EP0981320A1 - Composition for dyeing keratin fibres comprising a pyrazolin-4,5-dione and an aromatic primary amine - Google Patents

Abstract

The invention concerns a composition for dyeing keratin fibres, in particular human keratin fibres such as hair comprising at least one pyrazolin-4,5-dione of formula (I) and at least one aromatic primary amine. Said composition enables the dyeing of keratin fibres without an oxidising agent in shades which are strong, varied, resistant and less selective than those of prior art. The invention also concerns dyeing methods and devices using said composition.

Description

 KERATINIC FIBER DYEING COMPOSITION COMPRISING A PYRAZOLIN-4.5-DIONE AND AN AROMATIC PRIMARY AMINE.

The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one pyrazolin-4,5-dione and at least one primary aromatic or heteroaromatic amine, and the methods and devices for dye using this composition.

For dyeing keratin fibers, and in particular human keratin fibers such as the hair, it is known to use dye compositions containing oxidation dye precursors, generally called oxidation bases, which are colorless compounds or weakly colored, and which, associated with oxidizing products, give rise to colored and coloring compounds by a process of oxidative condensation.

It is also known to vary the shades obtained with these oxidation bases, by associating them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors. The colorings obtained are generally intense with good properties of resistance over time (tenacity) against external agents (light, bad weather, washing, permanent undulations, perspiration, friction). However, the development of color requires the presence of an oxidant, most generally, hydrogen peroxide, which results in more or less marked deterioration in the state of the fiber.

It is also known to dye keratin fibers with direct dyes which are applied under mild conditions and which therefore generally respect the condition of the fiber. However, the shades obtained with these direct dyes are not very intense and often need to be reinforced. In addition, their resistance to external agents is less good, in particular the resistance to washing, and it is often considered insufficient.

To remedy these various drawbacks, it has already been proposed to dye the hair without oxidant, with dye compositions combining either (a) 2,3-indolinedione also called "isatin" or one of its derivatives, or (b) a derivative of 1, 2-ethanedione, either (c) a derivative of 1, 3-propanedione, or (d) a derivative of indolinone, with one or more aromatic amines and / or amino acids and / or oligopeptides and / or amino sugars and / or phenolic derivatives. Such dye compositions have been described in the following documents: - for 2,3-indolinedione and its derivatives: patents and patent applications US-4,750,408, EP- 0359465, EP- 0497697, EP- 0502783, EP- 0502784, EP- 0634923, EP- 0750490, DE- 4 314 317, DE- 4314318, DE- 4 409143, - for 1, 2-ethanedione derivatives: patent applications

DE- 4317855, DE- 4318742, DE- 4335625,

- for 1, 3-propanedione derivatives: patent applications DE- 4335626, DE- 4335627, DE- 4335628

- for indolinone derivatives: patent application DE-4335623.

However, the colorings obtained using said associations are not always satisfactory, in particular as regards certain properties such as gloss, power, tenacity and selectivity. Regarding selectivity, a good hair dye must be as homogeneous as possible from the root to the tip of the hair, it is said that it is not or not very selective.

However, hair dyes not comprising an oxidizing agent, such as direct dyes or dyes obtained using combinations of isatin, 1, 2-ethanedione, 1, 3-propanedione, or indolinone mentioned above, generally have the drawback of being very selective. There is therefore a real need to be able to have hair dye compositions which do not contain an oxidizing agent, in order to respect the state of the fiber, and generate powerful shades while being not very selective.

It is after extensive research carried out on the question that the plaintiff has now discovered, in a totally unexpected and surprising manner, that one could obtain varied and at the same time, brilliant shades, powerful, tenacious and not very selective, by applying to the keratin fibers, in the absence of an oxidizing agent, a dye composition containing at least one pyrazolin-4,5-dione of formula (I) and at least one aromatic or heteroaromatic amine of formula (II) defined below.

This discovery is the basis of the present invention.

The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, containing, in a medium suitable for dyeing, (i) at least one pyrazolin-4,5-dione of formula (I ) and (ii) at least one aromatic or heteroaromatic amine of formula (II), defined below.

Another subject of the invention is a two-component composition for which, in a medium suitable for dyeing, one contains at least one pyrazolin-4,5-dione of formula (I), the other an aromatic amine or heteroaromatic of formula (II), formulas (I) and (II) defined below, and which, stored separately, are (i) mixed at the time of use for application to keratin fibers or (ii ) applied sequentially to said fibers.

It also relates to the dyeing processes using these compositions.

Another object of the invention relates to a device with several compartments, or “kits”, for dyeing keratin fibers, characterized in that it comprises at least two compartments, one of which contains a composition containing , in a medium suitable for dyeing, at least one pyrazolin-4,5-dione of formula (I), and the other contains a composition containing, in a medium suitable for dyeing, at least one aromatic or heteroaromatic amine of formula (II) which is capable of reacting without oxidizing agent with the pyrazolin-4,5-dione of formula (I) to form a dye (formulas (I) and (II) defined below. However, other characteristics, aspects and advantages of the invention will appear even more clearly on reading the description which follows, as well as the various concrete examples, but in no way limiting, intended to illustrate it.

- (i) The pyrazolin-4,5-diones according to the present invention are compounds of formula (I) below:

in which, Ri represents:

a hydrogen atom, a linear or branched C-i-Cg alkyl radical optionally substituted by an OH, COOH, C-1-C4 alkoxy, C1-C4 hydroxyalkyl or C1-C4 dialkylamino radical,

a radical:

R ₃ in which m = 1, 2 or 3; n = 1, 2 or 3;

R = hydrogen or methyl; R. = methyl, hydroxy, linear or branched C ^ Cg alkoxy, linear or branched CΛ -C- hydroxyalkyl,

a radical ^{r 2} ′ ps in which p = 1 or 2 and R- represents a phenyl radical substituted or not,

a radical ^ ^{~ 2 ~} ^ j ^ s in which q = 1 or 2, and R _β represents a thienyl, furyl, pyridyl or piperidinyl radical or a non phenyl radical substituted or substituted by a maximum of 2 radicals chosen from methyl, trifluoromethyl, sulfonyl or methoxy radicals,

-a phenyl radical unsubstituted or substituted by one to five radicals chosen from: -COOH, -CH ₂ COOH, -N0 _2> -OH, -SO3H, -CH ₂ OH, -OCF3, -CF3, -SO ₂ CH ₃ , -SO ₂ NH ₂ , -SO ₂ NHC ₂ H ₅ , -SO ₂ NHCH ₂ CH ₂ OH, -CON (CH ₃ ) ₂ , -CON (C ₂ H ₅ ) ₂ , -CH ₂ N (CH ₃ ) ₂ , -CH ₂ N (C ₂ H ₅ ) ₂ , -NHCOCH3, -NHCOC ₂ H ₅ , a halogen atom such as Cl, Br or F, an alkyl radical in C _, - C linear or branched, a radical -ZR-, in which Z denotes O or S and Ry denotes H, or linear or branched C 1 -C alkyl,

a benzyl radical unsubstituted or substituted by a radical -COOH,

a pyridyl, pyrimidinyl, pyrazinyl, thiazinyl, benzothiazolyl, benzimidazolyl, thienyl, imidazolyl, thiazolyl, 1,2,4-triazolyl, indazolyl, indolyl, quinolyl or isoquinolyl radical

and R2 represents: -a hydrogen atom, a linear or branched C-i-Cβ alkyl radical optionally substituted by a C-ι-C4 hydroxy or alkoxy radical,

a phenyl radical substituted or not by a halogen atom (Cl, Br, F), a nitro radical, a trifluoromethyl radical,

a phenyl radical substituted at most by 3 radicals chosen from C1-C4 alkyl, C-1-C4 alkoxy, C1-C4 dialkylamino or C1-C2 alkylthio,

-a radical in which r = 1, 2 or 3, and Rg denotes a radical -SO3H, C ₁ -C ₂ alkylthio, or benzylthio, a methoxycarbonyl radical, or ethoxycarbonyl, a phenyl radical optionally substituted by an atom halogen (CI, Br, F), a C ..- C3 alkyl radical, a C ..- C3 alkoxy radical, a C dialkylamino radical _| -C ₄ , or C_ alkylthio _| -C ₂ ,

a C ₁ -C ₄ alkoxy radical; a phenoxy radical optionally substituted by one or more halogen atoms (Cl, Br, F); a trifluoromethyl, acetamido, carboxyl, methoxycarbonyl, ethoxycarbonyl radical; a thienyl, furyl, pyridyl or pyrazolyl radical,

it being understood that when R ₂ denotes an alkyl or phenyl radical, R ₂ can be linked to the carbon atom of the pyrazolinic nucleus via a heteroatom denoting O, NH, or S,

and the cosmetically acceptable salts of these compounds.

Among the pyrazolin-4,5-diones of formula (I) which can be used in the dyeing compositions according to the present invention, the compounds of formula (I) are more particularly preferred for which,

RH denotes: -a hydrogen atom,

-a alkyl, C ^ -C ₄ linear or branched, optionally substituted by hydroxy or alkoxy radical C _j -C ₂ (CH -) R

a radical ² q ⁶ in which q = 1 or 2, and Rg denotes a phenyl radical optionally substituted by a methyl, trifluoromethyl or sulfonyl radical,

-a phenyl radical optionally substituted by a C _ alkyl radical, - C ₂ , a C_ alkoxy radical _| -C ₂ , a radical -SOgH, -COOH, -OH, -CF3, -NO ₂ , or a halogen atom (Cl, Br, F),

and those of formula (I) for which R ₂ denotes:

-a hydrogen atom, -a alkyl, C.-C., linear or branched, optionally substituted by hydroxy or alkoxy radical, C _j -C ₂

-a phenyl radical optionally substituted by a halogen atom (Cl, Br, F), a C ..- C ₄ alkyl radical, a C _ alkoxy radical, - C ₂ , a C-ι-C dialkylamino radical ₂ ,

-a alkoxy C ..- C3, a trifluoromethyl radical, an acetamido radical, a dialkylamino radical in C _, - C _2, carboxyl, methoxycarbonyl or ethoxycarbonyl, furyl, thienyl, pyridyl or pyrazolyl.

Among the said pyrazolin-4,5-diones, mention may in particular be made of the following compounds:

- 3-methyl-1-phenyl-pyrazolin-4,5-dione; 1-phenyl-pyrazolin-4,5-dione; 3-tert-butyl-1-phenyl-pyrazolin-4,5-dione; 1,3-diphenyl-pyrazolin-4,5-dione; 1-phenyl-3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1-phenyI-3- (4'-methoxyphenyl) - pyrazolin-4,5-dione; 1-phenyl-3- (4'-nitrophenyl) -pyrazoiin-4,5-dione; 3-methoxy-1-phenyl-pyrazolin-4,5-dione; 3-ethoxy-1-phenyl-pyrazolin-4,5-dione; 3-acetamido-1-phenyl-pyrazolin-4,5-dione; 3-carboxy-1-phenyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-phenyl-pyrazolin-4,5-dione; 2'-furyl-1-phenyi-pyrazolin-4,5-dione;1-phenyl-3-trifluoromethyl-pyrazoiin-4,5-dione; 1 - [(3'-trifluoromethyl) -benzyl)] - 3-methyl-pyrazolin-4,5-dione; 1 - [(1'-phenyl) - ethyl)] - 3-methyl-pyrazolin-4,5-dione; 3-methyl-pyrazolin-4,5-dione; 1,3-dimethyl-pyrazolin -4,5-diόne; 3-methyl-1- (4'-nitrophenyl) -pyrazolin-4,5-dione; 3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-pyrazolin-4,5-dione; 1-methyl-pyrazolin-4,5-dione; 1-methyl-3-phenyl-pyrazolin-4,5-dione; 1-methyl-3- (4'-chlorophenyl) -pyrazolin-4,5-dione; 1-methyl-3- (3'-methoxyphenyl) -pyrazαlin-4,5-dione; 1-methyl-3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1-methyl-3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1-methyl-3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1-methyl-3- (2'-furyl) -pyrazolin-4,5-dione; 1-methyl-3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-1-methyl-pyrazolin-4,5-dione; 3-acetamido-1-methyl-pyrazolin-4,5-dione; 3-carboxy-1-methyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-methyl-pyrazolin-4,5-dione; 1-methyl-3-trifluoromethyl- pyrazolin-4,5-dione; 1-methyl-3-tert-butyl-pyrazolin-4,5-dione; 1-ethyl-pyrazolin-4,5-dione; 1-ethyl-3-methyl-pyrazolin-4,5-dione; 1-ethyl-3-phenyl-pyrazolin-4,5-dione; 1-ethyl-3- (4'-chlorophenyl) -pyrazolin-4,5-dione; 1-ethyl 3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1-ethyl-3- (4'-methoxyphenyl) - pyrazolin-4,5-dione; 1-ethyl-3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1-ethyl-3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1-ethyl-3- (2'-furyl) -pyrazolin-4,5-dione; 1-ethyl-3-methoxy-pyrazolin-4,5-dione; 1-ethyl-3-ethoxy-pyrazolin-4,5-dione; 1-ethyl-3-acetamido-pyrazolin-4,5-dione; 1-ethyl-3-carboxy-pyrazolin-4,5-dione; 1-ethyl-3-methoxycarbonyl-pyrazolin-4,5-dione; 1-ethyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-ethyl-3-tert-butyl-pyrazolin-4,5-dione; 1-isopropyl-pyrazolin-4,5-dione; 1-isopropyl-3-methyl-pyrazolin-4,5-dione; 1-isopropyl-3-phenyi-pyrazolin-4,5-dione; 1-isopropyl-3- (4'-chlorophenyl) - pyrazolin-4,5-dione; 1-isopropyl-3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1-isopropyl-3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1-isopropyl-3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1-isopropyl-3- (4'-methylphenyl) -pyrazoiin-4,5-dione; 1-isopropyl-3- (2'-furyl) -pyrazolin-4,5-dione; 1-isopropyl-3-methoxy-pyrazolin-4,5-dione; 1-isopropyl-3-ethoxy-pyrazolin-4,5-dione; 1-isopropyl-3-acetamido-pyrazolin-4,5-dione; 1-isopropyl-3-carboxy-pyrazoiin-4,5-dione; 1-isopropyl-3-methoxycarbonyl-pyrazolin-4,5-dione; 1-isopropyl-3-tert-butyl-pyrazolin-4,5-dione; 1-isopropyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-tert-butyl-pyrazolin-4,5-dione; 1-tert-butyl-3-methyl-pyrazolin-4,5-dione; 1-tert-butyl-3-phenyl pyrazolin-4,5-dione; 1-tert-butyl-3- (4'-chlorophenyl) -pyrazolin-4,5-dione; 1-tert-butyl-3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1-tert-butyl -3- (4'-methoxyphenyl) -pyrazoiin-4,5-dione; 1-tert-butyl-3- (3'-nitrophenyl) - pyrazolin-4,5-dione; 1-tert-butyl-3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1- tert-butyl-3- (2'-furyl) -pyrazolin-4,5-dione; 1- tert-butyl-3-methoxy-pyrazolin-4,5-dione; 1-tert-butyl-3-acetamido-pyrazolin-4,5-dione; 1-tert-butyl-3-carboxy-pyrazolin-4,5-dione; 1-tert-butyl-3-methoxycarbonyl-pyrazolin-4,5-dione; 1- tert-butyl-3-trifluoromethyl-pyrazoiin-4,5-dione; 1,3-ditert-butyl-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-methyl-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-phenyl-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (4'-chlorophenyl) -pyrazolin-4,5-dione; the 1- (4'- methylphenyl) -3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) - 3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (4'-methylphenyl) pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (2'-furyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (2'-thienyl) -pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3- (5'-pyrazolyl) -pyrazoiin-4,5-dione; 1- (4'-methylphenyl) -3-methoxy-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-ethoxy-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-dimethylamino-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-diethylamino-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-acetamido-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-carboxy-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-methoxycarbonyl-pyrazolin-4,5-dione; 1- (4'-methylphenyl) -3-ethoxycarbonyl-pyrazoiin-4,5-dione; 1-benzyl-pyrazolin-4,5-dione; 1-benzyl -3-methyl-pyrazolin-4,5-dione; 1-benzyl-3-phenyl-pyrazolin-4,5-dione; 1- benzyl-3- (4'methylphenyl) -pyrazolin-4,5-dione; 1-benzyl-3- (3'-methoxyphenyl) - pyrazolin-4,5-dione; 1-benzyl-3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- benzyl-3- (3'-nitrophenyl) -pyrazoiin-4,5-dione; 1-benzyl-3-tert-butyl-pyrazolin-4,5-dione; 1-benzyl-3-methoxy-pyrazolin-4,5-dione; 1-benzyl-3-acetamido-pyrazolin-4,5-dione; 1-benzyl-3-carboxy-pyrazolin-4,5-dione; 1-benzyl-3-methoxycarbonyl-pyrazolin-4,5-dione; 1-benzyl-3- (2'-furyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-methyl-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-phenyl-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3- (4'-chlorophenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) - 3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-methoxy-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-ethoxy-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-acetamido-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-carboxy-pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-methoxycarbonyl-pyrazolin-4,5-dione; 3- (2'-furyl) -1- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-methoxyphenyl) -3-trifluoromethyl-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-methyl-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-phenyl-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) - 3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3- (4'-methoxyphenyl) - pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3- (3'-nitrophenyl) -pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-methoxy-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-ethoxy-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-acetamido-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-carboxy-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-methoxycarbonyl-pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3- (2'-furyl) -pyrazolin-4,5-dione; 1- (4'-chlorophenyl) -3-trifluoromethyl-pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3-methyl-pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3-phenyl-pyrazoiin-4,5-dione; 1- (4'-nitrophenyl) -3- (4'-methylphenyl) -pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3- (4'-methoxyphenyl) -pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3- (3'-nitrophenyl) - pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3-carboxypyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3- (2'-furyl) -pyrazolin-4,5-dione; 1- (4'-nitrophenyl) -3-trifluoromethyl-pyrazolin-4,5-dione; 3-trifluoromethyl-pyrazolin-4,5-dione; pyrazolin-4,5-dione; 3-methyl-pyrazolin-4,5-dione; 3-phenyl-pyrazolin-4,5-dione; 3- (4'-methylphenyl) -pyrazolin-4,5-dione; 3- (4'-methoxymethyl) -pyrazolin-4,5-diorie; 3- (4'-nitrophényi) -pyrazoiin-4,5-dione; 3-methoxy-pyrazolin-4,5-dione; 3-acetamido-pyrazolin-4,5-dione; 3-carboxy-pyrazolin-4,5-dione; 3-methoxycarbonyl-pyrazolin-4,5-dione; 3- (2'-furyl) -pyrazolin-4,5-dione.

According to the present invention, it is very particularly preferred to use the pyrazolin-4,5-diones of formula (I) for which, cumulatively, Rj is chosen from hydrogen or methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl and R2 is chosen from hydrogen or methyl, phenyl, methoxyphenyl, methoxy, ethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, acetamido, trifluoromethyl or furyl radicals.

Thus, in the dye compositions according to the invention, it is more particularly preferred to use 3-methyl-1-phenyl-pyrazolin-4,5-dione; 3-methyl-pyrazolin-4,5-dione; 1,3-dimethyl-pyrazolin-4,5-dione; 1-ethyl-3-methyl- pyrazolin-4,5-dione; 1-isopropyl-3-methyl-pyrazolin-4,5-dione; 1-tert-butyl-3-methyl-pyrazolin-4,5-dione; 1-methyl-3-phenyl-pyrazolin-4,5-dione; 1- methyl-3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 3- (2'-furyl) -1-methyl-pyrazolin-4,5-dione; 1-methyl-3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-1-methyl-pyrazolin-4,5-dione; 3-diethylamino-1-methyl-pyrazolin-4,5-dione; 3-acetamido-1-methyl-pyrazolin-4,5-dione; 1-phenyl-pyrazolin-4,5-dione; 1-methyl-pyrazolin-4,5-dione; 1-ethyl-pyrazolin-4,5-dione; 1-isopropyl-pyrazolin-4,5-dione; 1-tert-butyl-pyrazolin-4,5-dione; 3-methoxy-1-phenyl-pyrazolin-4,5-dione; 3-ethoxy-1-phenyl-pyrazolin-4,5-dione; 3-acetamido-1-phenyl-pyrazolin-4,5-dione; 1-phenyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-methyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-isopropyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-ethyl-3-trifluoromethyl-pyrazolin-4,5-dione; 3-thfluoromethyl-pyrazolin-4,5-dione; 3-carboxy-1-phenyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-phenyl-pyrazolin-4,5-dione; 3-ethoxycarbonyl-1-phenyl-pyrazolin-4,5-dione; 3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-pyrazolin-4,5-dione; 3-carboxy-1-methyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-methyl-pyrazolin-4,5-dione; 3-ethoxycarbonyl-1-methyl-pyrazolin-4,5-dione; 1- (n-propyl) -pyrazolin-4,5-dione; 1- (n-propyl) -3-trifluoromethyl-pyrazolin-4,5-dione; 3- (2'-furyl) -1- (n-propyl) -pyrazolin-4,5-dione; 3- (2'-furyl) -1-phenyl-pyrazolin-4,5-dione; 1-phenyl-3-tert-butyl-pyrazoiin-4,5-dione; 1,3-diphenylpyrazolin-4,5-dione; 1-methyl-3-tert-butyl-pyrazolin-4,5-dione; 1- (n-propyl) - 3-tert-butyl-pyrazolin-4,5-dione; 3-carboxy-1-methyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-phenyl-pyrazolin-4,5-dione.

The pyrazoiin-4,5-diones according to the invention can be prepared according to known methods comprising the following steps (the meanings of R_, and R ₂ are as given above).

The first process consists in: a) reacting a pyrazolin-5-one ® with a nitroso-aromatic compound so as to obtain the corresponding 4-arylimino-pyrazolin-5-one ©:

Φ ®

this reaction being preferably carried out in a lower alcohol such as methanol, ethanol or isopropanol, at a temperature between 65 ° C and 85 ° C, at reflux of the solvent used, and preferably in the presence of a weak base of carbonate or bicarbonate type, in catalytic amount,

b) then hydrolyzing the 4-arylimino pyrazolin-5-one®, preferably in a strong acid medium, to obtain the corresponding pyrazolin-4,5 dione derivative of formula (I):

(D In such a process, the aromatic nitroso derivative of the first step is preferably a p-nitrosodialkylaniline of formula © ':

in which R 'and R "represent a linear or branched CC ₄ alkyl radical.

The acid hydrolysis of the second step of the preparation process according to the invention is preferably carried out with dilute sulfuric acid or aqueous hydrochloric acid, at room temperature, in the presence of a co-solvent of pyrazolin-4 , 5-dione immiscible with water, which advantageously extracts the compound as it is formed, facilitating its isolation with very high purity. The water-immiscible cosolvent can be a halogenated solvent such as, for example, dichloromethane or 1,2-dichloroethane. In a preferred embodiment of the invention, the water-immiscible cosolvent is an ether such as diethyl or diisopropyl ether.

The second process consists in:

a) reacting bromine on a pyrazolin-5-one of formula Φ to obtain the corresponding 4,4-dibromo-pyrazolin-5-one of formula © (step a),

b) then reacting lead diacetate so as to form the corresponding diacetate of formula ©, an unstable intermediate product which spontaneously leads, by elimination of acetic anhydride, to the pyrazolin-4,5-dione derivative of formula (I) desired (step b), these two steps a and b therefore being carried out according to the following reaction scheme: Step a

© ®

Etap

© (D

Step a of dibromation is preferably carried out in an aqueous medium in the presence of 2 equivalents of bromine, at ambient temperature. The reaction is generally complete in a few hours: the dibromo derivative precipitates as it is formed, which allows isolation by simple filtration with high purity.

Step b is advantageously carried out in a few hours at reflux of acetic acid, the lead dibromide which forms being able to be separated very easily by simple filtration. - (ii) The aromatic or heteroaromatic amines which can be used according to the present invention have the following formula (II):

R ₉ NH ₂ (II) in which Rg represents:

a 5 or 6-membered ring which can contain a maximum of 3 identical or different heteroatoms, chosen from oxygen, nitrogen or sulfur,

-a set of 2 or 3 rings each comprising 5 to 6 links, the set containing a maximum of 9 heteroatoms, identical or different, chosen from oxygen, nitrogen or sulfur, said rings being joined or linked together by l intermediary of a heteroatom (O, N, S) or of a polymethylenic radical containing from 1 to 5 carbon atoms, which can be linear or branched, saturated or unsaturated, and contain, linked or intercalated in the main chain one or more oxygen, sulfur, nitrogen, or sulphoxide, sulphone, disulphide, amino, C _> - C _2l hydroxyl, quaternary ammonium, ureido, amide or ester;

'e (s) cycle (s) or heterocycle (s) designated by R _g may be unsubstituted or substituted by a maximum of 7 substituents chosen from amino, hydroxy, cyano, trifluoromethyl, linear C _, - C ₄ alkyl or branched, C _j -C ₄ alkoxy, mono- or di-aikylamino C _, - C ₄ , carboxyl, C _ alkoxycarbonyl, - C ₂ , sulfonyl, sulfonamido, acetamido, amido, mercapto, C ^ -C ₄ alkylthio , nitro, C_ alkylsulfone _| -C ₂ , C _, hydroxyalkyl, C ₄ , keto, or a Cl, Br, or F atom, and their cosmetically acceptable salts.

Said aromatic or heteroaromatic amines are preferably chosen from anilines, aminoindoles, aminoisoindoles, aminobenzothiazoles, aminobenzimidazoles, aminobenzoxazoles, aminoquinolines, aminesoquinolines, aminobenzoxazines, aminotetrahydroquinoxalines, aminobenzothiazines, aminotetrahydroisoquinolines, aminoindazoles, aminopyridines, aminopyrimidines, aminotriazines, aminopyrroles, aminoprazoles, aminofurazins, aminofurans, aminofurans, amino aminotriazoles, aminouracils, aminothiouracils, aminojulolidines, aminopyrazolones.

Such amines are known as such, have been prepared in the prior art, and are in particular the following:

- paraphenylenediamine,

- paratoluenediamine,

- 2-isopropyl-paraphenylenediamine,

- 2-β-hydroxyethyl-paraphenylenediamine, - 2-β-hydroxyethyloxy-paraphenylenediamine,

- 2,6-dimethyl-paratoluenediamine,

- 2,6-diethyi-paraphenylenediamine,

- 2,3-dimethyl-paraphenylenediamine,

- N, N-bis- (2-hydroxyethyl) -paraphenylenediamine, - 4-amino-1- (2-methoxyethyl) -aminobenzene,

- 2-chloro-paraphenylenediamine,

- paraaminophenol,

- 4-amino-3-methylphenol,

- 4-amino-3-fluorophenol, - 4-amino-3-hydroxymethylphenol,

- 4-amino-2-methylphenol,

- 4-amino-2-hydroxymethylphenol,

- 4-amino-2-methoxymethylphenol,

- 4-amino-2-aminomethylphenol, - 4-amino-2- (2-hydroxyethylaminomethyl) -phenol,

- 2-aminophenol,

- 2-amino-1-hydroxy-5-methylbenzene, - 2-amino-1-hydroxy-6-methylbenzene,

- 5-acetamido-2-aminophenol,

- 4,5-diamino-1, 3-dimethylpyrazole, - 4,5-diamino-1-ethyl-3-methylpyrazole,

- 4,5-diamino-1-n-propyl-3-methylpyrazole,

- 4,5-diamino-1-isopropyl-3-methylpyrazole,

- 3,4-diamino-5-methylpyrazole,

- 1-methyl-4,5-diaminopyrazole, - 3,4-diaminopyrazole,

- 4,5-diamino-1-propyl-pyrazole,

- 4,5-diamino-1-methyl-3-tert-butyl-pyrazole,

- 9-aminojulolidine,

- 3,7-diaminopyrazolopyrimidine, - 1,2-methylenedioxy-4-methoxy-5-aminobenzene,

- 2-methyl-3,5-diaminoindazole,

- 3,4-diamino-1,5-dimethylpyrazole,

- 4,5-diamino-1, 3-dimethylisoxazole,

- 4,5-diamino-1, 3-dimethylisothiazole,

- 4,5-diamino-thiouracil,

- 4,5-diamino-uracil,

- 2- (2-acetamidoethoxy) -1, 4-diaminobenzene,

- 3-amino-1- (4-aminophenyl) -pyrazoline, - 4-amino-1- (4-aminophenyl) -pyrazole,

- 2,3-diaminopyridine,

and their cosmetically acceptable salts.

Within the meaning of the present invention, the cosmetically acceptable salts of the compounds of formula (I) and of the aromatic or heteroaromatic amines of formula (II) can be hydrochlorides, sulphates, hydrobromides or tartrates.

The concentration of pyrazolin-4,5-dione of formula (I) in the dye composition according to the present invention is preferably between approximately 0.01 and 5%, and even more preferably between approximately 0.15 and 2% by weight, based on the total weight of the dye composition.

The concentration of aromatic or heteroaromatic amine in the dye composition according to the present invention is preferably between approximately 0.01 and 5%, and even more preferably between approximately 0.15 and 2% by weight, relative to the total weight of the dye composition.

The medium suitable for dyeing is preferably an aqueous medium consisting of water and / or cosmetically acceptable organic solvents, and more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, ethylene glycol and its monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, the monoethyl ether or the monobutyl ether of diethylene glycol, in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition. It is also possible to add to the dye composition according to the invention fatty amides such as the mono- and di-ethanolamides of acids derived from copra, lauric acid or oleic acid, at concentrations of between approximately 0, 05 and 10% by weight. It is also possible to add to the dye composition according to the invention surfactants well known from the prior art and of anionic, cationic, nonionic, amphoteric, zwitterionic type or their mixtures, preferably in a proportion comprised between about 0.1 and 50% by weight and advantageously between approximately 1 and 20% by weight relative to the total weight of the composition.

Thickening agents can also be used in an amount ranging from about 0.2 to 20%. Said dye composition may also contain various usual adjuvants such as antioxidants, perfumes, sequestering agents, dispersing agents, hair conditioning agents, preserving agents, opacifying agents, as well as any other adjuvant used usually in tincture of keratin materials. Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged.

The dye composition according to the invention can be formulated at acidic, neutral or alkaline pH, the pH possibly varying for example from 2 to 12 and preferably from 3 to 9, and being able to be adjusted by means of alkalinizing agents or d previously known acidifying or buffering agents. As alkalizing agents, there may be mentioned ammonia, alkali carbonates, alkanolamines, for example mono- and triethanolamines and their derivatives, sodium or potassium hydroxides, and the compounds of formula:

in which, R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R ₁₀ R _{11 (R 12} and R _13, simultaneously or independently of one another represent hydrogen, alkyl C, -C ₄ alkyl or hydroxy C, -C _4. The acidifying agents are conventionally mineral or organic acids such as hydrochloric, tartaric, citric and phosphoric acids. Among the buffers, mention may be made, for example, of potassium diacid phosphate / sodium hydroxide.

The composition applied to the hair can be in various forms, such as in the form of a liquid, cream, gel or in any other form suitable for dyeing keratin fibers. In particular, it can be packaged under pressure in an aerosol can in the presence of a propellant and form a foam.

Another object of the present invention relates to a process for dyeing keratin materials, in particular human keratin fibers such as the hair, consisting in applying a dye composition containing, in a medium suitable for dyeing, at least one pyrazolin-4 , 5-dione of formula (I) and an aromatic or heteroaromatic amine of formula (II), on dry or wet keratin fibers, allowing the composition to act on the fibers for an exposure time varying between 3 and 60 minutes approximately, preferably between 5 and 45 minutes approximately, at a temperature varying between 20 ° C and 50 ° C approximately, to rinse, possibly to wash, then to rinse again, and to dry.

Another variant of the process constitutes another object of the invention, and consists in applying to the keratin fibers, simultaneously or sequentially (i) a dye composition containing, in a medium suitable for dyeing, at least one pyrazolin-4,5- dione of formula (I), and (ii) a composition essentially containing an aromatic or heteroaromatic amine of formula (II) in a medium suitable for dyeing.

Concrete examples illustrating the invention will now be given. EXAMPLES OF TINCTORIAL COMPOSITIONS

In examples 1 to 4, the shades obtained on hair were quantified with the Minolta CM 2002 colorimeter. The criterion of selectivity of the dye was evaluated by means of the color variation index I, calculated according to the following NICKERSON equation. :

I = (C / 5) x 2ΔH + 6ΔV + 3ΔC (see in this regard "Journal of the Optical Society of America", 1944, Sept., Vol 34, n ° 9, pp 550-570), equation in which, the parameters H, V, C represent those of the MUNSELL notation (Standard ASTM D 1535-68), which defines the color [H: denoting the shade or HUE, V: denoting the intensity or VALUE, and C: denoting the purity or CHROMATICITY].

EXAMPLE 1:

The dye composition in accordance with the following invention was prepared just before use:

3-methyl-1-phenyl-pyrazolin-4,5-dione 0.940 g (o.oo moie)

Paraphenylenediamine 0.540 g (o.oo moie)

Ethyl alcohol 40.0 g

Citric acid q.s pH 2

Water q.s.p 100,0 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. '' about 20 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in a shade numbered 8. OR 4.0 / 2.4 on non-permanent hair and 6.4R 3.4 / 3.1 on permanent hair. From these Munsell figures, we calculated the difference in coloring (using Nickerson's equation), which exists between permanent and non-permanent hair. This difference which represents the "selectivity" of the dye was equal to 7.2.

Comparative EXAMPLE 2:

The following dye composition according to the prior art was prepared, just before use:

Isatin (prior art dye) 0.735 g (0.005 mole)

Paraphenylenediamine 0.540 g (o.oo moie)

Ethyl alcohol 40.0 g

Citric acid q.s pH 2 water q.s.p 100, 00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, according to the same protocol as in Example 1. The hair was dyed in a shade numbered 6.9 YR 4.9 / 4.3 on non-permanent hair and 3.6 YR 4.0 / 5.6 on permanent hair.

From these Munsell figures, we calculated the difference in coloring (using Nickerson's equation), which exists between permanent and non-permanent hair. This difference which represents the "selectivity" of the dye was equal to 15.0.

Compared with the selectivity of the dye of Example 1 according to the invention which was only 7.2, the selectivity of the dye of Example 2 (15.0) according to the prior art is much higher; it has thus been demonstrated that a permed hair comprising non-permed roots will present, after dyeing by means of composition 1 according to the invention, a more uniform coloring (less selective) than by means of composition 2 of the art prior. EXAMPLE 3:

The dye composition in accordance with the following invention was prepared just before use:

3-methyl-1-phenyl-pyrazolin-4,5-dione 0.940 g (o.oo moie)

2-β-hydroxyethyl-paraphenylenediamine, 2HCI 1.120 g (o.oo moie)

Ethyl alcohol 40.0 g

Citric acid q.s pH 2

Water q.s.p 100,0 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, according to the same protocol as in Example 1.

The hair was dyed in a shade numbered 4.9 R 3.6 / 2.3 on non-permanent hair and 2.7 R 3.0 / 2.9 on permanent hair.

From these Munsell figures, we calculated the difference in coloring (using Nickerson's equation), which exists between permanent and non-permanent hair. This difference which represents the "selectivity" of the dye was equal to 7.4.

Comparative EXAMPLE 4:

The following dye composition according to the prior art was prepared, just before use:

Isatin (dye of the prior art) 0.735 g (o.oo moie)

2-β-hydroxyethyl-paraphenylenediamine, 2HCI 1, 120 g (o.oo moie)

Ethyl alcohol 40.0 g

Citric acid qs pH 2 water qs 100, 00 g The above composition was applied to locks of natural hair; gray with 90% white, permanent and non-permanent, following the same protocol as in Example 1.

The hair was dyed in a shade numbered 5.6 YR 4.4 / 3.3 on non-permanent hair and 0.9 YR 3.4 / 4.9 on permanent hair.

From these Munsell figures, we calculated the difference in coloring (using Nickerson's equation), which exists between permanent and non-permanent hair. This difference which represents the "selectivity" of the dye was equal to 17.0.

Compared with the selectivity of the dye of Example 3 according to the invention which was only 7.4, the selectivity of the dye of Example 4 (17.0) according to the prior art is much more high; it has thus been demonstrated that a permanent hair having non-permanent roots will present, after dyeing by means of composition 3 according to the invention a more uniform coloring (less selective) than by means of composition 4 of the prior art .

EXAMPLE 5

The dye composition in accordance with the following invention was prepared just before use:

3-methyl-1-phenyl-pyrazolin-4,5-dione 0.94 g (o.oos mole)

4,5-diamino-1-methyl-3-tert-butyl-pyrazole, 2HCI 1, 21 g (o.oo moie)

Hydroxypropylguar sold. under the name

Jaguar HP-60 by the company Mayhall 1, 00 g

Alkyl (C-β / C-io 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by the company Seppic 5.00 g MA. . ***

Ethyl alcohol 10.00 g

Preservatives q.s

Monoethanolamine q.s pH 6

Demineralized water qs ... 100.00 g MA * = Active Matter

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. '' about 20 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in an iridescent-copper shade on non-permanent hair and copper-red shade on permanent hair.

EXAMPLE 6

The dye composition in accordance with the following invention was prepared just before use:

3-methyl-1-phenyl-pyrazolin-4,5-dione 0.94 g (o.oo moie)

3,7-diaminopyrazolopyrimidine, 2HCI 1, 11 g (o.oo moie)

Hydroxypropylguar sold. under the name

Jaguar HP-60 by the company Mayhall 1, 00 g

Alkyl (Cβ / C-io 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by Seppic 5.00 g MA ^*

Ethyl alcohol ... 10.00 g

Preservatives q.s

Monoethanolamine q.s pH 4

Demineralized water q.s.p .... 100.00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. 'about 50 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in an intense copper-red shade on non-permanent hair and powerful copper-red on permanent hair.

EXAMPLE 7 The following dye composition according to the invention was prepared, just before use:

3-methyl-1-phenyl-pyrazolin-4,5-dione 0.94 g (o.oos mole)

2- (2-acetamidoethoxy) -1, 4-diaminobenzene, 2HCI .... 1.41 g (o.oos moie) Hydroxypropylguar sold under the name

Jaguar HP-60 by the company Mayhall 1, 00 g

Alkyl (Cβ / C-io 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by Seppic 5.00 g MA *

Ethyl alcohol 10.00 g

Preservatives q.s

Monoethanolamine q.s pH 6

Demineralized water q.s.p .... 100.00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. 'about 50 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in an intense purplish red shade on non-permanent hair and on permanent hair.

EXAMPLE 8

The dye composition in accordance with the following invention was prepared just before use:

1-methyl-3-tert-butyl-pyrazolin-4,5-dione 0.84 g (o.oo moie) paraphenylenediamine 0.54 g (o.oo moie)

Hydroxypropylguar sold under the name

Jaguar HP-60 by the company Mayhall 1, 00 g

Alkyl (C8 / C-10 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by Seppic 5.00 g MA ^*

Ethyl alcohol 10.00 g

Preservatives ..... q.s

Monoethanolamine q.s pH 6

Demineralized water q.s.p .... 100.00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. 'about 50 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in an iridescent-copper shade on non-permanent hair and on permanent hair.

EXAMPLE 9

The dye composition in accordance with the following invention was prepared just before use:

1-methyl-3-phenyl-pyrazolin-4,5-dione 0.94 g (o.oo half) paraphenylenediamine 0.54 g (o.oos mole)

Hydroxypropylguar sold under the name

Jaguar HP-60 by the company Mayhall 1, 00 g

Alkyl (C8 / C ^< | o 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by Seppic 5.00 g MA *

Ethyl alcohol 10.00 g

Preservatives qs Monoethanolamine qs pH 6

Demineralized water q.s.p .... 100.00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. 'about 50 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in a deep purple-iridescent shade on non-permanent hair and on permanent hair.

EXAMPLE 10

The dye composition in accordance with the following invention was prepared just before use:

1, 3-diphenyl-pyrazolin-4,5-dione 1, 25 g (O.oos mole) paraphenylenediamine 0.54 g (O.oos m ^' goose)

Hydroxypropylguar sold under the name

Jaguar HP-60 by Mayhall 1.00 g

Alkyl (Cβ / C-io 50/50) polyglucoside (2) in 60% aqueous solution, sold under the name

Oramix CG110 by Seppic 5.00 g MA *

Ethyl alcohol 10.00 g

Preservatives q.s

Monoethanolamine q.s pH 9

Demineralized water q.s.p .... 100.00 g

The above composition was applied to locks of natural hair, gray with 90% white, permanent and non-permanent, at a rate of 6 g of composition per 3 g of hair, and left to stand for 30 minutes at room temperature. 'about 50 ° C. After rinsing with running water, washing with a conventional shampoo, rinsing again and drying, the hair was dyed in a golden-ashy shade on non-permanent hair and slightly coppery golden on permanent hair.

Claims

1- Composition for dyeing keratin fibers, in particular human keratin fibers such as hair, characterized in that it comprises, in a medium suitable for dyeing, (i) at least one pyrazolin-4,5-dione of formula (I) in which, Ri represents: a hydrogen atom, a linear or branched C- | -C6 alkyl radical optionally substituted by an OH, COOH, C1-C4 alkoxy, C-1-C4 hydroxyalkyl or C-1-C4 dialkylamino radical, - a radical: R ₃ in which m = 1, 2 or 3; n = 1, 2 or 3; R3 = hydrogen or methyl; R ₄ = methyl, hydroxy, linear or branched C1-Cc alkoxy, linear or branched C-hydroxyalkyl, a radical ^{r 2} ′ p ⁵ in which p = 1 or 2 and R5 represents a substituted or unsubstituted phenyl radical, a radical ^ ~ ^{2 "} ^ ^R s in which q = 1 or 2, and R _β represents a thienyl, furyl, pyridyl or piperidinyl radical or a phenyl radical unsubstituted or substituted by at most 2 radicals chosen from methyl radicals, trifluoromethyl, sulfonyl or methoxy, -a phenyl radical unsubstituted or substituted by one to five radicals chosen from: -COOH, -CH ₂ COOH, -N0 _2> -OH, -SO3H, -CH ₂ OH, -OCF ₃ , -CF3, -SO ₂ CH ₃ , -SO ₂ NH ₂ , -SO ₂ NHC ₂ H ₅ , -SO ₂ NHCH ₂ CH ₂ OH, -CON (CH ₃ ) ₂ , -CON (C ₂ H ₅ ) ₂ , -CH ₂ N (CH ₃ ) ₂ , -CH ₂ N (C ₂ H ₅ ) ₂ , -NHCOCH3, -NHCOC ₂ H ₅ , a halogen atom such as Cl, Br or F, an alkyl radical in C ,, - C ₃ linear or branched , a radical -ZR in which Z denotes O or S and Ry denotes H, or linear or branched C ₃ -C ₃ alkyl, a benzyl radical unsubstituted or substituted by a radical -COOH, -OCH ₃ , or -SO ₃ H, a pyridyl, pyrimidinyl, pyrazinyl, thiazinyl, benzothiazolyl, benzimidazolyl, thienyl, imidazolyl, thiazolyl, 1,2,4-triazolyl, indazolyl, indolyl, quinolyl or isoquinolyl radical and R2 represents: a hydrogen atom, a linear or branched C-i-Cβ alkyl radical optionally substituted by a hydroxy or C1-C4 alkoxy radical, a phenyl radical substituted or not by a halogen atom (Cl, Br, F), a nitro radical, a trifluoromethyl radical, a phenyl radical substituted at most by 3 radicals chosen from C-1-C4 alkyl, C1-C4 alkoxy, C-J-C4 dialkylamino or C-J-C2 alkylthio, - (- CH, -) - R „ a radical ^{2 r 8} in which r = 1, 2 or 3, and Rg denotes a radical -SO ₃ H, C ₁ -C ₂ alkylthio, or benzylthio, a methoxycarbonyl radical, or ethoxycarbonyl, a phenyl radical optionally substituted by a halogen atom (Cl, Br, F), alkyl C _, - C ₃ alkoxy, C _, - C _3, a dialkylamino radical in C _, - C _4, alkylthio C ₁ -C ₂ , -a C-ι-C ₄ alkoxy radical; a phenoxy radical optionally substituted by one or more halogen atoms (Cl, Br, F); a trifluoromethyl, acetamido, carboxyl, methoxycarbonyl, ethoxycarbonyl radical; a thienyl, furyl, pyridyl or pyrazolyl radical, it being understood that when R ₂ denotes an alkyl or phenyl radical, R ₂ can be linked to the carbon atom of the pyrazolinic nucleus via a heteroatom denoting O, NH, or S, and, (ii) an aromatic or heteroaromatic amine of formula (II) R ₉ NH ₂ (II) in which R _g represents: a 5 or 6-membered ring which can contain a maximum of 3 identical or different heteroatoms, chosen from oxygen, nitrogen or sulfur, -a set of 2 or 3 rings each comprising 5 to 6 links, the set containing a maximum of 9 heteroatoms, identical or different, chosen from oxygen, nitrogen or sulfur, said rings being joined or linked together by l intermediate of a heteroatom (O, N, S) or of a polymethylenic radical containing from 1 to 5 carbon atoms, which can be linear or branched, saturated or unsaturated, and contain, linked or intercalated in the main chain, one or more atoms of oxygen, sulfur, nitrogen, or sulfoxide, sulfone, disulfide, amino, C ₁ -C ₂ alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups; the cycle (s) or heterocycle (s) designated by R _g may be unsubstituted or substituted by a maximum of 7 substituents chosen from amino, hydroxy, cyano, trifluoromethyl, C _, - C ₄ alkyl linear or branched radicals , alkoxy in C _, - C ₄ , C _ mono- or di-alkylamino, - C ₄ , carboxyl, C _ alkoxycarbonyl, - C ₂ , sulfonyl, sulfonamido, acetamido, amido, mercapto, C _ alkylthio, - C ₄ , nitro, alkylsulfone in C ^^, hydroxyalkyl in C. _j -C ₄ , keto, or an atom of Cl, Br, or F, and the cosmetically acceptable salts of these compounds of formulas (I) and (II). 2- dye composition according to claim 1, characterized in that the pyrazolin-4,5-diones are chosen from those of formula (I) for which: R ₁ denotes: -a hydrogen atom, a linear or branched C ₄ -C ₄ alkyl radical, optionally substituted by a C ₂ -C ₂ hydroxy or alkoxy radical, - (- CH, -) - R ₆ a radical ² q ⁶ in which q = 1 or 2, and Rg denotes a phenyl radical optionally substituted by a methyl, trifluoromethyl or sulfonyl radical, -a phenyl radical optionally substituted by an alkyl radical in a C ₁ -C ₂ alkoxy radical, a -SO ₃ H, -COOH, -OH, -CF ₃ , -NO ₂ radical, or a halogen atom (Cl, Br, F), and those of formula (I) for which R ₂ denotes: a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical, optionally substituted with a hydroxy or C ₂ -C ₂ alkoxy radical, a phenyl radical optionally substituted with a halogen atom (Cl, Br, F), alkyl, C ,, - C ₄ alkoxy radical C ^ -C _j, a dialkylamino radical in C _.- C _2, -a alkoxy radical C _t -C ^, a trifluoromethyl radical, an acetamido radical, a dialkylamino radical in C_ _j -C ₂ alkyl, a carboxyl, a methoxycarbonyl or ethoxycarbonyl radical, a furyl radical, thienyl, pyridyl or pyrazolyl. 3- dye composition according to claims 1 and 2, characterized in that the pyrazolin-4,5-diones are chosen from those of formula (I) for which, cumulatively, R- | is chosen from hydrogen or methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl radicals, and R2 is chosen from hydrogen or methyl, phenyl, methoxyphenyl, methoxy, ethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl radicals, acetamido, trifluoromethyl or furyl. 4- dye composition according to any one of claims 1 to 3, characterized in that the pyrazolin-4,5-diones of formula (I) are: 3-methyl-1-phenyl-pyrazolin-4,5 -dione; 3-methyl-pyrazolin-4,5-dione; 1,3-dimethyl-pyrazolin-4,5-dione; 1-ethyl-3-methyl-pyrazolin-4,5-dione; 1-isopropyl-3-methyl-pyrazolin-4,5-dione; 1-tert-butyl-3-methyl-pyrazolin-4,5-dione; 1-methyl-3-phenyl-pyrazolin-4,5-dione; 1-methyl-3- (3'-methoxyphenyl) -pyrazolin-4,5-dione; 3- (2'-furyl) -1-methyl-pyrazolin-4,5-dione; 1-methyl-3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-1-methyl-pyrazolin-4,5-dione; 3-diethylamino-1-methyl-pyrazolin-4,5-dione; 3-acetamido-1-methyl-pyrazolin-4,5-dione; 1-phenyl-pyrazolin-4,5-dione; 1-methyl-pyrazolin-4,5-dione: 1-ethyl-pyrazolin-4,5-dione; 1-isopropyl-pyrazolin-4,5-dione; 1- tert-butyl-pyrazolin-4,5-dione; 3-methoxy-1-phenyl-pyrazolin-4,5-dione; 3-ethoxy-1-phenyl-pyrazolin-4,5-dione; 3-acetamido-1-phenyl-pyrazolin-4,5-dione; 1-phenyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-methyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-isopropyl-3-trifluoromethyl-pyrazolin-4,5-dione; 1-ethyl-3-trifluoromethyl-pyrazolin-4,5-dione; 3-trifluoromethyl-pyrazolin-4,5-dione; 3-carboxy-1-phenyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-phenyl-pyrazolin-4,5-dione; 3-ethoxycarbonyl-1-phenyl-pyrazolin-4,5-dione; 3-methoxy-pyrazolin-4,5-dione; 3-ethoxy-pyrazolin-4,5-dione; 3-carboxy-1-methyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-methyl-pyrazolin-4,5-dione; 3-ethoxycarbonyl-1-methyl-pyrazolin-4,5-dione; 1- (n-propyl) -pyrazolin-4,5-dione; 1- (n-propyl) -3-trifluoromethyl-pyrazolin-4,5-dione; 3- (2'-furyl) -1- (n-propyl) -pyrazolin-4,5-dione; 3- (2'-furyl) -1-phenyl- pyrazolin-4,5-dione; 1-phenyl-3-tert-butyl-pyrazolin-4,5-dione; 1,3-diphenylpyrazolin-4,5-dione; 1-methyl-3-tert-butyl-pyrazolin-4,5-dione; 1- (n-propyl) - 3-tert-butyl-pyrazolin-4,5-dione; 3-carboxy-1-methyl-pyrazolin-4,5-dione; 3-methoxycarbonyl-1-phenyl-pyrazolin-4,5-dione, and their cosmetically acceptable salts. 5- dye composition according to claim 1, characterized in that the aromatic or heteroaromatic amines of formula (II) are chosen from anilines, aminoindoles, aminoisoindoles, aminobenzothiazoles, aminobenzimidazoles, aminobenzoxazoles, aminoquinoiines, aminoisoquinolines, aminobenzoxazines, aminotetrahydroquinoxalines, aminobenzothiazines, aminotetrahydroisoquinolines, aminoindazoles, aminopyridines, aminopriimines, aminonaphthalenes, aminopyrinins, aminopyrines aminoisoxazoles, aminoisothiazoles, aminotriazoles, aminouracils, aminothiouracils, aminojulolidines, aminopyrazolones. 6- dye composition according to claim 5, characterized in that the amines are: paraphenylenediamine; paratoluenediamine; 2-isopropyi-paraphenylenediamine; 2-β-hydroxyethyl-paraphenylenediamine; 2-β-hydroxyethyloxy-paraphenylenediamine; 2,6-dimethylparatoluenediamine; 2,6-diethyl-paraphenylenediamine; 2,3-dimethyl-paraphenylenediamine; N, N-bis- (2-hydroxyethyl) -paraphenylene diamine; 4-amino-1 - (2-methoxyethyl) -aminobenzene; 2-chloro-paraphenylenediamine; paraaminophenol; 4-amino-3-methylphenol; 4-amino-3-fluorophenol; 4-amino-3-hydroxymethylphenol; 4-amino-2-methylphenol; 4-amino-2-hydroxymethylphenol; 4-amino-2-methoxymethylphenol; 4-amino-2-aminomethylphenol; 4-amino-2- (2-hydroxyethylaminomethyl) -phenol; 2-aminophenol; 2-amino-1-hydroxy-5-methylbenzene; 2-amino-1-hydroxy-6-methylbenzene; 5-acetamido-2-aminophenol; 4,5-diamino-1,3- dimethylpyrazole; 4,5-diamino-1-isopropyl-3-methylpyrazole; 4,5-diamino-1-ethyl-3-methylpyrazole; 4,5-diamino-1-n-propyl-3-methylpyrazole; 3,4-diamino-5-methylpyrazole; 1-methyl-4,5-diaminopyrazole; 3,4-diaminopyrazole; 4,5-diamino-1-propyl-pyrazole; 4,5-diamino-1-methyl-3-tert-butyl-pyrazole; 9-aminojulolidine; 3,7-diaminopyrazoiopyrimidine; 1,2-methylenedioxy-4-methoxy-5-aminobenzene; 2-methyl-3,5-diaminoindazole; 3,4-diamino-1,5-dimethylpyrazole; 4,5-diamino-1, 3-dimethylisoxazole; 4,5-diamino-1, 3-dimethylisothiazole; 4,5-diamino-thiouracil; 4,5-diamino-uracil: 2- (2-acetamidoethoxy) -1, 4-diaminobenzene; 3-amino-1- (4-aminophenyl) -pyrazoline; 4-amino-1- (4-aminophenyl) -pyrazole; 2,3-diaminopyridine, and their cosmetically acceptable salts. 7- Dye composition according to any one of the preceding claims, characterized in that it has a pH of between 2 and 12. 8- dye composition according to any one of the preceding claims, characterized in that the compound of formula (I) is present in a concentration ranging from 0.01 to 5% by weight relative to the total weight of the composition. 9- Dye composition according to any one of the preceding claims, characterized in that the aromatic or heteroaromatic amine of formula (II) is present in a concentration ranging from 0.01 to 5% by weight relative to the total weight of composition. 10- Dyeing composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing is an aqueous medium consisting of water and / or organic solvents chosen from alcohols, glycols and glycol ethers, in proportions of between 0.5 and 20% by weight relative to the total weight of the composition. 11- Two-component dye composition for which, in a medium suitable for dyeing, one contains at least one pyrazolin-4,5-dione of formula (I) defined in claims 1 to 4, the other an amine aromatic or heteroaromatic of formula (II) defined in claims 1, 5 and 6, which, stored separately, are (i) mixed at the time of use for application to keratin fibers or (ii) applied sequentially on said fibers. 12- Process for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that the dye composition defined according to any one of claims 1 to 11 is applied to dry or wet keratin fibers , and that after having allowed the composition to act for approximately 3 to 60 minutes, at a temperature varying between approximately 20 ° C. and 50 ° C., the fibers are rinsed, they are optionally washed, rinsed again and then dried . 13- Device with several compartments, or “kits”, for dyeing keratin fibers, characterized in that it comprises at least two compartments, one of which contains a composition containing, in a medium suitable for the dye, at least one pyrazolin-4,5-dione of formula (I) as defined in claims 1 to 4, and the other contains a composition containing, in a medium suitable for dyeing, an aromatic or heteroaromatic amine of formula (II) as defined in claims 1, 5 and 6, capable of reacting without oxidant with the pyrazolin-4,5-dione of formula (I) to form a dye.