223] The (poly)amine compound(s) may be triamine, i.e., contain three primary and / or secondary amine groups. Spermidine is an example of a triamine compound.

[0224] The (poly)amine compound(s) may be polyamines, i.e., contain more than two primary and / or secondary amine groups, preferably primary (NH2). Polylysine is an example of a (poly)amine compound.

[0225] The (poly)amine compound(s) may be chosen from among the amino alkoxysilanes, in particular those of formula R'iSi(OR'2)z(R'3)x, in which:

[0226] - R' i is a linear or branched, saturated Ci-C6 hydrocarbon chain or unsaturated, cyclic or acyclic substituted by a group chosen from the primary amine group NH2 or secondary amine group -N(H)R with R representing a C1-C4 alkyl, aryl, or benzyl substituted by an amino group or by a C1-C4 aminoalkyl group; R'i may be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group C(O), R'i being linked to the silicon atom directly via a carbon atom,

[0227] - R'2 and R'3, whether identical or different, represent a linear (Ci-C6)alkyl group or branched,

[0228] - z denotes an integer from 1 to 3, and

[0229] - x denotes an integer from 0 to 2,

[0230] with z + x = 3.

[0231] In particular, R is an acyclic chain. Preferably, R is a linear or branched, saturated or unsaturated Ci-C6 hydrocarbon chain, substituted by an amine group -NH2 or -N(H)R, where R represents a C1-C6 alkyl, a C3-C6 cycloalkyl, or a C6 aromatic. More preferably, R'i is a linear, saturated C1-C6 hydrocarbon chain substituted with an amine group NH2. Even more preferably, R'i is a linear, saturated C2-C4 hydrocarbon chain substituted with an amine group NH2.

[0232] In particular, R'2 represents an alkyl group comprising 1 to 4 carbon atoms, preferably R'2 represents a linear alkyl group comprising 1 to 4 carbon atoms, and more preferably R'2 represents the ethyl group.

[0233] In particular, R'3 represents an alkyl group comprising from 1 to 4 carbon atoms, preferably, R'3 represents a linear alkyl group comprising from 1 to 4 carbon atoms, and more preferably R'3 represents the methyl or ethyl group. Preferably, z is equal to 3.

[0234] In particular, the (poly)amine compound(s) may be selected from amino alkoxysilanes having only one primary and / or secondary amine group, preferably primary (NH2) such as 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxy-silane, p-aminophenyltrimethoxysilane, and N-(2-aminoethylaminomethyl)-phenethyltrimethoxysilane.

[0235] The (poly)amine compound(s) may be selected from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferably 3-aminopropyltriethoxysilane (APTES) or its oligomers.

[0236] The (poly)amine compound(s) may be monoamine and may be chosen from polydialkylsiloxanes in particular of formula (IV) H2N-ALK-Si(R'2)(R'3)-O-[ Si(R'2)(R'3)-O]n- Si(R'2)(R'3)-R'4(IV)

[0237] Formula (IV) wherein ALK represents a (Ci-C4)alkylene group, linear or branched, preferably linear such as propylene, R'2 and R'3, identical or different, preferably identical, represent a (Ci-C4)alkyl group such as methyl, and R'4 represents a (Ci-C6)alkyl group, linear or branched, preferably at C4 such as n-butyl, n represents an integer greater than or equal to 2, preferably the value of n is such that the weight-average molecular weight of the polydimethylsiloxane ranges from 500 to 3000 g.mol'. Examples of polydimethylsiloxanes (IV) include those sold under the names "MCR-A11" and "MCR-A12" by the company Gelest.

[0238] The (poly)amine compound(s) may be diaminated, i.e., may contain two primary and / or secondary amine groups, preferably primary (NH2). More particularly, they may be selected from compounds of formulas (V) and (VI):

[0239] ALK[(O-ALK')m-NH2]2 (V) or

[0240] H2N-ALK-Si(R')2-[O-Si(R')2]mO-Si(R)2-ALK'-NH2 (VI)

[0241] formulas (V) and (VI) wherein ALK and ALK', identical or different, represent a (Ci-C6)alkylene group, linear or branched, preferably linear such as propyl, R', identical or different, represents a (Ci-C4)alkyl group such as methyl, m being an integer greater than or equal to 0, preferably the value of m is such that the weight-average molecular weight of compound (V) or (VI) ranges from 500 g.mol1 to 55000 g.mol1. Examples of compounds of formula (VI) include those sold under the names "DMS-A11", "DMS-A12", "DMS-A15", "DMS-A21", "DMS-A31", "DMS-A32" and "DMS-A35" by the company Gelest.

[0242] The (poly)amine compound(s) which are diaminized are particularly chosen from among the diaminized polyethers in particular of formula H2N-ALK-O-[ALK'-O]m-ALK”-NH2 with ALK, ALK' and ALK”, identical or different representing a (Ci-C6)alkylene group, linear or branched, and m representing an integer greater than or equal to 0, such as 4,7,10-trioxa-l,13-tridecanediamine or the compounds; in particular known under the reference Jeffamine of the Huntsman company; and more particularly polyethylene glycol and / or polypropylene glycol a, co-diamine (with amine function at the end of the chain) such as those sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003.

[0243] The (poly)amine compound(s) may be triamine, i.e., may contain three primary and / or secondary amine groups, preferably primary (NH2). More particularly, triamine polyethers may have the formula ALK'”[(O-ALK')m-NH2]3, with ALK' as defined above, ALK'” representing a trivalent (Ci-C6)alkylene group, linear or branched, and m representing an integer greater than or equal to 0.

[0244] As (poly)amine compounds which are triamined, triamine polyethers, known under the reference Jeffamine from the Huntsman company, are particularly cited; and in particular polyethylene glycol and / or polypropylene glycol a, co-diamine (with amine function at the end of the chain) such as those sold under the names Jeffamine T-403.

[0245] As (poly)amine compounds which are triamined, triamine polyethers are particularly cited, and in particular polyethylene glycol and / or polypropylene glycol a, co-triamine (with amine function at the end of the chain) such as those sold under the names Jeffamine T-403.

[0246] The (poly)amine compound(s) may comprise more than three primary and / or secondary amine groups, preferably primary (NH2).

[0247] When the (poly)amine compound(s) have more than three primary and / or secondary amine groups, they may be chosen from poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary lateral amine functions, such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl) methacrylate.

[0248] In addition, the polyamine compounds can be selected from chitosans (in particular poly(D-glucosamine)), and polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains.

[0249] When the (poly)amine compound(s) are selected from chitosans (in particular poly(D-glucosamine)), and polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains, they may in particular be selected from poly(alkylene (C2-C5)imines), and preferably polyethyleneimines and polypropyleneimines, in particular poly(ethyleneimine), in particular that sold under reference 408700 by Aldrich Chemical or under the trade name Lupasol by BASF, in particular with a molecular weight between 1,200 and 25,000 g.mol poly(allylamine), in particular that sold under reference 479136 by Aldrich Chemical; polyvinylamines and their copolymers, in particular with vinylamides, in particular vinylamine / vinylformamide copolymers such as those marketed under the name Lupamin® 9030 by BASF; polyamino acids with NH2 groups such as polylysine, in particular that sold by JNC Corporation (formerly Chisso); amino dextran, in particular that sold by CarboMer Inc; polyvinyl amino alcohol, in particular that sold by CarboMer Inc; acrylamido(Ci-C6)alkylamine-based copolymers, in particular acrylamidopropylamine-based copolymers; and poly(D-Glucosamine), for example, sold under the reference Kionutrime CSG® by Kytozyme.

[0250] Polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains may be selected from the following formulas (VII):

[0251] Ra-Si(Rb)(Rc)-O-[Si(Rb)(Rc)-O]m-[Si(ALK1-NH2)(Ra)-O]n-Si(Rb)(Rc)-Ra(VII)

[0252] formula (VII) wherein Ra, identical or different, represents a hydroxyl or (Ci-C4)alkyl group, Rb and Rc, identical or different, preferably identical, represent a (Ci-C4)alkyl group such as methyl, ALK1 represents a (Ci-C6)alkylene group, linear or branched, optionally interrupted by an N(H) group, m and n are integers greater than or equal to 1, preferably m and n are such that the average molecular mass by weight of the compound of formula (VII) ranges from 1000 g.mol1 to 500000 g.mol1.

[0253] Preferably, formula (VII) is such that Ra, Rb, and Rc represent a methyl group, ALK1 represents a propylene group, and the values ​​of n and m are such that the weight-average molecular weight of the polydimethylsiloxane ranges from 1000 g.mol1 to 55000 g.mol'. Examples of polydimethylsiloxanes of formula (VI) include those sold under the names "AMS-132", "AMS-152", "AMS-162", "AMS-163", "AMS-191", and "AMS-1203" by the company Gelest.

[0254] Advantageously, formula (VII) is such that Ra represents a hydroxyl or (Ci-C4)alkyl group such as methyl, ALK1 represents a (C5-C6)alkylene group substituted by an NH group, preferably ALK1 represents -(CH2)3-N(H)-(CH2)2-, and m and n are such that the weight average molecular mass of the compound of formula (VI) ranges from 5000 g.mol1 to 500000 g.mol1.

[0255] As an amino polymer, polytetrahydrofuran (or polytetramethylene glycol) α, co-diamine, polybutadienes α, co-diamine may also be cited.

[0256] The (poly)amine compound(s) may be selected from hyperbranched polymers comprising at least one amino group and dendrimers bearing at least one amino group such as PAMAM polyamidoamine dendrimers with an ethylenediamine core and a terminal amine function.

[0257] Preferably, the (poly)amine compound(s) iii) are chosen from among non-polymeric (poly)amine diaminic compounds, non-polymeric (poly)amine triamine compounds, diaminic polymers, triamine polymers, polyamine polymers having more than 3 amine functions and mixtures thereof; more particularly among polymeric or non-poly)amine diaminic or triamine compounds or having more than 3 primary amine functions.

[0258] More preferably still, the (poly)amine compound(s) iii) are chosen from spermidine, triamine polyethers in particular polyethylene glycol and / or polypropylene glycol α,co-triamine (with terminal amine function), diaminopropanols, chitosans, polyamino acids in particular polylysine, and mixtures thereof.

[0259] Better still, the (poly)amine compound(s) iii) are chosen from spermidine, diaminopropanols, triamine polyethers, chitosans, polylysines and mixtures thereof; even better still from 1,3-diaminopropan-2-ol, spermidine, polyethylene glycol and / or polypropylene glycol α,co-triamine with terminal amine function such as the Jeffamines T marketed by the Huntsman company and in particular Jeffamine T403, polylysines and mixtures thereof.

[0260] Preferably, the total content of (poly)amine compound(s) iii) present in a composition is in the range of 0.01% to 60% by weight, preferably 0.1% to 50% by weight, more preferably 0.5% to 40% by weight, even more preferably 1% to 35% by weight, relative to the total weight of the composition comprising it / them.

[0261] Preferably, the total content of (poly)amine compound(s) selected from among diaminated (poly)amine compounds, triamined (poly)amine compounds, and mixtures thereof, present in a composition, is within the range of 0.01% to 60% by weight, preferably from 0.1% to 50% by weight, more preferably from 0.5% to 40% by weight, even more preferably from 1% to 35% by weight, relative to the total weight of the composition comprising them.

[0262] Preferably, the total content of (poly)amine compound(s) selected from diaminopropanols, triamine polyethers, and mixtures thereof, present in a composition, is in the range of 0.01% to 60% by weight, preferably 0.1% to 50% by weight, more preferably 0.5% to 40% by weight, even more preferably 1% to 35% by weight, relative to the total weight of the composition comprising them.

[0263] Preferably, when the (poly)amine compound(s) iii) and the compound(s) i) of formula (I) are present in the same composition, the weight ratio of the total content of compound(s) i) of formula (I) to the total content of (poly)amine compound(s) is in the range of 0.1 to 10; more preferably of 0.5 to 5; better of 0.8 to 2. Organic solvent

[0264] According to the process of the invention, the composition or compositions applied to the keratin fibers after step P may optionally include further one or more organic solvents.

[0265] Examples of organic solvents include: a) C2-C6 alkanols, such as ethanol and isopropanol; b) water-miscible polyols at room temperature (25 °C), in particular polyols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, such as glycerin, propylene glycol, 1,3-propanediol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, diglycerin; c) polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether; and d) aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0266] According to the invention, organic solvents do not carry an amine or thiol function and are in particular different from amino-alkanols such as diaminopropanols.

[0267] Preferably, the organic solvent(s) are chosen from polyols, preferably from polyols having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms, such as ethanol or glycerin.

[0268] Advantageously, the composition or compositions applied after step P are aqueous or hydroalcoholic (advantageously an ethanol / water mixture in particular in a volume ratio of between 1 / 99 to 99 / 1, more particularly between 10 / 90 to 90 / 10, even more particularly between 20 / 80 and 80 / 20, preferably 40 / 60 to 60 / 40 such as 50 / 50).

[0269] Preferably, the total content of organic solvent(s) in a composition applied after step P is in the range of 1% to 90% by weight, more preferably 30% to 80% by weight, more preferably 35% to 70% by weight, and even better 40% to 60% by weight, relative to the total weight of the composition.

[0270] Preferably, the composition(s) applied after step P, further include water.

[0271] Preferably, the total water content in a composition applied after step P is in the range of 1% to 99% by weight, more preferably 2% to 95% by weight, more preferably 3% to 90% by weight, relative to the total weight of the composition.

[0272] Preferably, when a composition applied after step P includes water, the pH of this composition is between 5 and 12, more preferably between 5 and 9, more preferably still between 6 and 8, better between 6.5 and 7.5.

[0273] The pH can be adjusted to the desired value by means of alkalizing agents or acidifying agents commonly used.

[0274] Examples of acidifying agents include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acids.

[0275] Among the alkalizing agents, ammonia, mineral or organic hydroxides can be cited.

[0276] The composition(s) applied after step P may also contain additives commonly used in cosmetics, such as antifoaming agents, thickening agents, moisturizing agents, clays, mineral fillers, UV filters, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, vitamins, preservatives, silicones, waxes, and their mixtures. These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

[0277] A person skilled in the art shall take care to choose any such additives and their quantities so that they do not impair the properties of the compositions of the present invention.

[0278] The use of this or these compositions applied after step P can be done on wet or dry hair, in rinsed or unrinsed mode.

[0279] The composition(s) applied after step P may optionally be formulated as a suspension, dispersion, gel, emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or multiple emulsion (W / O / W or polyol / O / W or O / O / O), in the form of a cream, foam, stick, vesicle dispersion, in particular of ionic or non-ionic lipids, bi-phase or multi-phase lotion. Process

[0280] The process according to the invention is a process for coloring keratin fibers comprising:

[0281] - at least one application step P on said keratin fibers of a composition comprising at least one protease-type enzyme, then

[0282] - the application to said keratin fibers, in one or more steps, of The following ingredients, included in one or more separate compositions:

[0283] i) at least one acetoacetate functional compound of formula (I) as defined above; and

[0284] ii) at least one coloring agent as defined above;

[0285] iii) at least one (poly)amine compound as defined above.

[0286] Step P, which involves applying a composition comprising at least one protease-type enzyme, is a pretreatment step. It is necessarily applied before the application of the other ingredients i), ii) and iii) to the keratin fibers.

[0287] The application step P can be carried out on dry or wet keratin fibers, as well as on all types of keratin fibers, light or dark, natural or colored, permed, bleached or straightened.

[0288] Step P is generally carried out at room temperature (between 15 and 30°C).

[0289] Step P may optionally be carried out after the application of shampoo.

[0290] After the completion of step P, a mechanical action may optionally be exerted on the hair such as combing, brushing, passing the fingers, preferably combing.

[0291] After completing step P, and possibly after combing, a setting time can be carried out.

[0292] In particular, during the exposure time, one can wait between 1 minute and 1 week, preferably between 5 minutes and 4 days, more preferably between 10 minutes and 2 days.

[0293] The setting time, after the completion of step P, can be carried out with a heating step for example at a temperature greater than or equal to 30°C.

[0294] After step P, the keratin fibers can be rinsed with water or undergo one or more shampooings, preferably the keratin fibers undergo one or more shampooings after step P.

[0295] After step P, and after possibly a setting time and then possibly rinsing with water or applying one or more shampoos, the keratin fibers can be left to air dry or dried, for example at a temperature greater than or equal to 30 °C.

[0296] The process according to the invention may further, after step P, include a step of applying heat to the keratin fibers using a heating tool.

[0297] The heat application step of the process of the invention can be carried out using a helmet, a hair dryer, a straightening or curling iron, or a Climazon. Preferably, the heat application step of the process of the invention is carried out using a hair dryer.

[0298] During the heat application step on the keratin fibers, a mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0299] When the heat application step on the keratin fibers is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

[0300] Preferably, if the keratin fibers are dried after step P, they are dried with an airflow in addition to the application of heat. This airflow during drying improves the individualization of the deposit.

[0301] After step P, the process of the invention implements one or more application steps of ingredients i), ii) and iii). This or these steps are said to be the keratin fiber coloring step(s).

[0302] According to one embodiment of the invention, ingredients i), ii) and iii) can be applied simultaneously to the keratin fibers.

[0303] According to another embodiment, ingredients i), ii) and iii), are applied successively to the keratin fibers.

[0304] Ingredient(s) i) may be applied in a first step to the keratin fibers, then ingredient(s) ii) may be applied in a second step to the keratin fibers, it being understood that ingredient(s) iii) may be applied together with i) and / or ii).

[0305] Ingredient(s) i) may be applied in a first step to the keratin fibers, then ingredient(s) iii) may be applied in a second step to the keratin fibers, it being understood that ingredient(s) ii) may be applied together with i) and / or iii), preferably together with i).

[0306] Ingredient(s) ii) may be applied in a first step to the keratin fibers, then ingredient(s) i) may be applied in a second step to the keratin fibers, it being understood that ingredient(s) iii) may be applied together with i) and / or ii).

[0307] Ingredient(s) iii) may be applied in a first step to the keratin fibers, then ingredient(s) i) may be applied in a second step to the keratin fibers, it being understood that ingredient(s) ii) may be applied together with i) and / or iii).

[0308] Preferably, ingredients i), ii) and iii) are applied simultaneously to the keratin fibers.

[0309] Ingredients i), ii) and iii) may be present in the same composition.

[0310] Ingredients i), ii) and iii) may also be present in compositions distinct.

[0311] Preferably, ingredients i), ii) and iii) are present in separate compositions. According to a preferred embodiment, the separate compositions containing ingredients i), ii) and iii) are mixed before application to the keratin fibers (i.e. extemporaneous mixing).

[0312] More preferably, ingredients i), ii) and iii) are present in at least two separate compositions, preferably in two separate compositions.

[0313] The ingredient(s) i) may be present in a first composition A and the ingredients ii) and iii) may be present together in a second composition B distinct from composition A.

[0314] Ingredients i) and ii) may be present together in a first composition A and ingredient(s) iii) may be present in a second composition B distinct from composition A.

[0315] The ingredient(s) i) may be present in a first composition A, the ingredient(s) ii) may be present in a second composition B distinct from composition A, and the ingredient(s) iii) may be present in a third composition C, distinct from compositions A and B.

[0316] Preferably, ingredients i) and ii) are present in a first composition A and ingredient(s) iii) are present in a second composition B distinct from composition A.

[0317] More preferably, the process of the invention comprises an application step T of a composition (CT) obtained from the mixture onto said keratin fibers. extemporaneous of a composition A comprising the compound(s) of formula (I) and the colorant(s) described above, with a composition B comprising the (poly)amine compound(s) described above; the application step T being carried out after said application step P.

[0318] According to a preferred embodiment, compositions A and B as defined above are mixed preferably less than 15 minutes before application to keratin fibers, more preferably less than 10 minutes before application, even more preferably less than 5 minutes before application.

[0319] The weight ratio between composition B and composition A is preferably from 0.1 to 10, more preferably from 0.5 to 5, even more preferably from 0.8 to 2.

[0320] Preferably, the application of the composition(s) on the keratin fibers during the coloring step is carried out by any conventional means such as a comb, fingers or by deposition techniques such as an aerosol.

[0321] After applying the composition(s) to the keratin fibers during the coloring step, the keratin fibers can be dried. Preferably, the keratin fibers are dried using a drying device such as a hood dryer, a hairdryer, or a climazon. When the drying step is carried out with a hood dryer or a hairdryer, the drying temperature is above 40°C.

[0322] After the drying step, a shaping step of the keratin fibers can be carried out using a keratin fiber shaping device such as a flat iron, a crimping or curling iron, or a steam iron, preferably a flat iron or a steam iron. Preferably, the shaping step is carried out at a temperature above 100°C. The iron can be applied to the keratin fibers in successive touches separated by a few seconds, or by progressive movement or gliding along the keratin fibers. Preferably, the iron is applied in a continuous movement from the root to the tip of the keratin fibers, in one or more passes.

[0323] After the staining step, a rinsing step of the keratin fibers can be carried out.

[0324] The term "rinsing step" refers to the application of water to the keratin fibers.

[0325] Preferably, no rinsing step is implemented after the coloring step. Multi-compartment device (kit)

[0326] The present invention also relates to a device for staining keratin fibers comprising several compartments containing: - a first compartment comprising a composition (CP) containing at least one protease-type enzyme as defined previously; - a second separate compartment containing at least one ingredient i) as defined above and possibly at least one ingredient ii) as defined above; preferably not containing any ingredient iii) as defined above; - a third separate compartment containing at least one ingredient iii) as defined above and possibly at least one ingredient ii) as defined above; preferably not containing any ingredient i) as defined above; and - possibly at least one fourth compartment containing at least one ingredient ii) as defined above; provided that at least one of the compartments contains at least one ingredient ii) as defined above.

[0327] Preferably, the device according to the invention contains: - a first compartment comprising a composition (CP) containing at least one protease-type enzyme as defined previously; - a second separate compartment containing at least one ingredient i) as defined above and at least one ingredient ii) as defined above; preferably not containing any ingredient iii) as defined above; - a third separate compartment containing at least one ingredient iii) as defined above and possibly at least one ingredient ii) as defined above; preferably not containing any ingredient i) as defined above; and - possibly a fourth compartment containing at least one ingredient ii) as defined above, preferably the device according to the invention not containing a fourth compartment. Examples Preparation of compounds

[0328] The compounds of formula (I) as described below are used in the compositions exemplified below:

[0329] Compound of formula (I) #1: Sucrose with acetoacetate function (8eq)

[0330] The compound of formula (I) #1 was synthesized according to the following scheme:

[0331] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular the 8 RI radicals represent -C(O)-CH2-C(O)-CH3

[0332] In a three-necked IL flask equipped with mechanical stirring and a distillation column, 100 g of sucrose and 406.55 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 4 h. After 4 h, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated in a rotary evaporator at 150°C under continuous vacuum. A viscous, orange-yellow liquid is obtained, which, upon analysis, corresponds to the expected product.

[0333] Compound of formula (I) #2: K-FLEX 7301 marketed by KING Industrie

[0334]

[0335] Polyamine compounds as described below are used in the Examples of compositions are given below: [Tables2] Polyamine Compound 1 Polyamine Compound 2 Spermidine CAS number: 124-20-9 Supplier: Sigma Aldrich 8-PolyLysine CAS number: 25988-63-0 Supplier: JNC Corporation H 0 nh2 H n h2n n Compound (Poly)amine 3 1,3-diaminopropane-2-ol CAS number: 616-29-5 Supplier: Fischer scientific HO^ NH2 Example 1

[0336] Compositions 1 to 7 as described in Tables 3 and 4 have been prepared: quantities are expressed as % mass of raw material as is, unless otherwise stated. Ingredients Formulas 1 2 3 4 5 Proteinase K(1) 0.1 - - - - hepes(2) q.s. 100 - - - - Sodium Chloride (pH = 7) 0.9 - - - - Tween 20 (pH = 7) 0.1 - - - - Sucrose Acetoacetate (Compound of formula (I)#l) - 8.8 - 16.0 - Spermidine - - 5.5 - - 8-PolyLysine(3) - - - - 32.0 Red Iron Oxide - 3.5 - 12.0 - Water / Ethanol (1 / 1 w / w) - q.s. 100 q.s. 100 q.s. 100 - Water - - - - q.s. 100

[0337] [Table 3]

[0338] (1) sold by Sigma Aldrich under the trade name “Proteinase K from Tritirachium album”

[0339] (2) sold by Sigma Aldrich (concentrated at 0.05 mol.L1 in water, pH = 7)

[0340] (3) sold by JNC Corporation (concentrated at 25% in water, pH = 7)

[0341] [Tables4] Ingredients Formulas 6 7 K-FLEX 7301 9.8 - 1.3 diaminopropane-2-ol - 3.5 Red iron oxide 2.0 - Water / ethanol (1 / 1 w / w) qsp 100 qsp 100

[0342] A composition Cl was prepared by mixing in a bowl and with a brush, formula 2 and formula 3, according to the weight ratio formula 2 / formula 3 of 1:1.

[0343] A composition C2 was prepared by mixing in a bowl and with a brush, formula 4 and 5, according to the weight ratio formula 4 / formula 5 of 2:1.

[0344] Formula 1 has also been used alone and is referred to as Tl in the following.

[0345] The compositions Tl, Cl and C2 are summarized in Table 5 below:

[0346] [Tables5] Compositions Mixture of formulas (Weight ratio) Tl Formula 1 Cl Formulas 2 + 3 (1:1) C2 Formulas 4 + 5 (2:1)

[0347] Protocol:

[0348] Two processes were implemented on 1g strands of damaged hair.

[0349] According to process 1, composition Tl (formula 1) was first applied to the Hair strands are prepared at a ratio of 5 g of the mixture per gram of strand. The strands are then covered with transparent plastic film for 42 hours at a temperature of 33°C. The strands undergo two repeated shampoos according to Shampoo Protocol 1 described below, referred to as Shampoo Protocol 1. After the two shampoos, the strands are blow-dried at 60°C.

[0350] Composition Cia was then applied to the strands previously treated with composition Tl at a rate of 1 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0351] According to process 2, water was applied to the hair strands at a rate of 5 g of composition per gram of strand. The strands were then covered with transparent plastic film for 42 hours at a temperature of 33°C. The strands underwent two repeated shampooings as described in Shampoo Protocol 1 described later. After the two shampooings, the strands were dried with a hairdryer at 60°C.

[0352] The Cia composition was then applied to the hair strands at a rate of 1 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0353] The process 1, hereinafter referred to as process PI, is a process according to the invention.

[0354] The process 2, hereinafter referred to as process P2, is a process according to the invention.

[0355] Two other processes were implemented on strands of 90% white, natural and cleansed hair.

[0356] According to process 3, composition T1 was first applied to the hair strands at a rate of 10 g of composition per gram of strand. The strands were then covered with transparent plastic film for 1 hour at a temperature of 33°C. The strands underwent two repeated shampooings as described in the shampooing protocol 1 described later. After the two shampooings, the strands were dried with a hairdryer at 60°C.

[0357] Composition C2 was then applied to the strands previously treated with composition T1 at a rate of 0.6 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0358] According to process 4, water was applied to the hair strands at a rate of 10 g of composition per gram of strand. The strands were then covered with transparent plastic film for 1 hour at a temperature of 33°C. The strands underwent two repeated shampooings as described in the shampooing protocol described later in section 1. After the two shampooings, the strands were dried with a hairdryer at 60°C.

[0359] Composition C2 was then applied to the hair strands at a rate of 0.6 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0360] The process 3, hereinafter referred to as process P3, is a process according to the invention.

[0361] Process 4, hereinafter referred to as process P4, is a comparative process. Shampoo Protocol 1

[0362] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then squeezed dry between two fingers.

[0363] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently massaging the strands of hair along their length (6 passes) for 15 seconds, from root to tip.

[0364] The strands of hair are then placed in a watch glass and left to rest for 1 minute.

[0365] Next, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then squeezed dry between two fingers before the next shampoo.

[0366] The processes applied are summarized in Table 6 below:

[0367] [Tableauxô] Processes Application of compositions PI (invention) Tl + C1 P2 (comparative) Water + Cl P3 (invention) Tl + C2 P4 (comparative) Water + C2 Results

[0368] The rise in colour was evaluated in the CIE L*a*b* system, using a Minolta CM3600D spectrophotometer (illuminant D65, angle 10°, specular component included).

[0369] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0370] The color uptake is assessed by the color difference AE between uncolored strands and after coloring. The higher the AE value, the greater the color uptake on the hair. The AE value is calculated according to the following equation: âE = V(i' - i»') 2 + (' - a0') 2 + (b* -

[0371] In this equation, L*, a* and b* represent the values ​​measured after hair coloring, and Lo*, a0* and b0* represent the values ​​measured before hair coloring.

[0372] The results are summarized in Table 7 below:

[0373] [Tables7] Processes Before coloring After coloring AE Lo* a0* b0* L* a* b* PI (invention) 55.98 -0.23 9.90 33.98 25.51 18.17 34.85 P2 (comparative) 55.98 -0.23 9.90 38.25 23.06 16.77 30.06 P3 (invention) 55.87 -0.13 11.51 30.17 25.74 18.72 37.17 P4 (comparative) 55.87 -0.13 11.51 30.58 23.34 17.25 34.98

[0374] The hair strands treated by the PI process according to the invention show a better color rise than the hair strands treated by the comparative P2 process.

[0375] The hair strands treated by the P3 process according to the invention show a better rise in colour than the hair strands treated by the comparative P4 process. Example 2

[0376] The compositions Tl, Cl and C2 are used again in the context of example 2.

[0377] In addition, a C3 composition was prepared by mixing in a bowl and with a brush, formula 6 and formula 7, according to the mass weight ratio formula 6 / formula 7 of 1:1.

[0378] The compositions used in Example 2 are summarized in Table 8 below:

[0379] [Tables8] Compositions Mixture of formulas (Weight ratio) Tl Formula 1 Cl Formulas 2 + 3 (1:1) C2 Formulas 4 + 5 (2:1) C3 Formulas 6 + 7 (1:1)

[0380] The PI to P4 processes as described in Example 1, have also been implemented in Example 2.

[0381] In addition, in this example 2, process 5 was carried out on strands of 90% white, natural and cleansed hair.

[0382] According to process 5, composition T1 was first applied to the hair strands at a rate of 10 g of composition per gram of strand. The strands were then covered with transparent plastic film for 10 minutes at a temperature of 33°C. The strands underwent two repeated shampooings according to Shampoo Protocol 2 described below and referred to as Shampoo Protocol 2. After the two shampooings, the strands were dried with a hairdryer at 60°C.

[0383] Composition C2 was then applied to the strands previously treated with composition T1 at a rate of 0.6 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0384] The process 5, referred to as process P5 hereafter, is a process according to the invention.

[0385] In addition, another process was implemented on strands of natural hair and 1g dry.

[0386] According to process 6, water was applied to the hair strands at a rate of 0.6 g of composition per gram of strand. The strands were then covered with transparent plastic film for 30 minutes at a temperature of 33°C. The strands underwent two repeated shampooings as described in Shampoo Protocol 2 described later. After the two shampooings, the strands were dried with a hairdryer at 60°C.

[0387] Composition C3 was then applied to the strands previously treated with composition T1 at a rate of 1 g of composition per gram of strand, using a pipette, distributing the composition on both sides of the strands. The strands were then dried with a hairdryer for 3 minutes, using a comb.

[0388] Process 6, referred to as process P6 hereafter, is a comparative process. Shampoo Protocol 2

[0389] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then squeezed dry between two fingers.

[0390] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently massaging the strands of hair along their length (6 passes) for 15 seconds, from root to tip.

[0391] The strands of hair are then placed in a watch glass and left to rest for 1 minute.

[0392] Next, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then squeezed dry between two fingers before the next shampoo.

[0393] The processes implemented in Example 2 are summarized in Table 9 below:

[0394] [Tables9] Processes Application of compositions PI (invention) Tl + C1 P2 (comparative) Water + Cl P3 (invention) Tl (1 hour) + C2 P4 (comparative) Water + C2 P5 (invention) Tl (10 minutes) + C2 P6 (invention) Water + C3

[0395] Each strand of hair treated by one of the processes PI to P6 was then subjected to 5 cycles of shampooing according to the shampoo protocol 2 above, in order to evaluate the tenacity (the persistence) to shampooing of the colour obtained.

[0396] Once the 5 cycles are completed, the hair strands are combed and dried. Results

[0397] The persistence of the color of the highlights was evaluated in the CIE L*a*b* system, using a Minolta CM3610d spectrophotometer (illuminant D65, angle 10°, specular component included).

[0398] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0399] Color permanence is assessed by the color difference AE between the colored strands before 5 shampooing cycles, and then after 5 shampooing cycles. The lower the AE value, the more the color persists through shampooing. The value of AE is calculated according to the following equation: âE = V(P - L^y + (a« - ayy + (b' - Ky In this equation, L*, a* and b* represent the values ​​measured after hair coloring and after undergoing the 5 shampoo cycles, and Lo*, a0* and b0* represent the values ​​measured after hair coloring but before the 5 shampoo cycles.

[0400] The results are summarized in Table 10 below:

[0401] [TableauxlO] Process After coloring After 5 shampoos AE Lo* a0* bo* L* a* b* PI (invention) 33.98 25.51 18.17 38.54 24.45 17.94 4.69 P2 (comparative) 38.25 23.06 16.77 48.14 10.00 11.72 17.14 P3 (invention) 30.17 25.74 18.72 32.20 24.49 17.82 2.54 P4 (comparative) 30.58 23.34 17.25 32.51 21.54 15.35 10.75 P5 (invention) 29.16 24.07 17.13 32.51 21.54 15.35 4.56 P6 (comparative) 37.83 23.81 19.42 55.02 1.24 11.46 29.5

[0402] Hair strands treated with the PI process according to the invention exhibit improved retention compared to horse strands treated with the comparative P2 process. Hair strands treated with the P3 and P5 processes according to the invention exhibit improved retention compared to horse strands treated with the comparative P4 process.

Claims

1. Demands A process for coloring keratin fibers comprising: - at least one application step P on said keratin fibers of a composition (CP) comprising at least one protease-type enzyme, then - the application to said keratin fibers, in one or more steps, of the following ingredients i), ii) and iii), which are included in one or more separate compositions: i) at least one compound of the following formula (I): in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or their combinations, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (CrC4)alkyl group; - X is a heteroatom or group chosen from O, S, N(R') or , -S- CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-; - n denotes an integer from 2 to 10, particularly from 3 to 9; and ii) at least one coloring agent selected from pigments, direct dyes, and mixtures thereof; and iii) at least one (poly)amine compound.

2. A method according to claim 1, characterized in that the protease-type enzyme(s) of said composition (CP) are selected from aminopeptidases, dipeptidases, dipeptidyl-peptidases, tripeptidyl-peptidases, peptidyl-peptidases, serine-type carboxypeptidases, metallocarboxypeptidases, cysteine-type carboxypeptidases, omega peptidases, serine endopeptidases, cysteine ​​endopeptidases, aspartic endopeptidases, metalloendopeptidases, threonine endopeptidases, and mixtures thereof; preferably the protease(s) are selected from serine endopeptidases, cysteine ​​endopeptidases, aspartic endopeptidases, aminopeptidases, and mixtures thereof, more preferably still from keratinases.

3. A process according to claim 1 or 2, characterized in that the total content of protease-type enzyme(s) in said composition (CP) is in the range of 0.0001% to 20% by weight, preferably 0.0005% to 10% by weight, more preferably 0.001% to 5% by weight, even more preferably 0.005% to 2% by weight, better 0.01% to 1% by weight, even better 0.05% to 1% by weight, relative to the total weight of the composition (CP).

4. A method according to any one of the preceding claims, wherein the compound(s) of formula (I) are selected from those of the following formula (la): (la) | OO in which: - R1 is as defined in claim 1, particularly represents a C2 to C1M hydrocarbon polyvalent radical, preferably C3-C12, preferably C4-C1O, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxyl groups OH, and / or b) optionally interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), preferably interrupted by one or more oxygen atoms in which R' is as defined in the preceding claim; - R2 is as defined in claim 1, preferably R2 represents a linear or branched (Ci-C6)alkyl group, preferably a (Ci-C4)alkyl group, more preferably methyl or tert-butyl such as methyl; and - n denotes an integer ranging from 2 to 10, preferably ranging from 2 to 9.

5. A method according to any one of the preceding claims, wherein the compound(s) of formula (I) are such that R1 represents: - a C6-C8 multipurpose hydrocarbon radical, linear or branched, unsaturated monocyclic or bicyclic, preferably monocyclic, optionally aromatic such as phenyl, - a C5-C12 multipurpose hydrocarbon radical, saturated monocyclic or bicyclic, optionally interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), wherein R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, preferably interrupted by one or more oxygen atoms; preferably R1 represents a monosaccharide or polysaccharide motif, in particular a disaccharide, on which n hydroxyl groups have been substituted by n -OC(O)-CH2-C(O)-R2 groups with R2 and n as defined in any one of claims 1 and 4, or - a versatile acyclic hydrocarbon radical in C2 to Ci2, preferably in C3-Ci0, linear or branched, saturated or unsaturated, preferably saturated.

6. A method according to any one of the preceding claims, wherein the compound(s) of formula (I) are such that:

7. n denotes an integer from 2 to 9, more particularly n denotes an integer from 3 to 9, more particularly from 4 to 9, such as 6 or 8. A method according to any one of the preceding claims, wherein the compound(s) of formula (I) are selected from the following compounds: (Compound) V CAS Chemical Name Chemical Structure (1) 700865-73-2 3-oxo-1,1-(1.7-heptanediyl) ester, of butanoic acid f; oqo (2) 632336-20-0 3-oxo-l,r-(l,8-octanediyl) ester, of butanoic acid x'' "■'•...Z' butanoic acid ester s- ' v'"' -X'' AA" (4) 174498-06-7 3-oxo-l,1-(1,3-propanediyl) butanoic acid oo ç ç ''■T** '"'"'N-'-''" (5) 160187-52-0 3 -oxo-1,2-dimethyl-1,2-ethyl-1,2-edyl ester of butapoic acid: (0 145020-19-5 3-oxo-2-buty-2-ethyl 1-1,3-propaediyl ester of butanoic acid 9 / :: i* z (7) 87530-36-7 3-oxo-14,2,2-tetramethyl-1,2-ethanediyl butanoic acid ester (8) 58213-75-5 3-oxo-14'-(1-methyl-1,3-propanediyl) butanoic acid ester O < ■■X x X,x. (9) 58213-74-4 3~oxo-l.l'-[2,2-dimethyl-1-(1-methylethyl)-1,3-n 9 VX / Y X'x' 'X propanediyl] ester of butanic acid (10) 39564-28-8 3-oxo-1,1'-(1,5-pentanediyl) ester of butanoic acid J 1 (H) 14276-67-6 3-oxo-14'-(2,2-dimethyl-1,3-propanediyl) ester of butanoic acid 0 < vx (12) 13018-41-2 3-oxo-1,4-butanediyl ester of butanoic acid. ç 9 XX X (13) 6079-90-9 3-oxo-1-methyl-1,2-ethanediyl ester of butanoic acid VV'x •-'^x x' (14) 5459-04-1 3-oxo-1,2-ethanediyl ester of butanoic acid 0 G (15) 2388-18-3 3 -oxo-1,1'- (1,6-hexanediyl) butanoic acid ester 3-oxo-1,6-hexanediyl acid ester (16) 32818-60-3 butanoic acid (9CI) bis(3-oxobutanoate) of l,l'-[2,2-Bis[(l,3-dioxobutoxy)methyl 1] -1,3-propanediyl] (17) 51980-20-2 bis(3-oxobutanoate) of 1,1-(2,2-Bis(hydroxymethyl)-1,3-propanediy 1] (18) (19) 130973-05-6 3-oxo-l,3,5- benzenetriyl ester of butanoic acid (20) 3-oxo-1,.2,4- 139264-86-1 benzenetriyl butanoic acid ester (21) 22208-25-9 Triethylolpropane triacetate K-FLEX 7301 (22) 2360524-48- (23) 66229-33-2 3 -oxo-2-butyI-2-[( 1.3-çüoxobuto^ 1,3-propanediyi butanoic acid ester (24) 1579231-50- 7 4,4-dimethyl-3 -oxo-, l,r-[2,2-bis[[(4,4-dimethyl-1,3-dioxqpentyl)oxy]m^ yl]-1,3-propanediyl] acid ester pentanoic. (25) 6079-98-7 tris(3-oxobutanoate) of l,l,r'-(l,2,3-propanetriyl) ü G 0 0 1: :! ' I) / Vy L o (26) tetra-acetoacetate of meso-erythritol j Qx n A— ° À >y 0^ O __ / --0 O- / A 0 T (27) 169533-29-3 aD-Glucopyranose, 1,2.notate) en-3.4 ?,6 § ''''y'" Y '*'■**' YTY 0'^' x- (28) 2254710-55- 5-amino-2- [[2.3,4-tris-O-(l,3-dioxobutyl)-D-xylopyranos'yljoxy] vx,dX.J benxacide (29) 1236300-10- 9 2,3.4,6-tetr?.kis(3~ oxobutanoate) of aDG^jçogyraji.ç§ide, 1,3,4,6-tetrakis-O-( 1,3-dipxpbutyl)-SSÎX-XX-Sfl.x-fel ......X^XM......k ,1. YY "Y~( (30) 96481-26-4 D-Gycopyranose, pentakis(3-oxobutanoate) 1 1 ,i.....LXV " (31) 944473-12-5 D-Glucitol, 1,4:3,6-diahydrobisate.( C3,0-ifo-butate >…..s “ (32) 2254710-49- 9 YwÇ'si î SX\ (33) sorbitol hexa-acetoacetate (34) D-Glucitol, 4-OpD-216756-89-7 galactopyranosyl-, polyacetoacetate with RI chosen from -C(O)-O2-C(O)-CH3,H with at least two RI radicals present - C(O)-GH2-C(O1-CH3 (35) 101655-52-1 Sucrose, polyacetoacetate with RI chosen from -C(O)-CH2-C(O)-CH3, H with at least two radicals RI represent -C(O)-CH2-C(O)-CH3

8.

9. in which RI, identical or different, represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent a -C(O)-CH2-C(O)-CH3 group, preferably at least three RI radicals represent a -C(O)-CH2-C(O)-CH3 group. A process according to the preceding claim, characterized in that the compound(s) of formula (I) are chosen from compounds (16), (18), (21), (35), (36), (37), (38), (39), (40), (46), and mixtures thereof; preferably from compounds (16), (21), (35), (38), (39), (46), and mixtures thereof; even more preferably from compounds (21), (35), (46), and mixtures thereof. A process according to any one of the preceding claims, characterized in that the content of compounds of formula (I) in a composition, is included in the range of 0.1% to 40% by weight, preferably 0.5% to 30% by weight, more preferably 1% to 25%, even more preferably 2% to 20% by weight, relative to the total weight of the composition containing it(s).

10. A method according to any one of the preceding claims, characterized in that the coloring agent(s) are chosen from pigments.

11. A process according to any one of the preceding claims, characterized in that the total content of coloring agent(s) in a composition is in the range of 0.001% to 20% by weight, preferably from 0.005% to 15% by weight relative to the total weight of the composition comprising it / them.

12. A process according to any one of the preceding claims, characterized in that the (poly)amine compound(s) are selected from spermidine, diaminopropanols, triamine polyethers, chitosans, polylysines and mixtures thereof; preferably from 1,3-diaminopropan-2-ol, spermidine, polyethylene glycol and / or polypropylene glycol α,co-triamine with terminal amine function, polylysines and mixtures thereof.

13. A method according to any one of the preceding claims, characterized in that the total content of (poly)amine compound(s) in a composition is in the range of 0.01% to 60% by weight, preferably from 0.1% to 50% by weight, more preferably from 0.5% to 40% by weight, even more preferably from 1% to 35% by weight, relative to the total weight of the composition comprising it / them.

14. A process according to any one of the preceding claims, characterized in that it comprises an application step T on said keratin fibers of a composition (CT) resulting from the extemporaneous mixing of a composition A comprising said compound(s) of formula (I) and said coloring agent(s), with a composition B comprising said (poly)amine compound(s); the application step T being carried out after said application step P.

15. A device for staining keratin fibers comprising several compartments containing: - a first compartment comprising a composition (CP) containing at least one protease-type enzyme as defined in claims 1 or 2; - a second separate compartment containing at least one ingredient i) as defined in any one of claims 1 and 4 to 8 and optionally at least one ingredient ii) as defined in claims 1 or 10; preferably not containing any ingredient iii) as defined in claims 1 or 12; - a third separate compartment containing at least one ingredient iii) as defined in claims 1 or 12 and optionally at least one ingredient ii) as defined in claims 1 or 10; preferably not containing any ingredient i) as defined in any one of claims 1 and 4 to 8; and - possibly at least one fourth compartment containing at least one ingredient ii) as defined in claims 1 or 10; provided that at least one of the compartments contains at least one ingredient ii) as defined in claims 1 or 10.