FR2857863A1 - Use of compositions containing ninhydrin derivatives to dye hair - Google Patents

Abstract

Composition (C1) containing at least one ninhydrin derivative (I) is used to dye hair. Composition (C1) containing at least one ninhydrin derivative of formula (I) is used to dye hair. [Image] X : S or Se; R : H, 1-9C alkyl, CN, halo, OR, NHR, N(R)2, mono- or di(1-6C hydroxyalkyl)amino, N+>(R)3, imidazolyl, pyridyl, SH, SR, 1-6C mercaptoalkyl, COR, COOH, COOR, NO2, sulfonato, a corresponding protonated group (e.g. ammonio, imidazolio or pyridinio) or an optionally fused mono- or polycyclic aromatic ring of at least 5 members, optionally including one or more heteroatoms (N, O, S and/or P). Independent claims are also included for: (1) cosmetic dye composition (C2) comprising at least one compound (I) and a surfactant and/or polymer; (2) ready-to-use cosmetic dye composition (C3) comprising at least one compound (I) and a compound (II) with a primary or secondary amine function and/or an activated methylene function; (3) multicomponent dyeing product comprising C1 and a composition (C4) comprising (II); (4) hair dyeing by applying C2 or C3 and rinsing and washing the hair when the desired color is attained; and (5) hair dyeing by applying C1 and C4 in any order.

Description

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Use in hair dyeing of ninhydrin derivatives bearing a heteroalkyl group
The present invention relates to hair dye compositions containing at least one ninhydrin derivative bearing a heteroalkyl group preferably associated with a primary or secondary amine functional compound or an activated methylene compound, a hair dyeing method using such compositions and a multicomponent coloring agent for carrying out such a method.

 For a long time, many people have been trying to change the color of their hair and in particular to hide their white hair. To do this, several technologies have been developed.

 It is known to dye human keratin fibers, and in particular the hair, with dye compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, give rise to colored compounds by a process of oxidative condensation.

These dyes are insoluble and are trapped inside the hair fiber.

 It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

 The colorations obtained have good toughness to shampoos.

However, the oxidation reaction is carried out using oxidizing products such as hydrogen peroxide in basic medium. These oxidizing agents attack the keratin of hair, the cosmetic and mechanical properties of which can be strongly degraded in case of repeated staining.

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 It is also known to dye human keratin fibers by direct dyeing, which consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers. Examples of direct dyes conventionally used are nitro, benzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane dyes or natural dyes.

 The colorations thus obtained are, of course, very chromatic and do not cause a chemical degradation of the keratin, but have the disadvantage of being only temporary or semi-permanent, that is to say to fade at better after only 4 to 5 shampoos.

 There is therefore still a need for coloring systems and methods which make it possible to obtain good toughness without involving the use of oxidizing agents capable of degrading the keratinous fibers.

 The Applicant has discovered with surprise that the use of ninhydrin derivatives bearing a heteroalkyl group described in more detail below allowed the dyeing of keratinous fibers, and in particular the hair, with tenacities equivalent to or even greater than those obtained by coloring. oxidation and this in the absence of strong oxidizing agents thus perfectly preserving the keratinous fibers.

 The aforementioned heteroalkyl-containing ninhydrin derivatives are preferably used in combination with labile hydrogen compounds, such as primary or secondary amines or activated methylene compounds.

 The colorations thus obtained have good chromaticities and are distinguished in particular by an excellent washing tenacity (several tens of shampoos).

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dans laquelle
X représente un atome de soufre ou un atome de sélénium,
R représente un substituant choisi parmi un atome d'hydrogène, un groupement alkyle en C1-C9 linéaire ou ramifié, un groupement cyano, un groupement halogéno, comme chloro, iodo, bromo et/ou fluoro, un groupement alcoxy eh Ci-Ce, un groupement amino, un groupement mono- ou di-(alkyle en CiC6)amino, un groupement mono- ou di-hydroxy(alkyle en Ci-C6)amino, un groupement tri(alkyle en Ci-C6)ammonio, un groupement imidazolyle, un groupement pyridinyle, un groupement thio, un groupement (alkyle en C1-C6)thio, un groupement thio(alkyle en Ci-Ce), un groupement (alkyle en C1-C6)carbonyle, un groupement hydrogénocarbonyle, des groupements hydroxycarbonyle, des groupements (alcoxy en C1-C6)carbonyle, des groupements nitro, des groupements sulfonato, les groupes protonés correspondants tels que ammonio, imidazolio, et/ou pyridinio ou représente un groupe aromatique comportant au moins 5 chaînons, monocyclique ou polycyclique à cycles condensés ou non condensés, comportant éventuellement un ou plusieurs hétéroatomes choisis parmi l'azote, l'oxygène, le soufre et/ou le phosphore. The subject of the invention is therefore the use, for the hair dyeing, of a composition containing, in a medium which is suitable for dyeing, at least one compound of formula (I) or its tautomeric form:

in which
X represents a sulfur atom or a selenium atom,
R represents a substituent chosen from a hydrogen atom, a linear or branched C1-C9 alkyl group, a cyano group, a halo group, such as chloro, iodo, bromo and / or fluoro, a C1-C6 alkoxy group, an amino group, a mono- or di-C 1-6 alkylamino group, a mono- or di-hydroxy (C 1-6) alkylamino group, a tri (C 1-6) alkylammonio group, an imidazolyl group. a pyridinyl group, a thio group, a (C 1 -C 6) alkylthio group, a thio (C 1 -C 6) alkyl group, a (C 1 -C 6) alkylcarbonyl group, a hydrogenocarbonyl group, hydroxycarbonyl groups, (C1-C6) alkoxycarbonyl groups, nitro groups, sulphonato groups, the corresponding protonated groups such as ammonio, imidazolio, and / or pyridinio or represents an aromatic group comprising at least 5 members, monocyclic or polycyclic with condensed rings; or not condensed, possibly including one or more heteroatoms selected from nitrogen, oxygen, sulfur and / or phosphorus.

 The monocyclic or polycyclic aromatic group R is preferably chosen from pyrrolyl, thiophenyl, furanyl, pyrazolyl, imidazolyl, phenyl, pyranyl, pyridinyl, pyrimidinyl, indolyl, quinolinyl, carbazolyl, chromenyl, biphenyl and naphthalenyl.

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 The monocyclic or polycyclic aromatic group R represents a thiophenyl, phenyl or naphthalenyl group.

 Preferably, the monocyclic or polycyclic aromatic group R may be substituted by one or more groups chosen from halo, chloro, iodo, bromo and / or fluoro groups, Ci-C 6 alkyl groups, hydroxyl groups, C 1 -C 6 alkoxy groups, Ce, amino groups, mono- or di- (C 1 -C 6) alkylamino groups, mono- or dihydroxy (C 1 -C 6) alkylamino groups, tri (C 1 -C 6) alkylammonio groups, imidazolyl groups, pyridinyl groups , thio groups, (C 1 -C 6) alkylthio groups, thio (C 1 -C 6) alkyl groups, (C 1 -C 6) alkylcarbonyl groups, hydrogenocarbonyl groups, hydroxycarbonyl groups, C 1 -C 6 alkoxycarbonyl groups, nitro groups , sulphonato groups, the corresponding protonated groups such as ammonio, imidazolio, and / or pyridinio.

 The compounds of formula (I) include, of course, also the acid addition salts and the corresponding base addition salts.

The ninhydrin derivatives of formula (I) above are used in the present invention in a cosmetically acceptable medium generally containing a significant fraction of water. When dissolved in such an aqueous medium, the ninhydrin derivatives of formula (I) are in hydration equilibrium with the geminated diol form (or carbonyl hydrate) corresponding to the following formula (I):

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Where ninhydrin derivatives of the formula (I) are referred to herein, these also still include not only the compounds of the formula (1) but also the corresponding hydrated forms of the formula (I) bis.

5-(méthylthio)ninhydrine (a)

5-(isopropylthio)ninhydrine (b)

5-(thiocyano)ninhydrine (c) Preferred examples of ninhydrin derivatives usable according to the present invention for coloring hair fibers are as follows:

5- (methylthio) ninhydrin (a)

5- (Isopropylthio) ninhydrin (b)

5- (thiocyano) ninhydrin (c)

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5-(butylthio)ninhydrine (d)

5-(octylthio)ninhydrine (e)

5-(phénylsulfanyl)ninhydrine (f)

5-(méthylsélénio)ninhydrine (g)

5- (butylthio) ninhydrin (d)

5- (octylthio) ninhydrin (e)

5- (phenylsulfanyl) ninhydrin (f)

5- (methylselenio) ninhydrin (g)

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5-(pentylsélénio)ninhydrine (h)

5- (Pentylselenio) ninhydrin (h)

5- (phenylselenio) ninhydrin (i)
The ninhydrin derivatives used in the present invention are known. The synthesis of the ninhydrin derivatives (a) to (i) above is described in the following publications: (a) 5- (methylthio) ninhydrin: Heffner RJ, Joullie MM, Synthetic routes to ninhydrin preparation of ninhydrin, 5-methoxyninhydrin and 5- (methylthio) ninhydrin, synth. Common. 1991, 21, 2231-2256.

(b) 5- (Isopropylthio) ninhydrin: Almog J., Hirschfeld A., Frank A., Grant H., Harel Z., Ittah Y., 5-methylthio ninhydrin and related compounds: a novel class of fluorogenic fingerprint reagents, Forens. Sci. 1992, 37, 688-694.

(c) 5- (thiocyano) ninhydrin: Almog J., Hirschfeld A., Frank A., Grant H., Harel Z., Ittah Y., 5-methylthio ninhydrin and related compounds: a novel class of fluorogenic fingerprint reagents, Forens. Sci. 1992, 37, 688-694.

(d) 5- (butylthio) ninhydrin: Della EW, Janowski WK, Pigou P.P., Taylor B.M., Synthesis of fingerprint reagents: aromatic nucleophilic substitution as a route to 5

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 substituted ninhydrins, synthesis, 1999, 12, 2119-2123.

(e) 5- (heptylthio) ninhydrin: Della EW, Janowski WK, PP Pigou, Taylor BM,
Synthesis of fingerprint reagents: aromatic nucleophilic substitution as a route to 5 substituted ninhydrins, synthesis, 1999, 12, 2119-2123.

 (f) 5- (phenylsulfanyl) ninhydrin: Della EW, Janowski WK, Pigou P, Taylor B.

 M. Synthesis of fingerprint reagents: aromatic nucleophilic substitution as a route to 5-substituted ninhydrins, synthesis, 1999, 12, 2119-2123.

 (g) 5- (methylselenio) ninhydrin: Della EW, Janowski WK, Pigou P, Taylor B.

M. Synthesis of fingerprint reagents: aromatic nucleophilic substitution as a route to 5-substituted ninhydrins, synthesis, 1999, 12, 2119-2123.

(h) 5- (pentylselenio) ninhydrin: Della EW, Janowski WK, Pigou P. Synthesis of fingerprint reagents: aromatic nucleophilic substitution of ninhydrin synthesis, 1999, 12, 2119-2123.

(i) 5- (phenylselenio) ninhydrin: Della E. W., Janowski W. K., Pigou P.

Synthesis of fingerprint reagents: aromatic nucleophilic substitution of ninhydrin synthesis, 1999, 12, 2119-2123.

 According to the present invention, the ninhydrin derivatives of formula (I) described above can be used alone for coloring hair fibers. Indeed, these compounds are capable of generating molecules stained with the amine functions of keratin (color reaction). Compounds of formula (I) may also be used together with at least one labile hydrogen compound selected from those having a primary or secondary amine function and those having an activated methylene function. It is of course also possible to use a mixture of such labile hydrogen compounds.

 The primary amine or secondary amine compounds are preferably aromatic amines.

 Examples of such aromatic amines are N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl)

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 ethyl) -N-ethyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-, 2 , 4- or 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3- or 4-aminophenol, 2- aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, ortho-phenylenediamine, p-phenylenediamine, ortho-toluenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminophenethol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylaminoaniline, 3-amino-4 - (2'-hydroxyethyloxy) aniline, 3,4-methylenediaminoaniline, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol , 2-methyl-5- (2-hydroxyethylamino) phenol, 6-methyl-3-amino-2-chlorophenol, 2- methyl-5-amino-4-chlorophenol, 3,4-methylenedioxyphenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2, 4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, 2-amino-, 3-amino or 4-aminophenylacetic acid, 2,3-, 2,4-, 2,5-, 3-acid 4- or 3,5-diaminobenzoic acid, 4-amino- or 5-amino-salicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino amino, 3-amino or 4-aminobenzene sulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid , 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, the acid 5aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5tetraaminobenzene, 2,4,5-triaminophenol, pentaminobenzene, hexaaminobenzene , 2,4,6-triaminoresorcinol, 4,5-diaminopyrochatecol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxypyrochatecol, and aromatic anilines and aromatic phenols having another aromatic residue, corresponding to the formula (II)

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(II) dans laquelle
R1 représente un groupe hydroxy ou amino éventuellement substitués par un groupe alkyle en Ci-4, hydroxyalkyle en Ci-4 ou (alcoxy en Ci-4)-(alkyle en CI-4),
R2, R3, R4, R5 et R6 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxy ou un groupe amino, éventuellement substitués par un groupe alkyle en CI-4, hydroxyalkyle en Ci-4 ou (alcoxy en C1-4)-(alkyle en Ci-4), ou un groupe acide carboxylique ou sulfonique,
Z représente une liaison directe, une chaîne hydrocarbonée en Ci.4, saturée ou insaturée, éventuellement hydroxylée, un groupe carbonyle, sulfonyle ou imino, un atome d'oxygène ou de soufre, ou un groupe de formule Q-(CH2-P-CH2-Q')o où P représente une liaison directe ou un groupe -CH2- ou-CHOH-, Q et Q' représentent, indépendamment l'un de l'autre, un atome d'oxygène, un groupe NR7où R7 représente un atome d'hydrogène, un groupe alkyle en Ci-4 ou hydroxyalkyle en C1-4, ou un groupe 0-(CH2)pNH ou NH-(CH2)p'-O où p et p' valent 2 ou 3 et o est un nombre entre 1 et 4.

(II) in which
R 1 represents a hydroxy or amino group optionally substituted by a C 1-4 alkyl, C 1-4 hydroxyalkyl or (C 1-4 alkoxy) - (C 1-4 alkyl) group,
R 2, R 3, R 4, R 5 and R 6 each independently represent a hydrogen atom, a hydroxy group or an amino group optionally substituted with a C 1-4 alkyl, C 1-4 hydroxyalkyl or (C 1-4 alkoxy) group; - (C 1-4 alkyl), or a carboxylic or sulfonic acid group,
Z represents a direct bond, a saturated or unsaturated, optionally hydroxylated, C1-4 hydrocarbon chain, a carbonyl, sulphonyl or imino group, an oxygen or sulfur atom, or a group of formula Q- (CH2-P- Where P represents a direct bond or a group -CH2- or -CHOH-, Q and Q 'represent, independently of one another, an oxygen atom, a group NR7 where R7 represents a hydrogen, C 1-4 alkyl or C 1-4 hydroxyalkyl, or O- (CH 2) pNH or NH- (CH 2) p'-O where p and p 'are 2 or 3 and o is a number between 1 and 4.

 The nonaromatic primary or secondary amines are, for example, 2-aminoethanol, 2-methoxyethylamine, 2-ethoxyethylamine, 2- (2-aminoethoxy) ethanol, 2- or 3-aminopropanol, 2,3-dihydroxypropylamine, 4-hydroxypropylamine, 2-aminopropane-1,3-diol, 2-amino-2-methylpropanol, 2-amino-2-methylpropane-1,3-diol, 2-amino-2-hydroxymethylpropane-1,3 diol, tetrahydropentylamine, pentahydroxyhexylamines such as glucamine, Dglucosamine, D-galactosamine, 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,3-diamino-2-propanol, 2- (2-Aminoethylamino) ethylamine,

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2- (2-aminoethylamino) ethanol, 3- (2-aminoethylamino) propylamine and 3- (2-aminoethylamino) propanol.

The compounds with activated methylene function are chosen for example from the following: 1,2,3,3-tetramethyl-3H-indolium iodide, p-toluenesulphonate
1,2,3,3-tetramethyl-3H-indolium, 1,2,3,3-tetramethyl-3Hindolium methanesulfonate, 1,3,3-trimethyl-2-methyleneindoline, iodide of 2, 3dimethylbenzothiazolium, 2,3-dimethylbenzothiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide , barbituric acid, thiobarbituric acid, acid
1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyl acetate, coumarone and 1-methyl-3-phenyl-2-pyrazolinone.

 These primary and secondary amines and these compounds with activated methylene functions as well as other compounds with labile hydrogen are also described in the patent applications DE 43 17 855, DE 197 17 222, DE 198 45 481 and DE 197 45 355 where they are used for dyeing keratin fibers in combination with compounds other than the ninhydrin derivatives of formula (I).

 When the ninhydrin derivatives of formula (I) are used in combination with a primary or secondary amine or with an activated methylene compound, it is necessary to keep these different reagents separately to avoid a premature color reaction. The contacting of the reagents is then done immediately before application to the hair, by extemporaneous mixing of two compositions respectively containing ninhydrin derivatives and compounds with labile hydrogen. The contacting of the reagents can be done directly on the hair by successive application of the different reagents.

 The invention therefore also relates to a multi-component hair coloring agent comprising # as a first component, a composition (a) containing at least one ninhydrin derivative of formula (I), and

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 as a second component, a composition (b) containing at least one primary or secondary amine functional compound or at least one activated methylene compound, as described above.

 This multi-component hair coloring agent is preferably in the form of a multi-compartment kit, with at least a first compartment containing the first component (composition (a)) and at least a second compartment containing the second component (composition (b)).

 The invention also relates to a dye cosmetic composition containing at least one ninhydrin derivative of formula (I) and at least one cosmetic active ingredient.

 The cosmetic active principles present in the cosmetic compositions of the present invention are chosen, for example, from vitamins, saccharides, oligosaccharides, hydrolysed or non-modified polysaccharides, modified or otherwise, amino acids, oligopeptides, peptides and hydrolysed proteins. or not, modified or not, amino polyacids, enzymes, branched or unbranched fatty acids and alcohols, animal, vegetable or mineral waxes, ceramides and pseudo-ceramides, hydroxylated organic acids, UV filters, agents antioxidants and anti-free radical agents, chelating agents, anti-dandruff agents, seborrhea regulating agents, soothing agents, cationic, anionic, nonionic or amphoteric surfactants, cationic, anionic, neutral or amphoteric polymers, organomodified silicones, mineral, vegetable or animal oils, polyisobutene and poly (oolefins), fatty esters, anionic polymers in dissolved or dispersed form, nonionic polymers in dissolved or dispersed form, reducing agents, solvents, hair dyes such as direct dyes or precursors of oxidation dye (bases and / or couplers) different from the primary or secondary amine compounds claimed, the oxidizing agents such as hydrogen peroxide possibly associated with persalts, the pigments and their mixtures.

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The cosmetic active ingredient is preferably present in a proportion of 0.001 to
50% by weight, in particular from 0.01 to 20% by weight, and ideally from 0.1 to
10% by weight, based on the total weight of the cosmetic composition.

 In a preferred embodiment of the cosmetic dye composition according to the invention, the cosmetic active ingredient is a surfactant and / or a polymeric agent (polymer), these agents may be of a nonionic, cationic, anionic or amphoteric nature.

 From the foregoing it follows that the hair dyeing compositions used in the present invention are storage stable when they contain, as sole coloring reagents, ninhydrin derivatives of formula (I) or (Ibis). But when they contain both ninhydrin derivatives of formula (I) or (Ibis) and labile hydrogen compounds such as primary or secondary amines or activated methylene compounds, these compositions must be used immediately after mixing of the composition containing the ninhydrin derivatives of formula (I) or (Ibis) with that containing the one or more labile hydrogen compounds.

 These ready-to-use coloring compositions, whether stable in storage or prepared immediately before use, preferably have a pH of between 2 and 12, and in particular between 3 and 11.

 Their content of ninhydrin derivatives of formula (I) is preferably between 0.0001% and 30% by weight.

 The labile hydrogen compounds used in combination with the ninhydrin derivatives of formula (I) are preferably present in a proportion of from 0.0001% to 30% by weight relative to the total weight of the composition.

 The present invention further relates to a hair dyeing method comprising applying to the hair a hair dye composition ready for use as described above. This composition is left in contact with the hair fibers for a time sufficient to obtain the desired color. This exposure time is generally between 5 minutes and 1

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 hour, and in particular between 15 and 30 minutes. The color reaction between the ninhydrin derivatives and the amine functions of keratin or the labile hydrogen compounds which may be present may be accelerated by heating the impregnated hair with the coloring composition. The heating temperature preferably does not exceed 80.degree. C., and in particular is less than or equal to 60.degree.

 After obtaining the desired coloration, the hair is rinsed and washed.

 When labile hydrogen compounds such as primary or secondary amines or activated methylene compounds are used, the reagents involved in the color reaction can also be applied in two stages, ie two compositions can be successively applied. different, respectively containing at least one ninhydrin derivative of formula (I) and at least one compound having a primary or secondary amine function or an activated methylene function.

 The present invention therefore also relates to a two-step hair dyeing process comprising applying to the hair one after the other, in any order, a composition (a) and a composition ( b) as defined above for the multicomponent coloring agent.

 This separate application of the two reactive compositions has the advantage of avoiding the manipulation of colored compositions and thus reduces the risk of staining of materials such as clothing.

 The Applicant has found that satisfactory capillary stains are also obtained when an intermediate rinsing step is inserted between the application of the first composition and the application of the second composition.

 In a manner analogous to that described above, the hair impregnated with composition (a) and / or (b) may be heated, preferably to a temperature of 80 ° C., and in particular to a temperature not exceeding 60 C, such heating to accelerate the color reaction and shorten the exposure time.

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Examples
The following composition is prepared: 5- (phenylsulfanyl) ninhydrin (= hydrate of the compound of formula (f)) 10 -2 moles Ethanol 50 g NaOH qsp pH 7 Distilled water qs 100 g
This composition is applied to two strands of natural hair and permed with 90% of white hair, 1 g each. The bath ratio is 5, the exposure time is 30 minutes and the temperature is 60 C. At the end of the exposure time, the locks are rinsed and then washed with a standard shampoo.

 The color intensity is evaluated by colorimetry according to the CIELAB system using a Minolta CM3600d colorimeter (illuminant D65, observation angle: 10, specular component included).

 The CIELAB notation system defines a color space in which each color is defined by 3 parameters (L *, a * and b *): - the parameter L * reflects the clarity of the color, the value of L * being equal to 0 for black and equal to 1 for absolute white. The higher the L * value, the less intense the color.

 the parameter a * corresponds to the axis of the green-red antagonistic pair and the parameter b * to the axis of the blue-yellow antagonistic pair.

The table below shows the parameters L *, a * and b * of strands of natural hair and hair permed before and after the rise of the color, as well as AE defined by the following equation:

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#E reflects the overall variation in color. Its value is all the greater as the color variation is important.

<Tb>
<Tb>

Hair <SEP> L * <SEP> a * <SEP> b * <SEP> AE <SEP> Color
<tb> natural <SEP> Before <SEP> staining <SEP> 62,80-0,10 <SEP> 9,52- <SEP> natural <SEP> After <SEP> staining <SEP> 25,86-4, 75 <SEP> -7.93 <SE> 45.72 <SEP> blue
<tb> permuted <SEP> Before <SEP> staining <SEP> 62,58-0,28 <SEP> 13,46- <SEP> permuted <SEP> After <SEP> staining <SEP> 21,91 <SEP> 1.20 <SEP> -2.64 <SEP> 46.23 <SEP> black
<Tb>

Claims (18)

1. Use for the hair coloration of a composition containing, in a medium suitable for dyeing, at least one compound of formula (I)

 (I) in which X represents a sulfur atom or a selenium atom, R represents a substituent chosen from a hydrogen atom, a linear or branched C1-C9 alkyl group, a cyano group, a halo group, a C1-C6 alkoxy group, an amino group or a mono- or di- (C1-C8) alkyl group; C6) amino, mono- or di-hydroxy (C1-C6) alkylamino group, tri (C1-C6) alkylammonio group, imidazolyl group, pyridinyl group, thio group, (C1-C6) alkylthio group, thio (C1-C6) alkyl group, (C1-C6) alkylcarbonyl group, hydrogenocarbonyl group, hydroxycarbonyl groups, (C1-C6) alkoxycarbonyl groups, nitro groups, sulphonato groups, the corresponding protonated groups such as ammonio, imidazolio, and / or pyridinio or represents an aromatic group comprising at least 5 members, monocyclic or polycyclic ring fused or uncondensed, optionally comprising one or more heteroatoms selected from nitrogen, oxygen, sulfur and / or phosphor e.  2. Use according to claim 1, characterized in that the monocyclic or polycyclic aromatic group R is chosen from pyrrolyl, thiophenyl, furanyl, pyrazolyl, imidazolyl, phenyl, pyranyl and pyridinyl groups. <Desc / Clms Page number 18>  pyrimidinyl, indolyl, quinolinyl, carbazolyl, chromenyl, biphenyl, naphthalenyl.  3. Use according to claim 2, characterized in that the monocyclic or polycyclic aromatic group R represents a thiophenyl, phenyl or naphthalenyl group.  4. Use according to claim 2 or 3, characterized in that the monocyclic or polycyclic aromatic group R is substituted by one or more groups selected from halo groups, C1-C6 alkyl groups, hydroxy groups, C1-C6 alkoxy groups. C6, amino groups, imidazolyl groups, pyridinyl groups, mono- or di- (C1-C6) alkylamino groups, mono- or di-hydroxy (C1-C6) alkylamino groups, tri (C1-C6) alkyl groups ) ammonio, thio groups, (C 1 -C 6) alkylthio groups, thio (C 1 -C 6) alkyl groups, (C 1 -C 6) alkylcarbonyl groups, hydrogenocarbonyl groups, hydroxycarbonyl groups, C 1 -C 6 alkoxy groups carbonyl, nitro groups, sulfonato groups, the corresponding protonated groups such as ammonio, imidazolio, and / or pyridinio.  5. Use according to any one of claims 1 to 4, characterized in that it further comprises at least one compound having a primary or secondary amine function or at least one activated methylene compound or a mixture of these compounds. this.  6. Use according to Claim 5, characterized in that the compound comprising a primary or secondary amine function is an aromatic amine chosen from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-pphenylenediamine and N- ( 2-hydroxy-ethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2, 3-, 2,4- or 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3- or 4- aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, orthophenylenediamine, p-phenylenediamine, ortho-toluenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2 , 5-diaminophenethol, 4-amino-3- <Desc / Clms Page number 19>

 methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylaminoaniline, 3-amino-4- (2 ') hydroxyethyloxy) aniline, 3,4-methylenediaminoaniline, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 6-methyl-3-amino-2-chlorophenol, 2-methyl-5-amino-4-chlorophenol, 3,4-methylenedioxyphenol, 5- (2-hydroxyethylamino) Methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, 2-amino-3-acid, amino or 4-aminophenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4- or 3,5-diaminobenzoic acid, 4-amino- or 5-amino-salicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-, 3-amino or 4-aminobenzene sulfonic acid, 3-amino-4-hydroxybenzenic acid 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4- amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4-tri-aminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5diaminopyrochatecol, 4,6-diaminopyrogallol, 3, 5-diamino-4hydroxypyrochatecol, and aromatic anilines and aromatic phenols having another aromatic residue, corresponding to the following formula (II) 11 in which <Desc / Clms Page number 20> Z represents a direct bond, a saturated or unsaturated, optionally hydroxylated, C1-C4 hydrocarbon chain, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group of formula Q- (CH2-P- Where P represents a direct bond or a group -CH2- or -CHOH-, Q and Q 'represent, independently of one another, an oxygen atom, a group NR7 where R7 represents a hydrogen atom, a C 1-4 alkyl or C 1-4 hydroxyalkyl group, or a 0- (CH 2) pNH or NH- (CH 2) p, -O group where p and p 'are 2 or 3 and o is a number between 1 and 4 or an aliphatic amine selected from 2-aminoethanol, 2-methoxyethylamine, 2-ethoxyethylamine, 2- (2-aminoethoxy) -ethanol, 2- or 3-aminopropanol, 2, 3-dihydroxypropylamine, 4-hydroxypropylamine, 2-aminopropane-1,3-diol, 2-amino-2-methylpropanol, 2-amino-2-methylpropane-1,3-diol, 2-amino-2 hydroxymethylpropane-1,3-diol, tetrahydropentylamine, pentahydroxyhex yamines such as glucamine, D-glucosamine, D-galactosamine, 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,3-diamino-2-propanol, 2- (2- aminoethylamino) ethylamine, 2- (2-aminoethylamino) ethanol, 3- (2-aminoethylamino) propylamine and 3- (2-aminoethylamino) propanol. R2, R3, R4, R5 and R6 each independently represent a hydrogen atom, a hydroxy group or an amino group, optionally substituted with C1-4alkyl, C1-4alkylalkyl or (C1-4alkoxy) - (C 1-4 alkyl), or a carboxylic or sulfonic acid group, R 1 represents a hydroxy or amino group optionally substituted by a C 1-4 alkyl, C 1-4 hydroxyalkyl or (C 1-4 alkoxy) - (C 1-4 alkyl) group,  7. Use according to claim 5, characterized in that the compound with an activated methylene function is selected from 1,2,3,3-tetramethyl-3Hindolium iodide, 1,2,3,3-p-toluenesulphonate. 3-tetramethyl-3H-indolium, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-ethylene-indoline, 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium toluenesulphonate, rhodanine, rhodanineacetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbituric acid, <Desc / Clms Page number 21>  thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbitic acid, oxindole, 3-indoxyl acetate, coumarone and 1-methyl-3-phenyl-2-pyrazinone.  8. Use according to any one of the preceding claims, characterized in that the composition has a pH of between 2 and 12, preferably between 3 and 11.  9. Use according to any one of the preceding claims, characterized in that the concentration of the compound of formula (I) is between 0.0001% and 30%, relative to the total weight of the composition.  10. Use according to any one of the preceding claims, characterized in that the concentration of the activated methylene compound or the compound having a primary or secondary amine function is between 0.0001% and 30%, based on the total weight of the composition.  11. Cosmetic dye composition comprising, in a medium suitable for dyeing keratinous fibers, at least one ninhydrin derivative of formula (I) as defined in claims 1 to 4 and at least one surfactant and / or a polymeric agent of nonionic, cationic, anionic or amphoteric nature.  12. A ready-to-use cosmetic composition containing at least one ninhydrin derivative of formula (I) as defined in claims 1 to 4 and at least one compound containing a primary or secondary amine function or at least one methylene-functional compound. activated or a mixture thereof.  13. Multi-component hair coloring agent comprising as a first component, a composition (a) containing at least one compound of formula (I) as defined in claims 1 to 4, and 'as a second component, a composition (b) containing at least one compound comprising a primary or secondary amine function or at least one activated methylene compound as defined in claims 5 to 7 or a mixture thereof. <Desc / Clms Page number 22>  14. hair dyeing agent according to claim 13, characterized in that it is in the form of a multi-compartment kit, with at least a first compartment containing the composition (a) and at least a second compartment containing the composition (b).  15. A hair dyeing method comprising applying to the hair, a hair dye composition according to any one of claims 1 to 10, a sufficient exposure time to achieve the desired color, then the rinsing and washing the hair.  16. Hair dyeing process according to claim 15, characterized in that it comprises heating the hair impregnated with hair dyeing composition to a temperature of 80 C, preferably 60 C.  17. A hair dyeing method comprising applying to the hair one after the other, in any order, a composition (a) and a composition (b) as defined in claim 13.  18. Hair dyeing process according to claim 17, characterized in that an intermediate rinsing step is inserted between the application of the first composition and the application of the second composition.  A hair coloring method according to any one of claims 17 or 18, comprising heating hair impregnated with composition (a) and / or (b) to a temperature of 80 ° C, preferably 60 ° C. .