WO2004068997A2

WO2004068997A2 - Cosmetic composition comprising a hydrogelling ionic amide and a dye

Info

Publication number: WO2004068997A2
Application number: PCT/FR2004/000227
Authority: WO
Inventors: Isabelle Rollat-Corvol; Katarina Benabdillah
Original assignee: L'oreal
Priority date: 2003-02-03
Filing date: 2004-02-02
Publication date: 2004-08-19
Also published as: WO2004068997A3; EP1594450A2

Abstract

The invention relates to a cosmetic composition, comprising, in aqueous medium or in water and a solvent, at least one dye, particularly a capillary dye and at least one non-phosphated, ionic, gelling molecular composition with a molecular weight less than 2,000 g/mol and comprising at least two amide groups, an asymmetric carbon and a fatty chain with at least eight carbon atoms.

Description

COSMETIC COMPOSITION COMPRISING A WATER-FREEZING IONIC AMIDE AND A DYE

The subject of the invention is a cosmetic composition comprising at least one dye, in particular a hair dye and at least one hydrogelling ionic amide. It also relates to a cosmetic dyeing process, in particular hair dyeing using this composition, as well as kits.

It is known to dye keratin fibers and in particular human hair, with dyeing compositions containing direct dyes, in particular nitro benzene dyes, acid azo dyes, cationic azo dyes, anthraquinone dyes, natural dyes.

These colorations can be carried out by direct application to the keratin fibers of the composition containing the direct dye (s) or by application of a mixture produced extemporaneously with a composition containing the direct dye (s) with a composition containing an oxidizing bleaching agent which is preferably hydrogen peroxide. We then speak of lightening direct coloring.

It is also known to dye keratin fibers and in particular human hair, with dyeing compositions containing precursors of oxidation dyes, generally called "oxidation bases", in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic bases.

The oxidation dye precursors are initially little or no colored compounds which develop their dyeing power within the hair in the presence of oxidizing agents, leading to the formation of colored compounds. The formation of these colored compounds results either from an oxidative condensation of the "oxidation bases" on themselves, or from an oxidative condensation of the "oxidation bases" on color-modifying compounds, or "couplers" , which are generally present in the dye compositions used in oxidation dyeing and are represented more particularly by metaphenylenediamines, meta-aminophenols and metadiphenols, and certain heterocyclic compounds. The variety of molecules involved, which are formed on the one hand by the "oxidation bases" and on the other hand by the "couplers", makes it possible to obtain a palette very rich in color.

To locate the coloring product when applied to the hair so that it does not run on the face or outside the areas which it is proposed to dye, we have hitherto used the use of traditional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, waxes or mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which, suitably chosen, generate the gelling effect when they are diluted with water and / or surfactants.

However, the Applicant has found that the thickening systems mentioned above did not make it possible to obtain powerful and chromatic shades of low selectivity and good toughness while ensuring a good cosmetic condition for the hair treated. Furthermore, it also found that the ready-to-use dye compositions containing the direct dye (s), and in addition the thickening systems of the prior art did not allow a sufficiently precise application without drips or drops in viscosity over time. .

Now, after significant research carried out on the question, the Applicant has now discovered that it is possible to obtain dye compositions which do not flow and therefore remain well located at the point of application, and which also allow '' obtain powerful and chromatic (light) shades with low selectivities and good toughness with respect to chemical agents (shampoo, perms ...) or natural agents (light, perspiration ...) while providing the hair with good properties cosmetics if we introduce:

- In the case of direct coloring:

(i) either in the composition containing at least one direct dye, or (ii) in the oxidizing composition used for the lightening direct coloring, or (iii) in the two compositions at the same time, an effective amount of at least one compound molecular non-phosphorus ionic thickener, of molecular weight less than 2000 g / mol;

- in the case of an oxidation dye: (i) either in the composition containing at least one oxidation dye, or (ii) in the oxidizing composition, or (iii) in the two compositions at the same time, a effective amount of at least one non-phosphorous ionic thickening molecular compound with a molecular weight of less than 2,000 g / mol.

These discoveries are the basis of the present invention.

The subject of the invention is a cosmetic composition comprising, in an aqueous medium or in a water-solvent medium, at least one dye, in particular direct or oxidation capillary and at least one non-phosphorous ionic thickening molecular compound, of molecular weight less than 2,000 g / mol and comprising at least: - two amide groups,

- an asymmetric carbon,

- a fatty chain comprising at least eight carbons.

By "molecular compound" is meant, within the meaning of the present invention, any compound whose backbone does not result from a polymerization. This does not exclude that the compound may contain one or more polyoxyalkylenated or polyoxyglycerolated groups.

By "ionic molecule" is meant, within the meaning of the present invention, a molecule comprising at least one quaternized nitrogen atom or a group chosen from the CO2M or SO3M group, M denoting a hydrogen atom or an ion derived from '' an alkali or alkaline earth metal or an ion derived from an organic amine.

Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers which contains at least one oxidation dye, at least one oxidizing agent and at least one ionic thickening molecular compound.

By “ready-to-use composition” is meant, within the meaning of the invention, the composition intended to be applied as it is to keratin fibers, ie it can be stored as it is before use or result of the extemporaneous mixture of two or more compositions.

Another object of the present invention relates to a dyeing process, in particular a hair dyeing process comprising the application of a cosmetic composition, comprising, in medium aqueous or in water-solvent medium, at least one dye, in particular direct capillary or of oxidation and at least one non-phosphorous ionic thickening molecular compound, of molecular weight less than 2000 g / mol and comprising at least:

- two amide groups, - an asymmetric carbon,

- a fatty chain comprising at least eight carbons.

The invention also relates to a process for the oxidative dyeing of keratin fibers, and in particular human keratin fibers such as the hair, consisting in applying to the fibers at least one coloring composition containing, in a medium suitable for dyeing, at least one oxidation dye, the color being revealed at alkaline, neutral or acidic pH, using an oxidizing composition containing at least one oxidizing agent which is mixed just at the time of use with the coloring composition or which is applied sequentially without intermediate rinsing, at least one non-phosphorus ionic thickening molecular compound, of molecular weight less than 2,000 g / mol and comprising at least:

- two amide groups,

- an asymmetric carbon,

a fatty chain comprising at least eight carbons, being present in the coloring composition or in the oxidizing composition or in each of the two compositions.

The invention also relates to dyeing devices or “kits” with several compartments.

A device with 2 compartments according to the invention comprises a compartment containing a coloring composition containing, in a medium suitable for dyeing, at least one oxidation dye, and another compartment containing an oxidizing composition containing, in a medium suitable for the dye, an oxidizing agent, the molecular compound according to the invention being present in the coloring composition or the oxidizing composition, or in each of the two compositions.

Another device, with 3 compartments according to the invention, comprises a first compartment containing a coloring composition containing, in a medium suitable for dyeing, at least one oxidation dye, a second compartment containing a oxidizing composition containing, in a medium suitable for dyeing at least one oxidizing agent, and a third compartment containing a composition containing, in a medium suitable for dyeing, at least one molecular compound according to the invention described above, the composition coloring agent and / or the oxidizing composition which may also contain a molecular compound according to the invention.

Another subject of the present invention is thus a direct dyeing composition for keratin fibers, in particular for human keratin fibers, and more particularly the hair, comprising, in a medium suitable for dyeing, at least one direct dye, which is characterized by the fact that it also contains at least one molecular compound according to the invention.

Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers which contains at least one direct dye, at least one oxidizing agent, and at least one molecular compound according to the invention.

The invention also relates to a process for the direct dyeing of keratin fibers, in particular human keratin fibers, and more particularly the hair, consisting in applying to the fibers a composition containing, in a medium suitable for dyeing, at least one direct dye. and at least one molecular compound according to the invention.

The invention also relates to a process for direct lightening dyeing of keratin fibers, in particular human keratin fibers, and more particularly the hair, consisting in applying to the fibers an extemporaneous mixture of a coloring composition containing, in a medium suitable for the dye, at least one direct dye, and of an oxidizing composition containing at least one oxidizing agent, the coloring composition and / or the oxidizing composition containing at least one molecular compound according to the invention.

The invention also relates to devices for the direct dyeing and the lightening direct dyeing of keratin fibers or "kits" with two compartments.

A device with two compartments for direct dyeing according to the invention comprises a first compartment containing, in a medium suitable for dyeing, at least one direct dye and a second compartment containing at least one molecular compound according to the invention. Other devices with 2 compartments for the lightening direct dye according to the invention comprise a compartment which contains a coloring composition containing, in a medium suitable for dyeing, at least one direct dye, and another compartment which contains an oxidizing composition containing , in a medium suitable for dyeing, an oxidizing agent, at least one molecular compound according to the invention.

However, other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

THICKENING MOLECULAR COMPOUND

In accordance with the invention, the non-phosphorous ionic thickening molecular compound has a molecular weight of less than 2,000 g / mol and it comprises at least: - two amide groups,

- an asymmetric carbon,

- a fatty chain comprising at least eight carbons.

The ionic molecular compound is preferably cationic.

More advantageously still, the fatty chain contains between 8 and 30 carbon atoms, and more preferably between 8 and 22 carbon atoms.

Preferably, the thickening molecular compound has a molecular weight of less than 100 g / mol, and preferably less than 800 g / mol.

Advantageously, at least one fatty chain is linked directly to the amide group, and in particular, at least one fatty chain is linked to the amide group by a carbonyl function. More preferably, the thickening molecular compound contains at least two fatty chains and, even more preferably, at least one fatty chain is part of an ester group. According to a preferred embodiment of the invention, the molecular thickening compound contains at least two sequences -CONH-.

In particular, the thickening compound is present in the aqueous medium at a concentration by weight of between 0.1 and 60%, and preferably between 0.25 and 25% by weight, relative to the total weight of the cosmetic composition.

Preferably, the composition forms a film after drying. In a preferred mode, the film is insoluble in pure water, at room temperature. On the other hand, it can be soluble, at acidic or alkaline pH.

As molecular thickening compound, mention may be made of 1- (11- ((((S) -1-ethoxycarbonyl-5 - ((l-oxododecyl) amino) ρentyl) amino) -l l-oxoundecyl) pyridinium bromide).

DIRECT DYE

The direct dyes that can be used according to the invention are preferably chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral acidic or cationic azo direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azines, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

The direct dye may or may not be soluble in the dye composition. In the latter case, we speak of coloring pigment. Preferably, the direct dye is soluble in the composition.

The pigments can be white or colored, mineral and / or organic, coated or not, spherical, platelet or other forms. They are intended to color and / or opacify the composition. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron or chromium, manganese violet, ultramarine blue and ferric blue. Among the organic pigments, there may be mentioned carbon black, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum. The pigments can be present in the composition in an amount of 0.05 to 40% by weight of the final composition, and preferably at 2 to 25% for a non-powdery composition. For a pulverulent composition, they can represent up to 70% of the total weight of the composition.

The nacres or nacreous pigments can be chosen from white nacreous pigments such as mica coated with titanium or bismuth oxychloride, colored nacreous pigments such as mica-titanium with iron oxides, mica-titanium with in particular ferric blue or chromium oxide, mica-titanium with an organic pigment of the aforementioned type. Mention may also be made of interference pigments of the liquid crystal or multilayer type. The pearlescent pigments can be present in the composition in an amount of 0.01 to 20% of the total weight of the composition, preferably at a rate of the order of 1 to 15%.

The composition may also contain inert fillers, insoluble in the physiologically acceptable medium. These fillers can be mineral or organic, lamellar, oblong or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide or Nylon® powders (Orgasol® especially sold by Atochem), poly-β-alanine and polyethylene, polytetra fluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow microspheres such as hollow spheres of polyvinylidene chloride such as Expancel® (Nobel Industry), acrylic particles such as Polytrap® (Dow Corning) and microbeads silicone resin (Tospearl® from Toshiba, for example), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hollow silica microspheres (Silica Beads from Maprecos), glass or ceramic microcapsules . The fillers can be present in an amount of 0.01 to 35% of the total weight of the composition, preferably 0.5 to 15%.

The composition may also comprise dyestuffs which are soluble in the physiologically acceptable medium, such as liposoluble dyes and water-soluble dyes.

Among the benzene direct dyes which can be used according to the invention, the following compounds may be mentioned without limitation: - 1, 4-diamino-2-nitrobenzene - 1-2-amino-nitro-4-α- hyαroxyethylaminobenzene

- 1-2-amino nitro-4-bis (α-hydroxyethyl) -aminobenzene -1, 4-Bis (α-hydroxyethylam o) -2-nitrobenzene

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

-1- α-hydroxyethylannno-2-nitro-4-aminobenzene

-1- α -hydroxyethylarnino-2-nitro-4- (ethyl) (α -hydroxyethyl) -aminobenzene

-l-amino-3-methyl-4- α -hydroxyethylamino-6-nitrobenzene

-l-amino-2-nitro-4- α -hyα ^ oxyethylamino-5-chlorobenzene

- 1, 2-Diamino-4-nitrobenzene

-l-amino-2- α -hydroxyethylamino-5-nitrobenzene

-1,2-Bis- (α-hydroxyethylamino) -4-nitrobenzene

-l-amino-2-tris (hyd ^ oxvméthyl) methylamino-5-nitrobenzene

- 1-Hydroxy-2-amino-5-nitrobenzene

- 1-Hydroxy-2-amino-4-nitrobenzene

-1-Hydroxy-3-nitro-4-aminobenzene

-1-Hydroxy-2-arnmo-4,6-dinitrobenzene

-1- α -hydroxyethyloxy-2- α -hydroxyethylamino-5-nitrobenzene

-l-Methoxy-2- α -hydroxyethylamino-5-nitrobenzene

-1- α -hyckoxy yloxy-3-methylamino-4-nitrobenzene

-1- α α .'- dihydroxypropyloxy-3-methylamino-4-nitrobenzene

-l-α-hydroxyethylamino-4-α, α-dihydroxypropyloxy-2-nitrobenzene

-1 -α, α'-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene

- 1 -α-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene

-l-α-hyα ^ oxyethylamino-3-methyl-2-nitrobenzene

- 1 -α-amdnoethylamino-5-methoxy-2-nitrobenzene

-l-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

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

-l-Hyα oxy-6-bis- (-hydroxyethyl) -amino-3-nitrobenzene

- 1 - -hydroxyethylamino-2-nitrobenzene

-l-Hydroxy-4-α-hyckoxyéthylamino-3-nitrobenzene.

Among the azo direct dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.

It may also be mentioned among the azo direct dyes, the following dyes described in the COLOR INDEX INTERNATIONAL ^3rd edition: Disperse Red 17 -Acid Yellow 9

-Acid Black 1

-Basic Red 22

-Basic Red 16 -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. Mention may also be made of l- (4'-aminodiphenylazo) -2-methyl-4bis- (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -l-naphthalene acid sulfonic acid.

Among the quinone direct dyes, the following dyes may be mentioned:

-Disperse Red 15 -Solvent Violet 13

-Acid Violet 43

-Disperse Violet 1

-Disperse Violet 4

-Disperse Blue 1 -Disperse Blue 1

-Disperse Blue 3

-Disperse Red 11

-Acid Blue 62

-Disperse Blue 7 -Basic Blue 22

-Disperse Violet 15

-Basic Blue 99 as well as the following compounds:

- 1 -N-methylmo holiniumpropylarnino-4-hydroxyanthraquinone -l-An mopropylar no-4-methylan ± ιoanthraquinone

- 1 -Animopropylaminoanthraquinone -5-α-hydroxyethyl-l, 4-diaminoanthraquinone

-2-Aminoéthylaminoanthraquinone

-l, 4-bis- (α, α'-dmyckoxypropylamino) anthraquinone.

Among the azine dyes, the following compounds may be mentioned:

-Basic Blue 17 -Basic Red 2.

Among the triarylmethane dyes which can be used according to the invention, mention may be made of the following compounds:

-Basic Green 1

-Acid blue 9

-Basic Violet 3

-Basic Violet 14 -Basic Blue 7

-Acid Violet 49

-Basic Blue 26

-Acid Blue 7

Among the indoamine dyes which can be used according to the invention, mention may be made of the following compounds:

-2-α-hydroxyétWyamino-5- | T5is- (α-4'-hydroxyethyl) amino] anilino-1,4-benzoquino -2-α-hydroxyethylan- no-5- (2'-methoxy-4'-amino ) arιilino-l, 4-benzoquinone -3-N (2'-CUoro-4'-hyd ^ oxy) phenyl-acetylammo-6-methoxy-l, 4-benzoquinone imine -3-N (3 '-Chloro-4 '-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine

-3- [4'-N- (Ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1,4-benzoquinone imine

Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna. OXIDATION COLO ANT

The oxidation dyes which can be used according to the invention are chosen from oxidation bases and / or couplers.

Preferably, the compositions according to the invention contain at least one oxidation base.

The oxidation bases which can be used in the context of the present invention are chosen from those conventionally known in oxidation dyeing, and among which mention may be made of ortho- and para-phenylenediamines, double bases, ortho- and para- aminophenols, the following heterocyclic bases and their addition salts with an acid:

The oxidation bases which can be used in the context of the present invention are chosen from those conventionally known in oxidation dyeing, and among which mention may be made of ortho- and para-phenylenediamines, double bases, ortho- and para- aminophenols, the following heterocyclic bases and their addition salts with an acid. We can notably cite:

(I) the paraphenylenediamines of formula (I) below and their addition salts with an acid:

in which: Ri represents a hydrogen atom, an alkyl radical in Cι-C, monohydroxyalkyle in CC, polyhydroxyalkyle in C ₂ -C alkoxy (Cι-C) alkyl (Cι-C), alkyl in Cj-C substituted by a nitrogen, phenyl or 4'-aminophenyl group; R ₂ represents a hydrogen atom, an alkyl radical CC ₄ monohydroxyalkyl, C ₁ -C ₄ polyhydroxyalkyl or C ₂ -C, alkoxy (C ₁ -C ₄₎ alkyl _(Cι-C4) alkyl or CC ₄ substituted by a nitrogen group;

Ri and R ₂ can also form, with the nitrogen atom which carries them, a 5 or 6-membered nitrogen heterocycle optionally substituted by one or more alkyl, hydroxy or ureido groups;

R ₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl radical in CC ₄ , sulfo, carboxy, monohydroxyalkyl in Cι-C ₄ or hydroxyalkoxy in Cι-C, acetylaminoalkoxy in Cι- C, CC ₄ mesylaminoalkoxy or C ₁ -C ₄ carbamoylaminoalkoxy,

R represents a hydrogen atom, a halogen atom or a Cι-C ₄ alkyl radical.

Mention may in particular be made, among the nitrogenous groups of formula (I) above, of the arnino, monoalkyl (Cι-C ₄ ) amino, dialkyl (Cι-C ₄ ) amino, trial l (Cι-C) amino, monohydroxyalkyl radicals (Cι-C) amino, imidazolinium and ammonium.

Among the paraphenylenediamines of formula (I) above, there may be mentioned more particularly paraphenylenediamine, paratoluylenediamine, 2-c oro-paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N, N-dimethyl-paraphenylenediamine, N, N-diethyl-paraphenylenediamine, N, N-Npropi-paraphenylenediamine, 4-amino-N , N-diethyl-3-methyl-aniline, N, N-bis- (β-hydroxyethyl) - paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methyl-aniline, 4 -N, N-bis- (β-hydroxyethyl) -amino 2-chloro-aniline, 2-β-hydroxyethyl- paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl- paraphenylenediamine, N- (β-hydroxypropyl ) -paraphenylenediamine, 2-hydroxymethyl- paraphenylenediamine, N, N-dimethyl-3-methyl-paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) -paraphenylened iamine, N- (β, γ-dihydroxypropyl) -paraphenylenediamine, N- (4 ^, -aminophenyl) -paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, 2-β-acetylaminoethyl paraphenylenediamine, N- (β-methoxyethyl) -paraphenylenediamine, 2-methyl-1N-β- hydroxyethyl-paraphenylenediamine, and their addition salts with an acid.

Among the para-phenylenediamines of formula (I) above, very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl- paraphenylenediamine, 2-β-hyάroxyethyl-ρaraphenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, 2,6-dimethyl-paraphenylene diamine, 2,6-diethyl- paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine N, N-bis- (β-hydroxyethyl) - paraphenylenediamine, 2-chloro-paraphenylenediamine, and their addition salts with an acid.

- (D) According to the invention, the term “double bases” is understood to mean compounds comprising at least two aromatic rings on which are carried amino and / or hydroxyl groups.

Among the double bases which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may in particular be made of the compounds corresponding to the following formula (H), and their addition salts with an acid:

in which :

- Zi and Z ₂ , identical or different, represent a hydroxyl radical or -NH _{2 which} can be substituted by a Cι-C alkyl radical or by a link arm Y;

- the link arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more Cι-C ₆ hydroxyl or alkoxy radicals;

- R ₅ and R ^ represent a hydrogen or halogen atom, a Cι-C alkyl radical, C] -C monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, Cι-C aminoalkyl or a linking arm Y;

- R ₇ , R ₈ , R ₉ , Rio, Ru and Rι ₂ , identical or different, represent a hydrogen atom, a connecting arm Y or a Cι-C alkyl radical; it being understood that the compounds of formula (H) have only one linker arm Y per molecule. Among the nitrogen groups of formula (H) above, there may be mentioned in particular the amino, monoall yl (Cι-C) amino, dialkyl (Cι-C ₄ ) amino, trialkyl (Cι-C) amino, monohydroxyalkyl ( Cι-C ₄ ) amino, imidazolinium and ammonium.

Mention may more particularly be made, among the double bases of formulas (H) above, of N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3- diamino-propanol, N, N'-bis- (β- hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) - tetramethylenediamine, N, N'-bis- (β -hydroxyethyl) -N, N'-bis- (4-arninophenyl) - tetramethylenediamine, N, N'-bis- (4-methyl-aminoρhenyl) -tetramemylenedianιine, N, N'-bis- (ethyl) -N, N'-bis- (4'-anήno-3'-methylphenyl) -éthylènediamine, le 1, 8-bis- (2,5-diaminophenoxy) - 3,5-dioxaoctane , and their addition salts with an acid.

Among these double bases of formula (II), N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propanol, l, 8 -bis- (2,5-diaminophenoxy) -3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred.

- (III) para-aminophenols corresponding to the following formula (lu), and their addition salts with an acid:

in which :

Rι ₃ represents a hydrogen atom, a halogen atom such as fluorine, an alkyl radical in -, monohydroxyalkyl in C ₁ -C ₄ , alkoxy (Cι-C ₄ ) alkyl (Cι-C) or aminoalkyl in Cι -C ₄ , or hydroxyalkyl (Cι-C) aminoalkyl in CC ₄ .

R14 represents a hydrogen atom or a halogen atom such as fluorine, a Cι-C ₄ alkyl radical, Cι-C monohydroxyalkyl, C ₂ -C polyhydroxyalkyl, -C ₄ aminoalkyl, CC ₄ cyanoalkyl or alkoxy (Cι-C) alkyl (Cι-C).

Among the para-aminophenols of formula (III) above, there may be more particularly mentioned para-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluoro-phenol, 4-amino - 3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-methoxymethyl-phenol, 4-am o-2-aminomethyl-phenol , 4-amino- 2- (β-hydroxyethyl-aminomethyl) -ρhenol, and their addition salts with an acid.

- (IV) the ortho-aminophenols which can be used as oxidation bases in the context of the present invention, are in particular chosen from 2-amino-phenol, 2-amino-1-hydroxy-5-methyl- benzene, 2-amino-1-hydroxy-6-methyl-benzene, 5-acetamido-2-amino-phenol, and their addition salts with an acid.

- (V) among the heterocyclic bases which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may more particularly be made of pyridine derivatives, pyrirnidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may be made more particularly of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3- amino-pyridine, 2,3-dian-rino-6-methoxy-ρyridine, 2- (β- methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino-pyridine, and their salts addition with an acid.

Among the pyrimidine derivatives, mention may be made more particularly of the compounds described for example in German patents DE 2,359,399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triammopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7- diamine; 2,5-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl-pyrazolo- [1,5-a] - pyrinιidine-3,5-diamine; 3-aπuno-pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino-pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrirnidin-7-ylamino) -ethanol; 2- (7-amino-pyrazolo- [1,5-a] -pyrimidin-3-ylamino) -ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) -amino] -ethanol; 5,6-dimethyl-ρyrazolo- [1,5-a] -pyrir dme-3,7-diamine; 2,6-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2, 5, N7, N7-tetramethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 3-anΗno-5-methyl-7-iπudazolylpropylamino-pyrazolo- [l, 5- a] pyrimidine; and their addition salts and their tautomeric forms, when there is a tautomeric equilibrium and their addition salts with an acid.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino-1-methyl-pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-l- (4'-chlorobenzyl) -pyrazole, 4,5-diamino 1, 3-dimethyl-pyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino 1-methyl-3-phenyl-pyrazole, 4-amino-1,3-dimethyl- 5-hydrazino-pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5- ^' amino- l-tert-butyl-3-methyl-pyrazole, 4,5-diamino-l- (β-hydroxyethyl) -3-methyl pyrazole, 4,5-diarnino-l- (β-hydroxyethyl) -pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl- 3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3 -hydroxymethyl-pyrazole, 4,5-diarnino-3-hydroxymethyl-l -methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-l -iso propyl-pyrazole, 4,5-diamino-3-methyl-1-isopropyl-pyrazole, 4-anιino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, 3,4,5 -triamino-ρyrazole, l-methyl-3,4,5-triamino-pyrazole, 3,5-diamino-1-methyl-4-methylamino-pyrazole, 3,5-diarnino-4- (β-hydroxyethyl ) amino-1-methyl-pyrazole, and their acid addition salts.

According to the present invention, the oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the composition and even more preferably from 0.005 to 8% by weight approximately of this weight.

The couplers which can be used in the dyeing process according to the invention are those conventionally used in oxidation dyeing compositions, that is to say meta-amitiophenols, meta-phenylenediamines, metadiphenols, naphthols and couplers heterocyclics such as, for example, indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines and their addition salts with an acid.

These couplers are more particularly chosen from 2,4-diamino l- (β-hydroxyethyloxy) -benzene, 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) amino-2-methyl- phenol, 3-amino-phenol, 2-methyl-3-amino-6-methyl-phenol, 3,5-diamino-2,6-dimethoxypyridine, 6-hydroxybenzomorpholine, l-β-hychoxyethylamino-3 , 4-methylenedioxy-benzene, l-methyl-2,6-bis (β-hydroxyethylamino) -benzene, 1,3-dihydroxy-benzene, 1,3- dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxy-benzene, 2-amino 4- (β- hydroxyethylamino) -l-methoxy-benzene, 1,3-diamino-benzene, l , 3-bis- (2,4-diaminophenoxy) - propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxy benzene, α-naphthol, 6-hydroxyindole, 4- hydroxy-indole, 4-hydroxy-N-methyl indole, 6-hydroxy-indoline, 2,6-dihydroxy-4-methyl-pyridine, 1H-3-methyl-pyrazole-5-one, l- phenyl-3-methyl-pyrazole-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo- [3,2-c] -1,4,4-triazole, 2,6 -dimethyl-pyrazolo- [1,5-b] -1,2,4-triazole and their addition salts with an acid.

When present, these couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the composition, and even more preferably from 0.005 to 5% by weight approximately.

The direct or oxidation dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the ready-to-use composition and even more preferably from 0.005 to 10% by weight approximately.

MIDDLE

The medium of the composition, suitable for dyeing, is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, l isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl ethers such as, for example, monoethyl ether or diethylene glycol monobutyl ether. The solvents can then be present 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.

The composition may also contain an effective amount of other agents, previously known in direct coloring, such as various usual adjuvants such as sequestrants such as EDTA and etidronic acid, UN filters, waxes, volatile silicones or not, cyclic or linear or branched, organomodified (in particular by amino groups) or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or pro vitamins such as panthenol, opacifiers, associative polymers. In the ready-to-use composition or in the oxidizing composition, the oxidizing agent is preferably chosen from urea peroxide, bromates or ferricyanides of alkali metals, persalts such as perborates and persulfates.

It is also possible to use, as oxidizing agent, one or more redox enzymes such as laccases, peroxidases and oxidoreductases with 2 electrons (such as Puricase), where appropriate in the presence of their respective donor or cofactor.

The pH of the ready-to-use composition applied to the keratin fibers

[composition resulting from the mixture of the dye composition and the oxidizing composition], is generally between the values 4 and 11. It is preferably between 6 and 10, and can be adjusted to the desired value by means of acidifying agents or basifying agents well known from the state of the art in dyeing keratin fibers.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, hydroxyalkylamines and ethylenediamines oxyethylenated and / or oxypropylenes, sodium or potassium hydroxides and the compounds of formula (XLX) below:

R '3.8 \ .R', 40

N - R - N (XIX)

R '3.9 '41

in which R is a propylene residue optionally substituted with a hydroxyl group or a Cι-C ₄ alkyl radical; R _38, R _39, R ₄₀ and R-π, identical or different, represent a hydrogen atom, an alkyl radical in C ₁ -C ₄ alkyl or hydroxyalkyl, Cι-C _4.

The acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or acids sulfonic.

The dyeing process according to the invention preferably consists in applying the ready-to-use composition, produced extemporaneously at the time of use from the coloring and oxidizing compositions described above, to the dry keratin fibers or wet, and leave it to act for a pause time varying, preferably from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes, to rinse the fibers, then optionally to wash them in shampoo, then to rinse again, and dry them.

A variant of this process consists in taking a composition comprising at least one oxidation dye but without molecular compound according to the invention, a second composition containing an oxidant and a third composition containing at least one molecular compound according to the invention and in performing an extemporaneous mixture of these three compositions at the time of use.

According to said methods, each of the compositions or several compositions may also contain at least one cationic or amphoteric polymer and at least one surfactant.

The direct dyeing process according to the invention preferably consists in applying the composition without oxidant ready for use, or the composition produced extemporaneously at the time of use from the coloring and oxidizing compositions described above, on dry or wet keratin fibers, and to let it act for a pause time varying, preferably from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers, then optionally washing them with shampoo, then rinse them again, and dry them.

A variant of this direct dyeing process consists in taking a coloring composition containing at least one direct dye but without molecular compound in accordance with the invention, another composition containing at least one molecular compound and in mixing these two at the time of use. compositions with the oxidizing composition, then apply and let the mixture act as above.

In a preferred direct dyeing process of the invention, when it is a direct dyeing (with a coloring composition) or a lightening direct dyeing (with a coloring composition and an oxidizing composition), the coloring composition and / or the oxidizing composition contains at least one cationic or amphoteric polymer and at least one surfactant.

According to the invention, the oxidation dyeing process consists in applying a ready-to-use composition containing at least one oxidizing agent and at least one oxidation dye, the coloring composition and / or the oxidizing composition containing at least one non-phosphorus ionic thickening molecular compound, of molecular weight less than 2,000 g / mol and comprising at least: - two amide groups,

- an asymmetric carbon, - a fatty chain comprising at least eight carbons, produced extemporaneously at the time of use from the coloring and oxidizing compositions described above, on dry or wet keratin fibers, and allowing it to act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers, then optionally washing them with shampoo, then rinsing them again, and drying them.

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 invention also relates to a cosmetic process comprising the application of a composition according to the invention.

The compositions can be in the form of fluid or thickened liquids, gels, creams, foams, W / O, O / W emulsions or multiple emulsions. They can be used, for example, as shampoos, rinsed or leave-in care, deep care masks, lotions or creams for treating the scalp and skin. They are used especially for hair.

These compositions can be packaged in an aerosol device in the presence of one or more propellants. These propellants are preferably selected from dimethyl her, alkanes, C ₃ - _5, 1,1-difluoroethane, mixtures of dimethyl ether and alkanes C. ₅ and mixtures of 1,1-difmoroethane and dimethyl ether and / or C ₃ alkanes. ₅ .

The composition of the invention can be a makeup product for the skin, the lips or keratin fibers such as foundations, blush or eyeshadow, mascaras, eyeliners, lipsticks, body makeup products (permanent tattoo). These products can also contain one or more cosmetic active ingredients or dermatological in order to provide a make-up treatment valence. Preferably, these makeup compositions only contain, as coloring agent, soluble or insoluble direct dyes.

These compositions for topical application can, moreover, constitute a cosmetic, dermatological, hygienic or pharmaceutical composition for protecting, treating or caring for the face, neck, hands or human body and for example constituting a care cream, a sunscreen or artificial tanning product, lip care or protection balm, ointment or dermatological ointment.

The present invention is illustrated below by way of an example.

EXAMPLE:

Example 1:

The following dye composition is produced:

Solution A

1 - (11 - (((1 S) - 1 -ethoxycarbonyl-5 - ((1 -oxododecyl) amino) pentyl) amino) - 11- oxoundecyl) pyridinium 0.5% m.a. 0.25% p-phenylene diamine

2-methyl 5-aminophenol 0.35% sequestering agent qs reducing agent qs pH agent 10% of an aqueous ammonia solution at 20% water qs 100%

Solution B: Hydrogen peroxide 20 volumes

Solutions A and B are mixed weight by weight before applying to hair.

Example 2:

The following dye composition is produced:

1- (11 - (((1 S) -l -ethoxycarbonyl-5 - ((l -oxododécyl) anιino) pentyl) amino) -l 1 -oxoundécyl) pyridinium 0.5% m.a. Basic Red 51 0.2%

PH agent qs pH = 8 ^Water qs l00%

After the application to hair, it was noted that these compositions gave more pronounced colorings than those of the reference compositions not containing 1- (11- (((1 S) -l-ethoxycarbonyl-5 - ((l- oxododecyl) amino) pentyl) amino) -1-oxoundecyl) pyridinium.

Claims

1. Cosmetic composition comprising, in aqueous medium or water + solvent, at least one dye, in particular a hair dye and at least one non-phosphorous ionic thickening molecular compound, of molecular weight less than

2,000 g / mol, this molecular compound comprising at least: - two amide groups, - an asymmetric carbon, a fatty chain comprising at least eight carbons.

2. Composition according to claim 1, characterized in that the ionic molecular compound is preferably cationic.

3. Composition according to any one of the preceding claims, characterized in that the thickening molecular compound contains at least two sequences -CONH-.

4. Composition according to any one of the preceding claims, characterized in that the fatty chain contains between 8 and 30 carbon atoms, and more preferably between 8 and 22 carbon atoms.

5. Composition according to any one of the preceding claims, characterized in that the thickening molecular compound is of molecular weight less than 100 g / mol, and preferably less than 800 g / mol.

6. Composition according to any one of the preceding claims, characterized in that at least one fatty chain is linked directly to the amide group. 7. Composition according to any one of claims 1 to 5, characterized in that at least one fatty chain is linked to the amide group by a carbonyl function.

8. Composition according to any one of the preceding claims, characterized in that the thickening molecular compound contains at least two fatty chains.

9. Composition according to any one of the preceding claims, characterized in that at least one fatty chain is part of an ester group.

10. Composition according to any one of the preceding claims, characterized in that the thickening compound is present in the aqueous medium at a concentration by weight of between 0.1 and 60%, and preferably between 0.25 and 25% by weight, relative to the total weight of the cosmetic composition.

11. Composition according to any one of the preceding claims, characterized in that the hair dye is a direct dye soluble or not soluble in the dye composition.

12. Composition according to claim 11, characterized in that the direct dye is soluble in the composition.

13. Composition according to claim 11, characterized in that the direct dye is chosen from neutral, benzene, neutral, acid or cationic direct dyes, neutral azo direct dyes, acids or cationic, quinonic direct dyes and in particular anthraquinone, neutral , acidic or cationic, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

14. Composition according to any one of claims 1 to 13, characterized in that the oxidation dye is chosen from oxidation bases and / or couplers.

15. Composition according to claim 14, characterized in that it contains at least one oxidation base.

16. Composition according to Claim 14, characterized in that the oxidation bases are chosen from ortho- or para-phenylenediamines, double bases, ortho- or para-aminophenols, and heterocyclic bases, as well as the salts of addition of these compounds with an acid.

17. Composition according to Claim 14, characterized in that the couplers are chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, heterocyclic couplers, and the addition salts of these compounds with an acid.

18. A dyeing method, in particular a hair dyeing method comprising the application of a cosmetic composition, comprising, in an aqueous medium or water + solvent, at least one direct hair dye or oxidation dye and at least one non-phosphorous ionic thickening molecular compound, of molecular weight less than 2,000 g / mol and comprising at least: - two amide groups,

- an asymmetric carbon,

- a fatty chain comprising at least eight carbons.

19. The method of claim 18, characterized in that a composition is applied comprising at least one direct hair dye.

20. Process for the direct lightening dyeing of keratin fibers, in particular human keratin fibers, and more particularly the hair, consisting in applying to the fibers an extemporaneous mixture of a coloring composition containing, in a medium suitable for dyeing, at least a direct dye, and an oxidizing composition containing at least one oxidizing agent, the coloring composition and / or the oxidizing composition containing at least one non-phosphorous ionic thickening molecular compound, of molecular weight less than 2,000 g / mol and comprising at least least:

- two amide groups, - an asymmetric carbon,

- a fatty chain comprising at least eight carbons.

24. An oxidation dyeing process consisting in applying a ready-to-use composition containing at least one oxidizing agent and at least one oxidation dye, the coloring composition and / or the oxidizing composition containing at least one ionic thickening molecular compound. non-phosphorus, of molecular weight less than 2000 g / mol and comprising at least:

- two amide groups,

- an asymmetric carbon, - a fatty chain comprising at least eight carbons, produced extemporaneously at the time of use from the coloring and oxidizing compositions described above, on dry or wet keratin fibers, and allowing it to act for a break time varying, preferably, from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, to rinse the fibers, then optionally to wash them in shampoo, then to rinse them again, and to dry them.