KR20060021898A - Dye Lightening Compositions Containing One or More Cationic Direct Dyes Having Mixed Chromophores - Google Patents

Abstract

The present invention relates to a cationic mixed dye comprising several chromophores which are connected to each other via a linking group, at least two of which are different and exhibit an absorbance value between 400 and 800 nm, an amount such that the pH of the composition is greater than 7 And dyeing lightening compositions containing an alkali and oxidizing agent in a suitable dyeing medium. The present invention can obtain particularly resistant coloring.

Description

Dyeing Lightening Compositions Containing One or More Cationic Direct Dyes with Mixed Chromophores {TINCTORIAL BRIGHTENER COMPOSITION CONTAINING AT LEAST ONE DIRECTLY CATION COLORANT HAVING MIXED CHROMOPHORES}

The present invention relates to dyeing compositions containing cationic direct dyes comprising different chromophores, in particular compositions for lightening dyeing of keratin fibers. The invention also relates to a dyeing method using the composition and to the use of said composition for lightening keratinous fibers.

Dyeing keratin fibers, especially human hair, using dye compositions containing oxidative dye precursors commonly known as oxidizing bases, such as ortho- or para-phenylenediamine, ortho- or para-aminophenol and heterocyclic compounds Is a known practice. These oxide bases are colorless or light colored compounds which, when combined with oxidation products, can produce colored compounds by oxidative condensation processes.

In addition, the color tones obtained by such oxidizing bases can be varied by combining them with couplers or color modifiers, the latter of which in particular are aromatic meta-diamines, meta-aminophenols, meta-diphenols, and indole It is known to be selected from certain heterocyclic compounds such as compounds.

Various molecules used as oxidation bases and couplers allow the obtaining of a wide range of colors.

This oxidative dyeing method consists of applying a base or mixture of bases and couplers to an aqueous solution of hydrogen peroxide as an oxidant, leaving the mixture to act on the fibers, and then rinsing the fibers. The pigmentation resulting from it is permanent and resistant and strong against external factors, especially light, bad weather, cleaning, sweating and friction. The process, which is usually carried out at basic pH, can dye and simultaneously light the fibers, which is reflected in the possibility of obtaining a final pigmentation which is brighter than the original color in practical application. In addition, the lightening of the fibers produces a uniform color in the case of gray hair, and has the advantageous effect of revealing the color in the case of hair which is inherently colored, i.e. more revealing it.

It is also known practice to dye keratin fibers by direct dyeing. The method commonly used in direct dyeing consists of applying colored molecules having affinity for the fibers and direct dyes, which are colored molecules, to the keratin fibers, leaving the dye to act on the fibers, and then rinsing the fibers.

For example, it is known practice to use direct dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine, or dyes of the azo, xanthene, acridine, azine or triarylmethane type.

Such direct dyes may consist of one or more chromophores, which may be the same or different. Dyes consisting of several chromophores are described, for example, in the documents FR 1 540 423, EP 1 133 975, EP 1 133 976, US 5 708 151 and WO 02/078596.

Coloring caused by the use of direct dyes is temporary or semi-permanent coloration, which is characterized by the nature of the interaction of binding the direct dye to keratin fibers, and their desorption from the surface and / or core of the fiber and its poor staining power. Because of their poor wash-fastness and perspiration-fastness.

Certain direct dyes can be combined with oxidants, which makes it possible to obtain lightening of the fibers upon dyeing. For example, patent application EP 810 851 describes dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine type, which can be mixed immediately with the oxidizing composition at basic pH. have.

However, the coloration obtained is not always satisfactory with regard to color fastness. It disappears upon shampooing and leaves the lightened keratin fibers visible. In addition, when the dyeing composition directly contains a mixture of dyes, color changes over time occur due to the difference in affinity of each dye for keratin fibers and their resistance to external agents such as shampoos.

It is an object of the present invention to provide a direct dye which can be used for lightening dyeing but does not have the drawbacks of existing direct dyes. In particular, one of the objects of the present invention is to provide a direct dye which is sufficiently stable in the presence of an oxidizing agent and / or an alkaline agent, so that the lightening and dyeing of the fiber can be simultaneously obtained. Another object of the present invention is to allow a variety of shades to be obtained without the problem of color change over time and to make the keratin fibers dyed as strongly as when using an oxidizing dye and as stable to light as the oxidizing dye and in bad weather, cleaning and It is to provide a direct dye that is resistant to sweating and long-lasting.

The object is a cationic mixed dye comprising several chromophores linked together via a linking group, two or more of which are different and exhibiting one or more absorption maxima between 400 and 800 nm, the pH of the composition being 7 The invention is achieved with a single subject of a lightening dyeing composition comprising an alkalizing agent in an amount to be in excess, and an oxidizing agent in a suitable dyeing medium.

The subject of the present invention is also a dyeing method using the composition.

Another subject of the invention is the use of the composition of the invention, in particular for dyeing keratin fibers, in particular human keratin fibers, such as hair, to obtain good shampoo fastness.

In particular, the compositions of the present invention make it possible to obtain lightening of keratinous fibers and color fastness to various external agents, in particular shampoos. In addition, the composition makes it possible to avoid the problem of color changing over time.

Cationic mixed direct dyes useful in the present invention are particularly stable in lightening compositions containing alkali agents such as aqueous ammonia and / or oxidants such as hydrogen peroxide. In particular, when a mixed dye is used in a non-lightening composition, ie a composition that does not contain an alkali or any lightening agent, and the mixed dye is used as an alkali agent, for example aqueous ammonia or an oxidant, for example an aqueous solution of hydrogen peroxide. When used together with the containing composition or simultaneously with the alkali and oxidizing agents, the coloring of the hair ends is not substantially altered.

In the context of the present invention, the term "cationic mixed dye" refers to a dye whose positive charge may form the entire part of the chromophore and / or the linking group, or, alternatively, the positive charge is present through substituents of the chromophore and / or linking group. Means dye.

According to the present invention, the term “chromophore” refers to radicals derived from dyes, ie radicals of molecules having one or more absorption maxima in the visible range (400 nm to 800 nm), the absorption of which is associated with prior oxidation or other species Does not require any combination of).

For the purposes of the present invention, chromophores are said to be different when their chemical structures are different. Such chromophores may be chromophores derived from different classes or from the same class, provided they have different chemical structures. For example, chromophores can be selected from azo dyes, but the chemical structures of the radicals that make up them differ.

According to one specific embodiment, the mixed dye comprises one or more cationic chromophores, preferably two or more cationic chromophores, whose linking groups may be possibly cationic or noncationic.

Chromophores useful in the present invention include radicals derived from the following dyes: acridine, acridon, anthrone, anthrapyrimidine, anthraquinone, azine, azo, azomethine, benzanthrone, benzimi Dazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, benzoquinone, bis-azine, bis-isoindolin, carboxanilide, coumarin, cyanine (azacarbocyanine, diaza Carbocyanine, diazamemicyanine, hemicyanine and tetraazacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane, dithiazine, flavantron and flavone Flavonoids, fluorindine, formazan, hydrazone, especially arylhydrazone, hydroxy ketone, indamine, indanthrone, indigoid and pseudo-indigoid, indophenol, indoaniline, isoindolin, isoindolin, iso Indolinone, isoviola Tron, lactone, methine, naphthalimide, naphthanilide, naphtholactam, naphthoquinone, nitro dyes, in particular nitro (hetero) aromatic dyes, oxadiazoles, oxazines, perylenes, perinones, perylenes, phena Gin, phenothiazine, phthalocyanine, polyene / carotenoid, porphyrin, pyrantrone, pyrazolanthrone, pyrazolone, pyrimidinoanthrone, pyranine, quinacridone, quinoline, quinophthalone, squaranes, steel Ben, tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane, xanthene.

As chromophores useful in the present invention, even more particularly, radicals derived from the following dyes may be mentioned: acridine, acridon, anthrone, anthraquinone, azine, azo, azomethine, benzanthrone, benzoquinone, bis -Azine, cyanine (azacarbocyanine, diazacarbocyanine, diazahemicyanine, hemicyanine and tetraacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine, diphenylmethane, dithiazine Flavonoids such as flavantrons and flavones, formazan, hydrazones, especially arylhydrazones, indamines, indanthrones, indigoides and pseudo-indigoides, indophenols, indoanilines, isobiolatrons, methines, naphthalimides , Naphtholactam, naphthoquinone, nitro dyes, especially nitro (hetero) aromatic dyes, phenazines, phenothiazines, phthalocyanines, polyene / carotenoids, porphyrins, pyrazolones, quinacridones, quinophthalones, te La imidazolium, thiazine, thioindigo, thio fatigue Nin, triarylmethane, xanthene.

Among the nitro chromophores that can be used according to the invention, radicals derived from the following compounds can be mentioned in a non-limiting manner:

1,4-diamino-2-nitrobenzene

1-amino-2-nitro-4- (β-hydroxyethylamino) benzene

1-amino-2-nitro-4-bis (β-hydroxyethyl) aminobenzene

1,4-bis (β-hydroxyethylamino) -2-nitrobenzene

1-β-hydroxyethylamino-2-nitro-4-bis- (β-hydroxyethylamino) benzene

1-β-hydroxyethylamino-2-nitro-4-aminobenzene

1-β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) aminobenzene

1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene

1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene

1,2-diamino-4-nitrobenzene

1-amino-2-β-hydroxyethylamino-5-nitrobenzene

1,2-bis (β-hydroxyethylamino) -4-nitrobenzene

1-amino-2- [tris (hydroxymethyl) methylamino] -5-nitrobenzene

1-hydroxy-2-amino-5-nitrobenzene

1-hydroxy-2-amino-4-nitrobenzene

1-hydroxy-3-nitro-4-aminobenzene

1-hydroxy-2-amino-4,6-dinitrobenzene

1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene

1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene

1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene

1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene

1-β-hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene

1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene

1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene

1-β-hydroxyethylamino-3-methyl-2-nitrobenzene

1-β-aminoethylamino-5-methoxy-2-nitrobenzene

1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

1-hydroxy-2-chloro-6-amino-4-nitrobenzene

1-hydroxy-6-bis (β-hydroxyethyl) amino-3-nitrobenzene

1-β-hydroxyethylamino-2-nitrobenzene

1-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Among the azo chromophores which can be used according to the invention, mention may be made of radicals derived from cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714 954.

Also mentioned are the radicals derived from the following azo dyes, described in the Color Index International Third Edition:

Disperse Red 17

Acid Yellow 9

Acid Black 1

Basic Red 22

Basic Red 76

Basic Yellow 57

Basic Brown 16

Acid Yellow 36

Acid Orange 7

Acid Red 33

Acid Red 35

Basic Brown 17

Acid Yellow 23

Acid Orange 24

Disperse Black 9

Also 1- (4'-aminodiphenylazo) -2-methyl-4- [bis (β-hydroxyethyl) amino] benzene and 4-hydroxy-3- (2-methoxyphenylazo) -1- Naphthalenesulfonic acid may be mentioned.

Among the quinone chromophores which may be mentioned, radicals derived from the following dyes:

Disperse Red 15

Solvent Violet 13

Acid Violet 43

Disperse Violet 1

Disperse Violet 4

Disperse Blue 1

Disperse Violet 8

Disperse Blue 3

Disperse Red 11

Acid Blue 62

Disperse Blue 7

Basic Blue 22

Disperse Violet 15

Basic Blue 99

And also the following compounds:

1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone

1-aminopropylamino-4-methylaminoanthraquinone

1-aminopropylaminoanthraquinone

5-β-hydroxyethyl-1,4-diaminoanthraquinone

2-aminoethylaminoanthraquinone

1,4-bis (β, γ-dihydroxypropylamino) anthraquinone.

Among the azine chromophores that may be mentioned are radicals derived from the following compounds:

Basic Blue 17

Basic Red 2

Among the indoamine chromophores which can be used according to the invention, mention may be made of radicals derived from the following compounds:

2-β-hydroxyethylamino-5- [bis (β-4′-hydroxyethyl) amino] anilino-1,4-benzoquinone;

2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone;

3-N (2'-chloro-4'-hydroxy) phenylacetylamino-6-methoxy-1,4-benzoquinoneimine;

3-N (3'-chloro-4'-methylamino) phenylureido-6-methyl-1,4-benzoquinoneimine;

3- [4'-N- (ethylcarbamylmethyl) amino] phenylureido-6-methyl-1,4-benzoquinoneimine.

Furthermore, mention may be made of the chromophores described in the documents US 5 888 252, EP 1 133 975, WO 03/029359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. In addition, a professional dictionary ["The chemistry of synthetic dye" (K. Venkataraman, 1952, Academic Press, vol. 1-7)], a professional dictionary ["Kirk-Othmer" "Chemical Technology", 1993, Wiley & Sons, chapter "Dyes and Dye Intermediate" and several chapters in the "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley & Sons.

Preferably, the chromophore is azo, xanthene, hydrazone, especially arylhydrazone, phenothiazine, acridine, cyanine, for example tetraazacarbocyanine, anthraquinone, methine, azomethine, diketopyrrolopyrrole, Indigoids and nitros, in particular nitro (hetero) aromatic chromophores.

According to one more specific embodiment, the chromophore is selected from azo, hydrazones, especially arylhydrazone, cyanine, for example tetraacarbocyanine, anthraquinone, methine, azomethine and nitro, in particular nitro (hetero) aromatic chromophores. do.

Mixed cationic dyes preferably comprise 2 to 4 different chromophores, preferably 2 or 3 different chromophores.

According to certain embodiments, the mixed dye is a cationic filler, which is at least di-cationic, produced by chromophores and / or linkers. According to a variant of this embodiment, at least two chromophores are cationic chromophores and the linking group is possibly cationic.

Preferably, the mixed dyes of the invention correspond to the formula:

Dye 1-L-Dye 2

[Wherein L is a cationic or noncationic linking group and Dye 1 and Dye 2 are different cationic chromophores].

Cationic chromophore (s) are typically chromophores containing quaternized nitrogen atoms.

The cationic chromophore is, for example, a chromophore comprising, directly or as a substituent: alkylammonium, imidazolium, pyridinium, quinolinium, acridinium, benzimidazolium, benzobistriazolium, benzo Pyrazolium (or indazolium), benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, Indoleum, Isoquinolinium, Naphthymidazolium, Naphtoxazolium, Naphthopyrazolium, Oxadiazolium, Oxazolium, Oxazolopyridinium, Phenazium, Phenoxazolium, Pyrazinium, Pyrazolium, Pyrazoyl Triazolium, pyridinoimidazolium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyryllium, triazium or xyllium radicals.

Preferably, the chromophore comprises directly or as substituents: alkylammonium, imidazolium, pyridinium, acridinium, benzimidazolium, benzopyrazolium (or indazolium), benzopyridazinium, b -Pyridinium, bis-tetrazolium, imidazopyridinium, indolium, naphthymidazolium, naphthopyrazolium, phenazinium, pyrazinium, pyrazollium, pyridinimidazolium, tetrazolium or xyllium radicals.

Examples of cationic chromophores useful in the present invention are already mentioned. Other examples are given in patent applications WO 95/01772, WO 95/15144, EP 714 954, EP 318 294 and WO 03/029359.

According to one variant, the mixed dye comprises a cationic azo chromophore. Such chromophores are described, for example, in EP 0 850 636, FR 2 788 433, EP 920 856, WO 99/48465, FR 2 757 385, EP-850 637, EP 918 053, WO 97/44004 , FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388 , DE 4 137 005, WO 01/66646, US 5 708 151, WO 95/01772, WO 95/15144, GB 1 195 386, US 3 524 842, US 5 879 413, EP 1 062 940, EP 1 133 976 , GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645, Acta Histochem. (1978), 61 (1), 48-52, Tsitologiya (1968), 10 (3), 403-5, Zh. Obshch. Khim. (1970), 40 (1), 195-202, Ann. Chim. (Rome) (1975), 65 (5-6), 305-14, Journal of the Chinese Chemical Society (Taipei) (1998), 45 (1), 209-211, Rev. Roum. Chim. (1988), 33 (4), 377-83, Text. Res. J. (1984), 54 (2), 105-7], Chim. Ind. (Milan) (1974), 56 (9), 600-3, Khim. Tekhnol. (1979), 22 (5), 548-53, Ger. Monatsh. Chem. (1975), 106 (3), 643-8, MRL Bull. Res. Dev. (1992), 6 (2), 21-7, Lihua Jianyan, Huaxue Fence (1993), 29 (4), 233-4, Ann. Chim. (Rome) (1975), 65 (5-6), 305-14, Dyes Pigm. (1992), 19 (1), 69-79, Days Pigm. (1989), 11 (3), 163-72.

In the context of the present invention, the term "linker" means an atom or group of atoms that separates the chromophore from the mixed dye. The atoms of the linking group are 30 nm relative to the absorption maxima of each chromophore whose position on the wavelength scale of the absorption maximum value (s) of the chromophore constituting the mixed dye is taken separately, ie not linked together via a linking group. It should be such that it changes more particularly not more than 15 nm, preferably not more than 10 nm, so as not to change beyond. The linking group may be cationic or noncationic. Preferably, the linking group is noncationic.

According to one variant, the linker is an atom or group of atoms that isolates each chromophore such that the electronic delocalization of each chromophore is stopped.

The linking group is, for example, C ₁ -C ₂₀ , preferably C ₁ -C ₁₄ , more particularly C ₁ -C ₆ , a linear, branched or cyclic, optionally substituted hydrocarbon-based chain, the carbon of said chain At least one of the atoms is possibly replaced with one or more heteroatoms such as sulfur, nitrogen, or oxygen and / or one or more groups, such as carbonyl groups, including heteroatoms, wherein the hydrocarbon-based chain is possibly unsaturated or One or more optionally substituted alkylene radicals; Optionally substituted arylene radicals; Optionally substituted divalent terephthalamide radical; Optionally substituted divalent heterocyclic radicals such as divalent triazine radicals, or —NH—CO— radicals.

Hydrocarbon-based chains, and alkyl (ene) radicals are, for example, one or more hydroxyl radicals, alkoxy radicals, in particular C1-C6 alkoxy radicals, C1-C6 (poly) hydroxyalkoxy groups, amino groups, one or more halogens, one Or an alkylamino group including one or more of the same or different C1-C6 alkyl radicals optionally having the above hydroxyl groups and the like.

Examples of linking groups that may be mentioned include the following: Alkylene, optionally substituted as indicated above, and optionally interrupted by groups containing one or more heteroatoms such as sulfur, nitrogen or oxygen, and / or heteroatoms such as carbonyl groups Radicals (C _n H _2n ), more particularly alkylene radicals having 1 to 14, preferably 1 to 6 carbon atoms, for example methylene, ethylene, propylene and the like; Optionally substituted (hetero) arylene radicals, such as optionally substituted phenylene or naphthylene, phenanthrylene, triazinyl, pyrimidinyl, pyridyl, pyridazinyl, or quinoxalinyl; Alkyl-aryl-alkyl radicals or alkyl-heteroaryl-alkyl radicals, more particularly having 1 to 6 carbon atoms.

The (hetero) arylene radicals mentioned above may be substituted with one or more of the following radicals: C1-C6 alkyl; C1-C6 alkoxy; C2-C6 (poly) hydroxyalkoxy; Amino; Or substituted with one or more identical or different C1-C6 alkyl radicals optionally having one or more hydroxyl groups and / or one or more C1-C6 alkyl, C1-C6 alkoxy, C2-C6 (poly) hydroxyalkoxy or amino groups, or one or more Amino substituted with a C6 aryl radical optionally substituted with an amino group substituted with one or more same or different C1-C6 alkyl radicals optionally having a hydroxyl group; Trifluoromethyl; Cyano; Alkylamido, in particular C1-C6 alkylamido; RCOO-, where R represents a C1-C6 alkyl radical.

More specific examples that may be mentioned include:

Wherein R may be H, CF ₃ , CO ₂ Me, CO ₂ Et, CN or CONH ₂ , and R ′ is one or more hydroxyl, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) hydride C ₁ -C ₈ alkyl radical optionally substituted with oxyalkoxy, amino, C ₁ -C ₂ (di) alkylamine or optionally substituted aryl radicals, hydrogen atom, R ″ represents one or more hydroxyl, C ₁ -C C ₁ -C ₄ alkyl radical optionally substituted with ₂ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy, amino, C ₁ -C ₂ (di) alkylamino or optionally substituted aryl radicals, hydrogen atom, n is greater than 0, more particularly 1 to 10, preferably 1 to 5; the electrical neutrality of the compound is ensured by at least one cosmetically acceptable anion An.

Linkers that may be mentioned include triazines described in WO 03/029359, alkylenes mentioned in US 5 708 151, and alkyl-aryl-alkyls described in US 5 708 151.

It should be noted that for the purposes of the present invention, any alkylene group in the main chain connecting Dye 1 / Dye 2 is considered to be a linking group.

An is an organic or inorganic anion, for example selected from: halides such as chloride, bromide, fluoride or iodide; Hydroxides, sulfates; Hydrogen sulfate; (C ₁ -C ₆ ) alkyl sulfates such as methyl sulfate or ethyl sulfate; Phosphate; Carbonates; Hydrogen carbonate; Perchlorate; acetate; Tartrate; Citrate; Oxalate; (C ₁ -C ₆ ) alkyl sulfonates such as methane sulfonate; Arylsulfonates optionally substituted with C ₁ -C ₄ alkyl radicals, for example 4-tolylsulfonate.

According to certain embodiments, the mixed dye may be represented by the following formula:

[Wherein L is a linking group as defined above and R 1 and R 1 ′ are at least one hydroxyl, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy, amino, C ₁ -C ₂ Independently selected from alkyl radicals optionally substituted with (di) alkylamino or optionally substituted aryl radicals, preferably C ₁ -C ₆ alkyl radicals and R 2 and R 2 ′ are at least one hydroxyl, C ₁ -C ₂ alkoxy, C ₁ -C ₆ alkyl radicals optionally substituted with C ₂ -C ₄ (poly) hydroxyalkoxy, amino or C ₁ -C ₂ (di) alkylamino radicals; Independently selected from optionally substituted phenyl radicals; An represents one or more identical or different, monovalent or polyvalent anions as defined above.

Examples of cationic direct dyes corresponding to the above formulas which may be mentioned include:

Compositions of the present invention typically contain a mixed dye in an amount of 0.001% to 20% by weight of the total weight of the composition. Preferably, the amount is from 0.005% to 10%, even more preferably from 0.01% to 5% by weight of the total weight of the composition.

The dyes of the invention can be prepared according to known chemical reactions, starting with a functionalized chromophore capable of reacting with the selected linking group. For example, if the linking group is a triazine group, then the chromophore should comprise reactive amino, OH or SH groups and the synthesis can be carried out according to the following scheme.

According to a first step, the first chromophore is mixed with a compound capable of forming or forming a linking group, for example cyanuric chloride. Once the reaction is complete, a second chromophore is added to the reaction medium. The sequence can be repeated as many times as there are reactive groups on the compounds capable of forming linking groups.

For the preparation of the mixed dyes Dye 1-L-Dye 2, the molar ratio of the linking group to dye 1 is usually 10: 1 to 0.5: 1, preferably 1: 1. The ratio can be changed if more than one linker or several chromophores are used.

The reaction temperature is usually from -10 ° C to + 130 ° C, preferably from -5 ° C to 100 ° C. The reaction time depends on the reactivity and the reaction temperature of the species present. Typically, the reaction time is 10 minutes to 8 hours, preferably 30 minutes to 4 hours.

The pH of the reaction is usually 3 to 10, preferably 4 to 8.

The reaction can be carried out alone or as a mixture in water and / or an organic solvent. Several publications describe reactions for chemical combinations between two identical chromophores. Examples that may be mentioned include the documents ISBN 0901956759, WO 02/78596, DE 198 45 640, WO 03/029359 and US 5 708 151.

In addition, the reaction, or the reaction of a linking group with two different compounds, which may or may not be dyes, is described in the literature, for example WO 03/029359, DE 3 335 956, WO 03/30909, WO 03/18021, Journal of Medicinal Chemistry 43 (9), 2000, 1892-97; Chemiker Zeitung 117 (7-8), 1987, 241-5.

The composition of the present invention contains an alkali agent which may be any alkali agent commonly used in cosmetics. Among these alkaline agents, mention may be made, for example, of aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and compounds of formula II:

[Wherein W is an unsubstituted or propylene moiety substituted with a hydroxyl group or a C ₁ -C ₄ alkyl radical; R _a , R _b , R _c and R _d may be the same or different and represent a hydrogen atom, a C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ hydroxyalkyl radical.

The pH of the dye composition of the present invention is preferably 8 to 11.

The composition of the present invention contains an oxidizing agent. Oxidants commonly used for oxidative staining of keratin fibers are, for example, hydrogen peroxide, urea peroxides, alkali metal bromates, persalts such as perborate and persulfate, peracid and oxidase enzymes, among which peroxidase, 2-electron Oxidoreductases such as uricases, and 4-electron oxygenases such as laccases may be mentioned. Hydrogen peroxide is particularly preferred.

The dye compositions according to the invention may contain one or more direct dyes commonly used in the field of keratin fiber dyeing. In this connection, mention may be made in particular of nitrobenzene dyes, azo direct dyes and methine direct dyes. The direct dye may be of nonionic, anionic or cationic character. Preferably, said additional direct dye is of cationic nature.

In addition, the dye compositions of the present invention may contain one or more oxidizing bases and / or one or more couplers commonly used for keratin fiber dyeing.

Among the oxidizing bases, mention may be made of para-phenylenediamine, bis (phenyl) -alkylenediamine, para-aminophenol, bis-paraaminophenol, ortho-aminophenol and heterocyclic bases, and addition salts thereof.

Among the couplers, particular mention may be made of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene-based couplers and heterocyclic couplers, and addition salts thereof.

In the compositions of the present invention, the coupler (s) are each typically present in an amount of approximately 0.001% to 10% by weight, preferably 0.005% to 6% by weight relative to the total weight of the dye composition.

The oxidizing base (s) present in the compositions of the present invention are each typically present in an amount of approximately 0.001% to 10% by weight, preferably 0.005% to 6% by weight relative to the total weight of the dye composition. .

Typically, addition salts of oxidative bases and couplers which can be used in the context of the present invention may be particularly selected from the following: addition salts with acids, such as hydrochloride, hydrobromide, sulfates, alkyl sulfates, for example Methyl or ethyl sulfate, citrate, succinate, tartrate, lactate, tosylate, benzenesulfonate, phosphate and acetate, and addition salts with bases such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines .

Suitable media for dyeing, also known as dye supports, are cosmetic media usually consisting of water or a mixture of water and one or more organic solvents for dissolving a compound that is not sufficiently soluble in water. As the organic solvent, for example, the following may be mentioned: C ₁ -C ₄ 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, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvent is preferably present in a proportion of preferably about 1% to 40% by weight, even more preferably about 5% to 30% by weight relative to the total weight of the dye composition.

In addition, the dye compositions according to the invention can be used in various auxiliaries commonly used in hair dyeing compositions such as anionic, cationic, nonionic, zwitterionic, or zwitterionic surfactants or mixtures thereof, anionic, cationic , Nonionic, zwitterionic or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, in particular anionic, cationic, nonionic and zwitterionic associative polymeric thickeners, antioxidants, penetrants, sequestrants, perfumes, It may contain a buffering agent, a dispersing agent, a packaging agent which may or may not be volatile or may be modified, for example silicone, film former, ceramide, preservative and opaque agent.

The adjuvants are typically present in amounts of 0.01% to 20% by weight, respectively, based on the weight of the composition.

Naturally, those skilled in the art will pay attention to the selection of any additional compound so that the advantageous properties essentially associated with the oxidative dye composition according to the invention are not adversely or substantially adversely affected by the intended addition (s). will be.

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

The method of the invention is a method of applying a composition according to the invention as defined above to a fiber. The oxidant may be added to the composition in use, or may be applied simultaneously or sequentially with the composition containing the mixed dye, starting with the oxidizing composition containing the oxidant. In this case, the oxidant is contained in a composition other than the composition containing the mixed dye.

According to one particular embodiment, a composition according to the invention containing a mixed dye is preferably mixed with a composition containing at least one oxidizing agent in a medium suitable for dyeing, in use, wherein the oxidizing agent is Present in an amount sufficient to achieve lightening. Thereafter, the obtained mixture is applied to keratinous fibers. After a working time of approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and dried.

The oxidizing composition may also contain various auxiliaries commonly used in hair dyeing compositions, as defined above.

The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers is preferably approximately 7-12, even more preferably 8-11. This can be adjusted to the desired value using the acidifying or basicizing agents generally used for dyeing keratinous fibers as defined above.

The ready-to-use composition which is finally applied to the keratin fibers may be in various forms suitable for dyeing keratin fibers, especially human hair, such as in the form of liquids, creams or gels or any other form.

Another subject of the invention is that, as a multi-compartment dyeing apparatus or "kit", the first compartment contains a lightening dye composition containing a mixed cationic dye as defined above and the second compartment contains an oxidizing agent. The device may be equipped with means for applying the desired mixture to the hair, such as the device described in patent FR-2 586 913 in the name of the applicant.

The following examples illustrate the invention without limiting its scope.

Synthesis Example

Step 1:

2.4 g of cyanuric chloride in 50 mL acetone were added to a 500 mL three neck flask with stirring at room temperature. The reaction medium was clear. A mixture consisting of water and ice with respective ratios 50 ml and 100 ml was added and the reaction medium was placed in an ice bath at 0 ° C.

After stirring for a few seconds, a whitish suspension was obtained. pH value was 2.8. 3.2 dissolved in 100 mL water using a dropping funnel, taking care to maintain the pH of the reaction medium at 4-6 with a saturated K ₂ CO ₃ solution and keeping the reaction medium at a temperature below 5 ° C. A solution containing g of (i) was added.

After this addition, a saturated K ₂ CO ₃ solution was added uniformly to stabilize the pH to 4.8. Thereafter, the mixture was returned to room temperature. HPLC (relative purity: 94%) and control mass (m / z: 363-365-367) indicate that reaction product (ii) was formed virtually alone.

Then, a solution consisting of 3.42 g of (iii) dissolved in 50 ml of a H ₂ O / EtOH mixture (1/1) in advance was added to the reaction medium, taking care to maintain the pH at 4-6. After addition, the pH was maintained at 4.9-5 for 15 minutes. The reaction medium was then heated to 44 ° C. for 2.5 hours. The reaction medium was returned to room temperature and then poured into a conical flask containing 1 L solution of isopropanol and acetone. A precipitate appeared. The precipitate was filtered off, dried in a desiccator and analyzed. 6.08 g (yield = 86%) of brown powder (product (iv)) were obtained with 98% purity (relative purity, HPLC).

Step 2:

9 g of (iv) dissolved in 300 ml water were placed in a three neck flask equipped with a condenser, pH probe and addition funnel containing 1N sodium hydroxide solution. The reaction medium was then heated to 85 ° C. (oil bath temperature: 96 ° C.) and the pH was adjusted to 7.7 to 8 using sodium hydroxide solution. While paying attention to monitoring pH (pH <8), amine (3 mL) diluted in 20 mL water was added very slowly. As soon as the addition was complete, the reaction medium was brought to 92 ° C. (oil bath temperature: 118 ° C.) and stirred until the pH was stabilized to a value of 7.7 to 8.

After reacting for 1 hour, the reaction medium was cooled and then poured into a conical flask containing 1 L of acetone. The product precipitated out. It was then filtered off, dried in a desiccator and analyzed. 7.1 g of brown powder (compound v) were obtained (yield = 82%, HPLC purity: 92%).

Mass (ESI +): m / z = 352

The following compounds were synthesized by carrying out Step 2 using the reactants shown below.

Dyeing example

The dyeing compositions described in Table 1 were prepared from dyes C1 to C5 (amount: 4.7 × 10 ⁻⁴ mol) and the following dyeing compositions:

Composition A

(50/50 C8 / C10) Alkyl polyglucoside as 60% buffered aqueous solution (sold under the trade name Oramix by SEPPIC) 10 g  Benzyl alcohol 10 g  Polyethylene Glycol 400 Containing 8 Ethylene Oxide Units 12 g  Mixed dyes C1 to C5 4.7 × 10 ^-4 mol  20.5% aqueous ammonia 13 g  Demineralized water 100 g of quantity

Composition B

(50/50 C8 / C10) Alkyl polyglucoside as 60% buffered aqueous solution (sold under the trade name Oramix by SEPPIC) 10 g  Benzyl alcohol 10 g  Polyethylene Glycol 400 Containing 8 Ethylene Oxide Units 12 g  Mixed dyes C1 to C5 4.7 × 10 ^-4 mol  Aminomethylpropanol Appropriate pH 10.5  Demineralized water 100 g of quantity

In use, each of the compositions was mixed with 40 V (weight for weight, pH = 3.5) aqueous hydrogen peroxide solution or acidified water (pH = 3.5).

After mixing, the pH of the dye composition was 9.5 to 10.

The mixture was then applied to the hair ends of natural gray (NG) or permanent waved gray (PG) hair, including 90% white hair. The standing time on the hair stage was 20 minutes at room temperature. The hair ends were then shampooed.

After drying, color inhalation was visually assessed by measuring L * a * b * (CM 2002 colorimeter, luminescence D65-10 ° CSI).

The results are compared in Table 1 below.

The comparison between the lightening and non-lightening conditions was calculated in the following way:

[Wherein L * _l , a * _l and b * _l represent colorimetric values under lightening conditions and L * _nl , a * _nl and b * _nl represent colorimetric values under non-lighting conditions].

The results show that a strong pigmentation is obtained which is not sensitive to the composition of the dyeing medium. Specifically, similar coloring is obtained under lightening conditions (medium A + H ₂ O ₂ ) and under non-lighting conditions (medium B + acidified water).

shampoo Color fastness

The following dyeing compositions were prepared from dyes C1 to C5 (4.7 × 10 ⁻⁴ mol) and dye support A.

Upon dyeing, the composition was mixed with 40 V aqueous hydrogen peroxide solution (weight to weight, pH = 3.5). After mixing, the pH of the dye composition was 9.5 to 10.

The colored hair ends were then shampooed six times, drying in between the two shampoo washes. Visually and by colorimeter measurements, the color after six shampoo washes was compared with the initial color of the dyed hair ends. Using L * a * b * values (L ₀ * a ₀ * b ₀ * before 6 shampoo washes and L ₁ * a ₁ * b ₁ * after 6 shampoo washes) measured for each type of hair tips According to the formula for ΔE, shampoo fastnesses were measured for dyed natural hair and dyed permanent waved hair.

Colorimeter measurements are compared in Table 2 below.

The results show that the lightening composition of the present invention has very good shampoo fastness and little selectivity between natural hair and permanently waved hair.

Claims (29)

A cationic mixed dye comprising several chromophores linked together via a linking group, two or more of which are different and exhibit one or more absorption maxima between 400 and 800 nm, an amount such that the pH of the composition is greater than 7 Lightening dyeing compositions which contain alkali and oxidizing agents in a suitable dyeing medium. The composition of claim 1, wherein the mixed dye is a composition in which the chromophore is selected from: acridine, acridon, anthrone, anthripyrimidine, anthraquinone, azine, azo, azomethine, benzanthrone, benzimi Dazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, benzoquinone, bis-azine, bis-isoindolin, carboxanilide, coumarin, cyanine (azacarbocyanine, diaza Carbocyanine, diazahemicyanine, hemicyanine and tetraazacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane and dithiazine chromophores, flavantrons and flavones; Flavonoids, fluorindine, formazan, hydrazone, especially arylhydrazone, hydroxy ketone, indamine, indanthrone, indigoid and pseudo-indigoid, indophenol, indoaniline, isoindolin, isoindolin, Isoindolinone, isobiol Tron, lactone, methine, naphthalimide, naphthanilide, naphtholactam, naphthoquinone, nitro dyes, in particular nitro (hetero) aromatic dyes, oxadiazoles, oxazines, perylenes, perinones, perylenes, phena Gin, phenothiazine, phthalocyanine, polyene / carotenoid, porphyrin, pyrantrone, pyrazolanthrone, pyrazolone, pyrimidinoanthrone, pyranine, quinacridone, quinoline, quinophthalone, squaranes, steel Ben, tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane, xanthene. The composition of claim 2 wherein the chromophore is selected from: acridine, acridon, anthrone, anthraquinone, azine, azo, azomethine, benzanthrone, benzoquinone, bis-azine, cyanine (azacar Bocyanine, diazacarbocyanine, diazahemicyanine, hemicyanin and tetraacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine, diphenylmethane and dithiazine chromophores, flavantrons and flavones Flavonoids such as formazan, hydrazone, especially arylhydrazone, indamine, indanthrone, indigoid and pseudo-indigoid, indophenol, indoaniline, isobiolatron, methine, naphthalimide, naphtholactam, naph Toquinones, nitro dyes, in particular nitro (hetero) aromatic dyes, phenazines, phenothiazines, phthalocyanines, polyene / carotenoids, porphyrins, pyrazolones, quinacridones, quinophthalones, stilbenes, tetrazolium, thiazines, Thio Indigo, thiopyronine, triarylmethane, xanthene. The method according to claim 2 or 3, wherein the chromophores are azo, xanthene, hydrazone and arylhydrazone, phenothiazine, acridine, diketopyrrolopyrrole, cyanine, in particular tetraacarbocyanine, anthraquinone, methine, Azomethine, indigoid and nitro, in particular a composition selected from nitro (hetero) aromatic chromophores. The composition according to any one of claims 1 to 3, wherein the mixed dye is dicationic. The composition of claim 4, wherein the mixed dye comprises two or three chromophores, at least two of the chromophores are cationic and the linking group is cationic or noncationic. 7. The mixed dye according to any one of claims 1 to 6, wherein the mixed dye corresponds to the formula Dye 1-L-Dye 2, wherein L is a cationic or noncationic linking group and Dye 1 and Dye 2 are different cations. A composition that is a sex chromophore. 8. The composition of claim 1, wherein the cationic chromophore (s) are chromophore (s) comprising quaternized nitrogen atoms. 9. The composition of claim 1, wherein the mixed dye comprises a cationic azo chromophore. 10. The linkage according to claim 1, wherein the linking group is selected from C ₁ -C ₂₀ , more particularly C ₁ -C ₁₄ linear, branched or cyclic, substitutable hydrocarbon-based chains. One or more of the carbon atoms of may be replaced by one or more heteroatoms such as sulfur, nitrogen or oxygen and / or by one or more groups comprising heteroatoms such as carbonyl groups, wherein the hydrocarbon-based chain may be unsaturated or one or more substitutions Alkylene radicals which may be; Arylene radicals which may be substituted; Divalent terephthalamide radical which may be substituted; A composition that may include a divalent heterocyclic radical, such as a divalent triazine radical, or an -NH-CO- radical. The position on the wavelength scale of the absorption maximum of the chromophore which comprises a mixed dye is 30 nm with respect to the absorption maximum of each chromophore taken separately, The linking device in any one of Claims 1-10. A composition comprising an atom or group of atoms that isolates each chromophore from a mixed dye in such a way that it is not altered in excess. The composition of claim 1 wherein the mixed dye corresponds to the formula:

[Wherein L is a linking group and R 1 and R 1 ′ are at least one hydroxyl, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy, amino, C ₁ -C ₂ (di) alkylamino Or an alkyl radical which may be substituted with an aryl radical which may be substituted, preferably a C ₁ -C ₆ alkyl radical and R 2 and R 2 ′ are one or more hydroxyl, C ₁ -C ₂ alkoxy, C ₂ C ₁ -C ₆ alkyl radicals which may be substituted with —C ₄ (poly) hydroxyalkoxy, amino or C ₁ -C ₂ (di) alkylamino radicals; Independently selected from phenyl radicals which may be substituted; An represents one or more identical or different, monovalent or polyvalent anions]. The composition of claim 11, wherein the mixed dye corresponds to the following structural formula:

. The composition of claim 1, wherein the anion An is an organic or inorganic anion selected from: halides such as chloride, bromide, fluoride or iodide; hydroxide; Sulfates; Hydrogen sulfate; (C ₁ -C ₆ ) alkyl sulfates, such as methyl sulfate or ethyl sulfate; Phosphate; Carbonates; Hydrogen carbonate; Perchlorate; acetate; Tartrate; Citrate; Oxalate; (C ₁ -C ₆ ) alkyl sulfonates such as methane sulfonate; Arylsulfonates that can be substituted with C ₁ -C ₄ alkyl radicals, such as 4-tolylsulfonate. The method according to any one of claims 1 to 12, wherein the amount of the mixed dye is from 0.001% to 20%, preferably from 0.005% to 10%, more preferably from 0.01% to 5% by weight of the total weight of the composition. Composition. The composition according to any one of claims 1 to 15, further containing at least one direct dye other than the mixed dye as defined in any of claims 1 to 13. The compound according to any one of claims 1 to 16, which is selected from para-phenylenediamine, bis (phenyl) -alkylenediamine, para-aminophenol, ortho-aminophenol and heterocyclic base, and addition salts thereof. A composition containing an oxidized base. 18. The composition according to any one of claims 1 to 17, containing a coupler selected from meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene-based couplers and heterocyclic couplers, and addition salts thereof. . The method according to claim 15 or 16, wherein the amount of each oxidation base is about 0.001% to 10% by weight relative to the total weight of the dye composition, and the amount of each coupler is about 0.001% by weight to the total weight of the dye composition. 10% by weight of the composition. 20. The composition of any one of the preceding claims, wherein the pH is 8-11. 19. The composition according to any one of claims 1 to 18, wherein the alkali agent is an alkanolamine such as aqueous ammonia, alkaline carbonate, mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the formula Compositions selected from compounds of: [Formula II]

[Wherein W is an unsubstituted or propylene moiety substituted with a hydroxyl group or a C ₁ -C ₄ alkyl radical; R _a , R _b , R _c and R _d may be the same or different and represent a hydrogen atom, a C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ hydroxyalkyl radical. 22. The composition of any one of claims 1 to 21, wherein the oxidant is hydrogen peroxide. A method for oxidative dyeing of keratin fibers, wherein the dyeing composition according to any one of claims 1 to 20 is applied to said fibers for a time sufficient for lightening and the desired coloring to be expressed. The method according to claim 21, wherein the oxidizing agent is contained in a composition other than the composition containing the mixed dye according to any one of claims 1 to 13. 14. A multi-compartment apparatus in which the first compartment comprises a dyeing composition containing an alkali agent and the mixed dye according to any one of claims 1 to 13, and the second compartment comprises an oxidizing agent. Use of the dye according to any one of claims 1 to 13 for the lightening dyeing of keratinous fibers. 25. Use according to claim 24 for obtaining good shampoo fastnesses. 25. Use according to claim 24 for obtaining good color fastness with time. 25. Use according to claim 24 for obtaining a dyeing composition that is stable over time.