FR2959934A1 - HAIR COLORING COMPOSITION COMPRISING CHROMANIC AND / OR CHROMENIC COLORANTS - Google Patents

Abstract

The invention relates to a dyeing composition for keratinous fibers, such as human keratinous fibers, and in particular the hair, comprising: one or more dyes chosen from chromenic dyes, chroman dyes, and mixtures thereof, one or several zinc salts, one or more organic compounds which are liquid at a temperature of 25 ° C and at atmospheric pressure (760 mmHg) and have a Hansen δH parameter value at 25 ° C of less than 16 MPa, and benzoic acid and / or one or more of its salts, the composition containing no chemical oxidant, other than oxygen from the air, as well as a method of use and its use.

Description

B10 / 0041EN GD / CV / SM OA 10 162

The invention relates to a fiber coloring composition. The invention relates to a composition for coloring fibers. The invention relates to a hair coloring composition. The invention relates to a hair coloring composition. keratinic compounds comprising one or more dyes chosen from chroman dyes, chroman dyes and mixtures thereof, one or more zinc salts, benzoic acid and / or one or more of its salts and one or more particular compounds.

The invention also relates to a process using said composition and to the use of said composition. It is known to dye keratinous fibers, and in particular human hair, with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho or para-phenylenediamines. aminophenols and heterocyclic compounds. These oxidation bases are generally associated with couplers. These bases and couplers are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. This type of oxidation dye makes it possible to obtain permanent dyes, but it leads to a degradation of the keratin fibers by the use of oxidizing agents. Furthermore, it is known to dye keratinous fibers, and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes which are used are in particular nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane or natural dyes. These dyes are colored molecules or dyes having a certain affinity for keratinous fibers. The compositions containing one or more direct dyes are applied to the keratinous fibers for a time necessary to obtain the desired coloration, and then rinsed. The resulting colorings are particularly chromatic colorations, which are however temporary or semi-permanent, because the nature of the interactions, which bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration. Nowadays, hair dyeing processes using natural products are more and more appreciated by users. It is known from FR 2 549 721 to use natural dyes for hair dyeing. However, the method described still needs to be improved in terms of efficiency. In addition, it is known to use organically grown inorganic zinc salts in hair dyeing as oxygen oxidation dye catalysts of air from specific oxidation dye precursors. In EP 335 403, the zinc salts are used for the gentle oxidation of hair by tannins such as catechin or tannic acid. In patents and patent applications FR 2 814 943, EP 1 424 060 and EP 1 210 931, the zinc salts are used in a catalytic system also comprising hydrogen carbonates to develop the color of oxidation dye precursors of the ortho type. -diphénols. Documents DE 4209897 and FR 2 722 685 also disclose oxidation dyeing processes based on indole or indoline compounds and zinc salts. However, these zinc derivatives are systematically used in oxidizing media. There is therefore a real need to develop hair coloring compositions leading to powerful colorings, low selective, resistant to external agents, in particular resistant to light, shampoo and weather, respecting the nature of the hair, from compositions containing natural dyes. This object is achieved by the present invention which relates to a coloring composition of keratin fibers, such as human keratin fibers, and in particular the hair, comprising: one or more dyes chosen from chroman dyes, chroman dyes, and their mixture - one or more zinc salts, - benzoic acid and / or one or more of its salts and - one or more organic compounds which are liquid at 25 ° C and at atmospheric pressure (760 mm Hg) having a value of the Hansen 6H parameter at 25 ° C lower than 16 Mpa ~ 2, the composition containing no chemical oxidant, other than oxygen in the air, with the exception of the following compositions ( % in g of MA) A Hemateine [l] 1% Chlorophyline [2] 0.19% Curcumin [3] 0.58% Sorghum 0.34% Ethanol 15% Benzyl alcohol 4% Benzoic acid 0.2 pH agent qsp pH = 8.8 Perfume qs Water qs 100 % (% in g of MA) BC Hemateine [1] 0.3% 0.3% Curcumin [2] 0.5% 0.5 % Chlorophylline [3] 0.15% 0.15% Sorghum 0.02% 0.02% Laccaic acid 0.01% 0.01% Ethanol 15% 16% Benzyl alcohol 5% 1% 3-phenyl-1-propanol - 0.5% 2-phenyl-1-ethanol - 1 % Benzoic acid 0.5 0.5% my Hydroxyethyl cellulose (MW: 720.000) 2% 2% [4] pH agent qsp pH = 8.8 qsp pH = 8.8 Perfume qs qs Water qs 100% qs 100% in combination with a phosphate composition zinc at 1% in zinc element. The subject of the invention is also a process for dyeing keratinous fibers, such as human keratinous fibers, and in particular the hair, comprising the application to said fibers of said composition in one or more steps. The invention finally relates to the use of said composition and a kit comprising said composition. Other features, aspects and advantages of the present invention will appear on reading the detailed description which follows. The composition according to the invention must not comprise any chemical oxidant other than oxygen in the air. By chemical oxidant is meant hydrogen peroxide, urea, alkali metal bromates, persalts such as perborates and persulfates. The dyes used in the composition according to the invention are dyes chosen from chroman dyes and chroman dyes.

According to the invention, the term "chromenic or chromanic dye" is intended to mean dyes which comprise in their structure at least one bicycle of formula (A) below: A the intracyclic bond representing a single carbon-carbon bond or a carbon-carbon double bond , as illustrated by the formula Al denoting the family of chromanes and the formula A2 denoting the family of chromanes below: Al A2

More particularly, the dyes of formula (A) are chosen from the dyes of the following formulas: -formula (I), comprising in its structure the bicycle of formula A2, R 4 OH 2 (I) HO in which: - represents a simple carbon-carbon bond or a carbon-carbon double bond, the linking of these bonds 10 denotes two simple carbon-carbon bonds and two carbon-carbon double bonds, said bonds being conjugated, X represents a grouping: // / HO- C or O = C - R ', R 2, R 3, R 4, R 5 and R 6, which may be identical or different, independently of one another represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group or an optionally substituted alkoxy group; or an optionally substituted acyloxy group, as well as its tautomeric and / or mesomeric forms, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its hydrates; and -formula (II), comprising in its structure the bicycle of formula Al OR12 R18 in which: -R11, R12, R13, R16, R19 and R20, identical or different, represent, independently of one another, a hydrogen atom; or a C1-C4 alkyl radical, -R14, R15, R17 and R18, which may be identical or different, represent, independently of one another, a hydrogen atom, a hydroxyl radical or a C1-C4 alkoxy radical, as well as its forms; tautomers and / or mesomers, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its hydrates. Regarding the dyes of formula (I) as defined above, these can be in two tautomeric forms noted (Ia) and (Ib): HO HO The alkyl radicals mentioned in the preceding definitions of the substituents are hydrocarbon radicals, saturated , linear or branched, generally C 1 -C 20, especially C 1 -C 10, preferably C 1 -C 6, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above, and preferably the alkoxy radicals are Ci-Cio, such as methoxy, ethoxy, propoxy and butoxy. The alkyl or alkoxy radicals, when substituted, may be substituted with at least one substituent carried by at least one carbon atom, chosen from: a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C 1 -C 10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a hydroxyl group, an amino group optionally substituted by one or two optionally substituted C 1 -C 3 alkyl radicals , said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which may or may not be different from nitrogen; quaternary ammonium -N + R'R "R" ', M- for which R', R ", R" ', which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical; preferentially methyl; an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-alkyl radical; -C2; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical; C1-C4, a phenyl radical; an aminosulfonyl radical ((R) 2 N-SO 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, - a radical; carboxylic acid in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; 9 - a nitro group; a carboxy or glycosylcarbonyl group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy group; and a phenyl group optionally substituted by one or more hydroxyl groups. By glycosyl radical is meant a radical derived from a mono or polysaccharide.

Preferably, the alkyl or alkoxy radicals of formula (I) are unsubstituted. According to one particular embodiment of the invention, the dyes of formula (I) comprise an R 6 radical representing a hydroxyl group.

Another particular embodiment of the invention relates to the dyes of formula (I), for which the radical R 1 represents a hydrogen atom or a hydroxyl group. More particularly, the composition according to the invention comprises one or more dyes of formula (I) chosen from hematoxylin, haematein, brazilin, braziline, santalines, santarubines and their tautomeric and / or mesomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, as well as hydrates.

HO HO HO O OH H HO HO Hemeinine Braziléine HO HO OH O HO H HOHO Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) CAS 474-07-7) and their forms tautomers and / or mesomers, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, as well as the hydrates. Braziline is a conjugated form of a chromanic compound of formula A2. The diagram below shows the tautomeric structures (Ia) and (Ib) illustrated above. Among the hematoxylin / haematin and brazilin / braziline dyes, mention may be made by way of example of haematoxylin (Natural Black 1 according to the INCI name) and brazilin (Natural Red 24 according to the INCI name), dyes of the family of Indochromanes, which are commercially available. These may exist in an oxidized form and be obtained by synthesis or by extraction of plants or plants known to be rich in these dyes.

The dyes of formula (I) can be used in the form of extracts. The following plant extracts (genus and species) may be used: Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extraction of various parts of plants, such as, for example, the root, the wood, the bark or the leaf. According to a particular embodiment of the invention, the natural dyes of formula (I) are derived from logwood wood, pernambuco wood, sappan wood and brazil wood.

As regards the dyes of formula (II), the dyes used in the present invention are preferably those for which R 11 and R 13 represent an alkyl radical, preferably methyl. Preferably, R12, R16, R19 and R20 denote, independently of one another, a hydrogen atom or an alkyl radical, preferably methyl. Preferably, R14 and R17 denote, independently of one another, a hydrogen atom or an alkoxy radical, preferably methoxy. Preferably, R 18 and R 15 denote, independently of one another, a hydrogen atom, a hydroxyl radical or an alkoxy radical, preferably methoxy. A first particularly preferred family of dyes suitable for the present invention is that of the dyes of formula (II) above for which R12, R15, R16, R17, R19 and R20 each represent a hydrogen atom. R11 and R13 each represent a methyl radical and R14 represents a methoxy radical. Among the preferred dyes of this first family are those for which R18 represents a methoxy (santaline B) or hydroxy (santaline A) radical. A second particularly preferred family of dyes suitable for the present invention is that of the dyes of formula (II) above for which: -R11 and R13 each represent a methyl radical, -R17 represents the methoxy radical. A preferred dye of this second family is that for which, in addition, R19 represents a methyl radical, R20, R12, R14, R18 and R16 each represent a hydrogen atom, and R15 represents the hydroxyl radical (santarubine A).

A second preferred dye of this second family is that for which R18, R20, R12, R14 and R16 represent a hydrogen atom, R15 represents a methoxy radical and R19 represents a methyl radical (Santarubine B). A third preferred dye of this second family is that for which R 20, R 12, R 14, R 15, R 16 and R 19 represent hydrogen and R 18 represents the hydroxyl radical (santarubine C). Another preferred dye of this second family is that for which R15 represents a methoxy radical, and R18 and R14 represent a hydrogen atom and R20, R12, R16 and R19 represent a methyl radical (tetra-O-methylcantarubine). The dyes of formula (II) can be used in the form of extracts. Redwood plant extracts can be used, generally including Asian and West African redwood species of the genus Pterocarpus and the genus Raphia. These woods are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Raphia nitida. These woods can still be called padauk, sandalwood (sandalwood), narrawood, camwood or barwood.

Thus, usable extracts containing dyes of formula (II) in the present invention may for example be obtained from red sandalwood (Pterocarpus santalinus) by aqueous basic extraction, such as the product sold under the trade name Sandalwood Concentrate. SL 709C by the company COPIAA or else by means of a solvent extraction of sandalwood powder such as the product sold under the trade name Sandalwood Powder SL PP by the same company COPIAA. We can also mention the hydroalcoholic extract of Sandalwood powder red ALBAN MULLER company. Extracts also suitable for the present invention can be obtained from woods such as Camwood (Raphia nitida) or Barwood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus fractionated and then ground: a conventional alcoholic extraction or percolation is then carried out on this ground material to collect a powdery extract particularly suitable for the implementation of the present invention. The salts of the dyes of formula (I) and (II) of the invention may be cosmetically acceptable salts of acids or bases. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid leading to the chlorides. The bases can be mineral or organic. Especially the bases are alkali hydroxides, such as sodium hydroxide leading to sodium salts. Preferably, the dye (s) of formula (I) and (II) included in the composition according to the invention are derived from plant extracts. It is also possible to use mixtures of plant extracts. The natural extracts of the dyes according to the invention can be in the form of powders or liquids. Preferably, the extracts are in powder form. Preferably, the chromenic or chromanic dyes used are chosen from haematein, hematoxylin, brasiline, brasiline, santaline A. Even more preferentially, it is preferred to use the dyes of formula (I), and more particularly the haematein and brasiline. Preferably, the composition according to the invention comprises from 0.001% to 20% by weight of dyes chosen from chromene dyes, chroman dyes and their mixture relative to the total weight of the composition, preferably from 0.01% to 10% The composition according to the invention also comprises one or more zinc salts (Zn).

The zinc salts according to the invention may be of organic or mineral nature. When the zinc salt is an organic acid salt, it may contain one or more carboxylic acid (-COOH) and / or sulfonic acid (-SO3H), and / or phosphonic acid (-H2PO3), and / or acid functions. phosphinic (-H2PO2 or = HPO2), and / or phosphinous acid (= POH). Preferably, the organic acid according to the invention contains one or more carboxylic acid and / or sulphonic acid functions. The organic acid according to the invention may be saturated or unsaturated, linear, branched or cyclic. The zinc salt and organic acid according to the invention may in particular be chosen from zinc gluconate, zinc lactate, zinc glycinate, zinc aspartate and zinc pyrrolidone carboxylate (more commonly known as zinc pidolate). zinc), zinc phenolsulfonate, zinc salicylate, zinc citrate, zinc acetate and mixtures thereof. For the purposes of the present invention, the term "inorganic salts" means inorganic salts, that is to say not having in their structure a carbon atom bonded to at least one hydrogen atom.

Mineral salts are salts resulting from the action of a mineral acid or a mineral base on zinc. Among the salts, mention may be made of halides such as chloride, fluoride and iodide; sulphate, phosphate, nitrate, carbonate, zinc perchlorate and mixtures thereof.

Preferably, the zinc mineral salts used are zinc sulfate, zinc phosphate and zinc chloride. The zinc mineral salts can be introduced in solid form in the compositions, or can come from natural water, mineral or thermal, rich in these ions or seawater (dead sea in particular). They may also come from mineral compounds such as earth, rocks, ochres such as clays (eg green clay) or even plant extract containing them, as described for example in document FR 2 814 943.

As mineral rock containing zinc salts, mention may be made of the following rocks: Boyleite (ZnMg) SO4-4H2O Changoite Na2Zn (SO4) 2-4H2O Clinohedrite CaZn [SiO4] -H2O Gaultite Na4Zn2Si7O18-5H2O Goslarite ZnSO4-7H2O Hardystonite Ca2Zn [Si2O7] Hopeite Zn3 (PO4) 2-4H2O Hydrozincite Zn5 [(OH) 31 CO3] 2 IMA2008-048 Zn6 (PO4) 4-7H2O Minrecordite CaZn (CO3) 2 Osakaite Zn4 (SO4XOH) 6-5H2O Parahopeite Zn3 (PO4) 2 -4H2O Parascholzite CaZn2 (PO4) 2-2H2O Scholzite CaZn2 (PO4) 2-2H2O Simonkolleite Zn5 [(OH) 8 C12] -H2O Skorpionite Ca3Zn2 [(OH) 2ICO31 (PO4) 2] -H2O Smithsonite ZnCO3 Spencerite Zn4 [OHIPO4] 2-3H2O Tarbuttite Zn2 [OHIPO4] Basic Zinc Sulfate Zn4SO4 (OH) 6-4H2O Hydrate Willemite Zn2 [SiO4] Zinc silicate Zn3 Si4O10 (OH) 2-4H2O Zinkosite ZnSO4 Particularly, the zinc salts of the invention are of degree of oxidation 2: Zn (II). Even more preferentially, the zinc salts are chosen from zinc gluconate, zinc citrate, zinc glycinate, zinc phosphate, zinc sulphate and zinc chloride. Preferably, the composition according to the invention comprises from 0.001% to 20% by weight of zinc salts relative to the total weight of the composition containing them, preferably from 0.05 to 10% by weight.

The composition according to the invention also comprises particular liquid organic compounds. The liquid organic compound (s) having a value of the Hansen solubility parameter 6H as defined previously are for example described in the reference work "Hansen solubility parameters A user's handbook, Charles M. Hansen", CRC Press, 2000, pages This value reflects the 6H solubility parameter related to the formation of hydrogen bonds. It can be recalled that there are three major types of interactions in organic compounds, nonpolar interactions, permanent dipole-dipole interactions and hydrogen bonding interactions, the latter being the subject of the parameter defining the organic compound. in the present invention. As examples of compounds corresponding to this definition, mention may be made of propylene glycol derivatives, alkylene carbonates, benzyl alcohol, 2-pentanol and mixtures thereof. In particular, mention may be made of the following compounds Denomination Chemical formula (Mpa / z) Dipropylene glycol CH3O [CH2CH (CH3) O] 2H 11.2 methylether Tripropylene glycol methyl CH3O [CH2cH (CH3) O] 3H 10.4 ether Propylene glycol n-butyl C4H90CH2CH ( CH3) OH 9.2 ether (PnB) Propylene glycol n-propyl C9H7OCH2CH (CH3) OH 9.2 ether (PnP) Dipropylene glycol CH3000 [CH2CH (CH3) O] 2 8.0 monomethyl ether acetate CH3 Benzyl alcohol C6HSCH2OH 13.7 Ethylene glycol 2-ethyl hexyl C8H17OCH2CH2OH 5.1 2-pentanol ether CH3CH (OH) C3H7 13.3 As alkylene carbonate, there may be mentioned compounds of the following chemical formula: ## STR2 ## in which R = H, C 1 -C 8 alkyl or C 1 -C 4 hydroxyalkyl. By way of example, mention may be made of ethylene carbonate (R = H), propylene carbonate (R = CH 3), glycerine carbonate (R = CH 2 OH) or even butylene carbonate (R = CH 2 CH 3 ). Of the alkylene carbonates of the invention, propylene carbonate is preferred. According to a particular embodiment, the value 6H is preferably less than 14 MPa According to a particularly preferred embodiment, the value of the component 6H is greater than 0 Mpa. According to one variant, the value of bH is greater than 3 Mpa Y2 preferably greater than 4 Mpa Y2. The composition of the invention generally comprises a quantity of liquid organic compounds having a Hansen 6 H parameter of less than 16 Mpa Y 2 of between 0.1 and 80%, preferably of between 0.5 and 50% and even more preferentially of between 1 and 80%. and 30% of the total weight of the composition. The composition according to the invention comprises benzoic acid and / or one or more of its salts.

The salts of the benzoic acid may be alkali metal or alkaline earth metal salts, an ammonium salt, ion salts derived from organic amine. Preferably, the benzoic acid salts are chosen from sodium benzoate and potassium benzoate. Preferably, the composition according to the invention comprises from 0.001% to 20% by weight of benzoic acid and / or one or more of its salts relative to the total weight of the composition containing them, preferably from 0.05 to 10% by weight. % in weight.

The composition according to the invention may be in various galenic forms, such as a lotion, a mousse, a cream, a gel or in any other form suitable for dyeing keratinous fibers. It can also be packaged in pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. The composition according to the invention may comprise a medium suitable for dyeing, also called coloring medium, which may contain water, a mixture of water and one or more organic solvents or a mixture of organic solvents.

According to a particular embodiment of the invention, the cosmetic composition (s) according to the invention contain water. As organic solvent, mention may be made of liquid organic compounds of 6H less than 16, defined above, as well as, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol. Organic solvents other than liquid organic compounds of 6H less than 16 are present in proportions, preferably between 1 and 40% by weight relative to the total weight of the dye composition, and even more preferably between 5 and 30. about% by weight.

The composition according to the invention may comprise one or more additional direct dyes. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes other than chromans and chromenes of the invention, direct quinone dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azine, triarylmethane, indoamine, methines, styryl , porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes.

Among the natural direct dyes other than chromen and chromenes of the invention, lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins may be mentioned. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular the poultices or extracts based on henna, chlorophylline, sorghum extract, and laccaic acid. The additional direct dye (s) in the composition according to the invention preferably represent from 0.001% to 10% by weight approximately of the total weight of the composition.

The composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition according to the invention. When the chromanic chromanic dye (s) and their mixtures are in an aqueous composition, the pH of this aqueous dye composition is between 2 and 12, and even more preferably between 4 and 12, and particularly between 7 and 12. This pH can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents of the compositions used in the invention, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkaline agents used according to the invention, mention may be made by way of example of ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxides of sodium or of potassium and the compounds of formula (III) below: ## STR2 ## in which W is a propylene residue optionally substituted with a hydroxyl group or a C 1 -C 4 alkyl radical; ; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the coloring process according to the invention are not not, or not substantially, impaired by the addition or additions envisaged. The invention also relates to a method for dyeing keratinous fibers, such as human keratinous fibers, and in particular the hair, comprising applying to said fibers a composition as defined above. According to a first particular embodiment of the invention, the dyeing process is carried out in a single step, by application to the keratinous fibers of a dyeing cosmetic composition comprising: one or more dyes chosen from chromenic dyes, dyes Chromium, and their mixture - one or more zinc salts, - benzoic acid and / or one or more of its salts and - one or more organic compounds which are liquid at 25 ° C and at atmospheric pressure (760 mm Hg) having a Hansen parameter 6H value at 25 ° C of less than 16 MPa A, the composition containing no chemical oxidant, other than oxygen in the air, except for the following compositions ( % in g of MA) A Hemateine [l] 1% Chlorophyline [2] 0.19% Curcumin [3] 0.58% Sorghum 0.34% Ethanol 15% Benzyl alcohol 4% Benzoic acid 0.2 pH agent qsp pH = 8.8 Perfume qs Water qs 100 % (% in g of MA) BC Hemateine [1] 0.3% 0.3% Curc umine [2] 0.5% 0.5% Chlorophylline [3] 0.15% 0.15% Sorghum 0.02% 0.02% Lecazole Acid 0.01% 0.01% Ethanol 15% 16% Benzyl alcohol 5% 1% 3-phenyl-1-propanol - 0.5% 2- phenyl-l-ethanol - 1% Benzoic acid 0.5 0.5% my Hydroxyethyl cellulose (MW: 720,000) 2% 2% [4] pH agent qsp pH = 8.8 qsp pH = 8.8 Perfume qs qs Water qs 100% qs 100% in combination with a zinc phosphate composition at 1 g% zinc element.

The previously defined cosmetic composition can be applied as it is to the keratinous fibers. It can also be ready-to-use and result from an extemporaneous mixture of at least two compositions, which can be presented in a dyeing kit. Advantageously, at least one of said compositions containing, together or separately, the ingredients is aqueous.

The exposure time is generally set between 3 and 120 minutes, preferably between 10 and 60 minutes, and more preferably between 10 and 45 minutes. According to a second particular embodiment of the invention, the dyeing process is carried out, in several steps, by application to the keratinous fibers of several dyeing cosmetic compositions containing, together or separately, in the said composition or compositions, the following ingredients: one or more dyes chosen from chromanic dyes, chroman dyes, and their mixture - one or more zinc salts, benzoic acid and / or one or more of its salts and one or more liquid organic compounds with the temperature of 25 ° C and at atmospheric pressure (760 mm Hg) having a value of the Hansen 6H parameter at 25 ° C lower than 16Mpa ~ 2, the composition containing no chemical oxidant, other than the oxygen of air, with the exception of the following compositions (% in g of MA) A Hemateine [l] 1% Chlorophylline [2] 0.19% Curcumin [3] 0.58% Sorghum 0.34% Ethanol 15% Benzyl alcohol 4% Benzoic acid 0 .2 pH agent qsp pH = 8.8 Perfume qs Water qs 100% 20 (% of MA) BC Hematein [1] 0.3% 0.3% Curcumin [2] 0.5% 0.5% Chlorophylline [3] 0.15% 0.15% Sorghum 0.02 % 0.02% Laccaic acid 0.01% 0.01% Ethanol 15% 16% Benzyl alcohol 5% 1% 3-phenyl-1-propanol - 0.5% 2-phenyl-1-ethanol - 1% Benzoic acid 0.5 0.5% my Hydroxyethyl cellulose (PM : 720,000) 2% 2% [4] pH agent qsp pH = 8.8 qsp pH = 8.8 Perfume qs qs Water qs 100% qs 100% in combination with a composition of zinc phosphate at 1g% in zinc element. These steps may or may not be separated by an intermediate rinse. In the absence of such an intermediate rinsing, it is possible to spin with a towel or paper in order to eliminate the excess composition. In a first variant of a two-step process, the first step consists in applying to said fibers a cosmetic composition i) comprising the selected chromenic chromenic dye (s), and mixtures thereof as defined above, and one or more liquid organic compounds having a value of the Hansen 6H parameter at 25 ° C. of less than 16 MPa Y 2, benzoic acid and / or one or more of its salts, then in a second step, to apply to said fibers a cosmetic composition ii) comprising a or more zinc salts as defined above. In a second variant of two-step keratinous fiber staining process, the first step consists in applying to said fibers a composition ii) comprising one or more zinc salts as defined above, then in a second step, to be applied to said fibers a second cosmetic composition i) comprising the chosen chromanic chromanic dye (s) and their mixtures as defined above, and one or more liquid organic compounds having a value of the Hansen 6H parameter at 25 ° C. of less than 16 MPa Y.sub.2, benzoic acid and / or one or more of its salts. According to another embodiment of the invention, at least one of the compositions used in the process of the invention is anhydrous and may be in pulverulent or pasty form. When the composition is in pulverulent form, it may contain pulverulent ingredients other than the compounds present in compositions i) and ii). When the composition is in the form of a paste, it may optionally contain one or more organic inert liquids, preferably chosen from liquid petroleum jelly, polydecenes and fatty esters which are liquid at room temperature (25 ° C.) and at atmospheric pressure (760 mmHg). When the process uses a single composition containing the compounds of compositions i) and ii) and this composition is anhydrous, the locks of hair, on which the composition will be applied, are previously moistened. For these last two processes, the exposure time after application of the cosmetic composition for the first step is generally set between 3 and 120 minutes, preferably between 10 and 60 minutes, and more preferably between 10 and 45 minutes. The exposure time after application of the second cosmetic composition for the second step is generally set between 3 and 120 minutes, preferably between 3 and 60 minutes, and more preferably between 5 and 30 minutes. Whatever the mode of application, the application temperature is generally between room temperature (15 to 25 ° C) and 80 ° C and more particularly between 15 and 45 ° C. Thus, it is advantageous, after application of the composition according to the invention, to subject the hair to a heat treatment by heating at a temperature of between 30 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. It is also possible to use, as a means for heating and smoothing the hair, a heating iron at a temperature between 60 and 220 ° C and preferably between 120 and 200 ° C. The invention also relates to the use of the composition according to the invention for the dyeing of keratinous fibers, such as human keratinous fibers, and in particular the hair. A kit or device may be used for carrying out the method according to the invention. The kit may comprise at least two compartments - a first compartment comprising a cosmetic composition i) the selected chromenic colorant (s), and mixtures thereof as defined above and mixtures thereof, and one or more liquid organic compounds having a value of the parameter 6H Hansen at 25 ° C less than 16 MPa Y 2, benzoic acid and / or one or more of its salts, and a second compartment comprising a cosmetic composition ii) containing one or more zinc salts as defined herein -above. According to one variant, the kit further comprises an additional composition comprising one or more treatment agents. The compositions of the kit are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges.

The kit mentioned above can also be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in the patent FR 2,586,913.

EXAMPLES OF COLORING Example 1: The following coloring compositions were prepared from the following ingredients in the following proportions indicated in grams of active material: Coloring compositions according to the invention 1 2 Hemeine * 1g 1g Curcumin (E100) - 0.6g Cupric chlorophyllin (E141) - 0.2g Sorghum extract 0.3g Benzyl alcohol 4g 4g Benzoic acid 0.2g 0.2g Ethanol 15g 15g Thickener 2g 2g pH agent Qsp pH = 8.8 Qsp pH = 8.8 Perfume qs qs Water qs 100g qs 100g * Hematéine CAS = 475-25-2, sold under the reference 10 51230 by Fluka Couples of locks of hair with 90% natural and permed white hair are treated successively by: 1. A 7% aqueous solution of zinc gluconate 15 (marketed by Seppic under the name GIVOBIO G Zn) which is allowed to stand for 10 minutes at room temperature and then the 2.1a coloring composition 1 or 2 is filtered off and left for 30 minutes at 40 ° C. After application of these treatments, the locks are rinsed, shampooed and dried. Intensely colored locks are obtained - in violet with the composition 1 - and in black with the composition 2 and whose colors are stubborn.

Claims (19)

REVENDICATIONS1. Coloring composition for keratinous fibers, such as human keratinous fibers, and in particular the hair, comprising: one or more dyes chosen from chromanic dyes, chromanic dyes, and their mixture - one or more zinc salts, benzoic acid and / or one or more of its salts and one or more liquid organic compounds at a temperature of 25 ° C and at atmospheric pressure (760 mm Hg) having a value of the Hansen 6H parameter at 25 ° C less than 16 MPa ~ 2, the composition containing no chemical oxidant, other than oxygen in the air, with the exception of the following compositions (% in g of MA) A Hemateine [l] 1% Chlorophyline [ 2] 0.19% Curcumin [3] 0.58% Sorghum 0.34% Ethanol 15% Benzyl alcohol 4% Benzoic acid 0.2 pH agent qsp pH = 8.8 Perfume qs Water qs 100% (% g MA) BC Hemateine [1] 0.3% 0.3% Curcumin [2] 0.5% 0.5% Chlorophylline [3] 0.15% 0.15% Sorghum 0.02% 0.02% Lactic Acid 0.01% 0.01% Ethanol 15% 16% Benzyl alcohol 5% 1% 3-phenyl-1-propanol - 0.5% 2-phenyl-1-ethanol - 1% Benzoic acid 0.5 0.5% my Hydroxyethyl cellulose 2% 2% (MW: 720,000) [4] pH agent qsp qsp pH = 8.8 pH = 8.8 Perfume qs qs Water qs qs 100% 100 % in combination with a composition of zinc phosphate at 1 g% zinc element. 2. Composition according to claim 1, characterized in that the dye is chosen from the compounds of the following formulas: -formula (I): HO in which: - represents a single carbon-carbon bond or a double carbon-carbon bond, l linking these bonds denotes two single carbon-carbon bonds and two carbon-carbon double bonds, said bonds being conjugated, X represents a group: // / HO-C or O = C-R1, R2, R3, R4, R5 and R6, which may be identical or different, represent, independently of one another, a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, optionally substituted alkoxy, or an optionally substituted acyloxy group, as well as its tautomeric forms and / or mesomers, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its hydrates; and -formula (II): R 15 OR 16 R 18 in which: R 11, R 12, R 13, R 16, R 9 and R 20, which are identical or different, represent, independently of one another, a hydrogen atom or an alkyl radical; C1-C4, -R, 4, R, 5, R17 and R18, which are identical or different, represent, independently of one another, a hydrogen atom, a hydroxyl radical or a C1-C4 alkoxy radical, as well as its tautomeric forms; and / or mesomers, its stereoisomers, its addition salts with an acid or a basecosmetically acceptable, and its hydrates. 3. Composition according to Claim 1 or 2, characterized in that the dye is chosen from hematoxylin, braziline, haematein, braziléine, santalines, santarubines and their tautomeric and / or mesomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, as well as hydrates. 4. Composition according to any one of the preceding claims, characterized in that the dye is chosen from haematein and brazilein of the following structure: HO HO and Heamine Braziléine HO and tautomeric forms and / or mesomers, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, as well as hydrates. 5. Composition according to any one of the preceding claims, characterized in that the dye (s) is (are) present in the composition in a content of between 0.001% and 20% by weight relative to the total weight. of the composition, preferably from 0.01 to 10% by weight. 6. Composition according to any one of the preceding claims, characterized in that the zinc salts are chosen from zinc gluconate, zinc citrate, zinc acetate, zinc lactate, zinc glycinate, aspartate. zinc, zinc pyrrolidone carboxylate (more commonly known as zinc pidolate), zinc phenolsulfonate, zinc salicylate and mixtures thereof, and preferably zinc gluconate, zinc glycinate and zinc citrate. 7. Composition according to any one of the preceding claims, characterized in that the zinc salts are chosen from zinc halide, sulphate, phosphate, nitrate, carbonate and perchlorate, and mixtures thereof, and preferably from sulphate, phosphate and zinc chloride. 8. Composition according to claim 6 or 7, characterized in that the (s) zinc salts is (are) present in the composition in a content of between 0.001% and 20% by weight relative to the total weight of the composition, preferably from 0.05 to 10% by weight. 9. Composition according to any one of the preceding claims, characterized in that the liquid organic compound is selected from propylene glycol derivatives, alkylene carbonates, benzyl alcohol, 2-pentanol and mixtures thereof. 10. Composition according to claim 9, characterized in that the propylene glycol derivatives are chosen from dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-butyl ether (PnB), propylene glycol n-propyl ether ( PnP), dipropylene glycol monomethyl ether acetate and ethylene glycol 2-ethyl hexyl ether. 11. Composition according to any one of the preceding claims, characterized in that the (s) organic compound (s) liquid (s) is (are) present in the composition in a content between 0, 1% and 80% by weight relative to the total weight of the composition, preferably from 0.5 to 50% by weight. 12. Composition according to any one of the preceding claims, characterized in that the salts of benzoic acid are chosen from sodium benzoate and potassium benzoate. 13. Composition according to any one of the preceding claims, characterized in that the benzoic acid and / or its salts is (are) present in the composition in a content of between 0.001% and 20% by weight relative to to the total weight of the composition, preferably from 0.05 to 10% by weight. 14. A process for dyeing keratinous fibers, such as human keratin fibers, and in particular the hair, characterized in that it comprises a step of applying to the keratin fibers a cosmetic composition as defined in any one of the claims. 1 to 13. 15. The method of claim 14, characterized in that it comprises only one step of applying the composition as defined in any one of claims 1 to 13. 16. The method of claim 14, characterized in that it comprises two steps consisting in the first step to be applied to the keratin fibers a cosmetic composition i) comprising one or more chromenic chromic dyes, and mixtures thereof as defined in any one of claims 1 to 5, and one or more organic compounds liquid at 25 ° C and at atmospheric pressure (760 mm Hg) having a Hansen 6H parameter value at 25 ° C of less than 16 MPa. / 2 as defined in any one of claims 1, 9 to 11, and benzoic acid and / or one or more of its salts as defined in any one of claims 1, 12 and 13, and in a second step of applying a cosmetic composition ii) comprising one or more zinc salts, as defined in any one of claims 1, 6 to 8. 17. The method of claim 14, characterized in that it comprises two steps consisting in the first step to be applied to the keratin fibers a composition ii) comprising one or more zinc salts, as defined in any one of claims 1, 6 to 8, then in a second step of applying a composition i) comprising one or more chromenic chromic dyes, and mixtures thereof as defined in any one of claims 1 to 5, and one or more organic compounds which are liquid at room temperature. at 25 ° C and at atmospheric pressure (760 mm Hg) having a value of the Hansen 6H parameter at 25 ° C of less than 16 MPa 1/2 as defined in any one of claims 1, 9 to 11 and benzoic acid and / or one or more of its salts as defined in any of claims 1, 12 and 13. 18. Use of the composition as defined in any one of claims 1 to 13 for dyeing keratinous fibers, such as human keratinous fibers, and in particular the hair. 19. Kit comprising at least two compartments -a first compartment comprising a cosmetic composition i) containing one or more chromanic chromanic dyes, and mixtures thereof as defined in any one of claims 1 to 5, and one or more liquid organic compounds having the temperature of 25 ° C. and at atmospheric pressure (760 mmHg) having a value of the Hansen 6H parameter at 25 ° C. of less than 16 MPa 1/2, as defined in any one of Claims 1, 9 to 11; and benzoic acid and / or one or more of its salts as defined in any one of claims 1, 12 and 13, a second compartment comprising a cosmetic composition ii) containing one or more zinc salts such as defined in any one of claims 1, 6 to 8.