Hair dyeing composition comprising an oxidation dye, a scleroglucan gum and an alkaline agent such as an amino acid

Information

  • Patent Grant
  • 11278487
  • Patent Number
    11,278,487
  • Date Filed
    Thursday, June 20, 2019
    4 years ago
  • Date Issued
    Tuesday, March 22, 2022
    2 years ago
Abstract
The disclosure relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as hair, comprising one or more oxidation dyes, one or more scleroglucan gums in a total weight content greater than or equal to 0.5% relative to the total weight of the composition, one or more alkaline agents selected from amino acids, the amino acid(s) being present in a total weight content greater than or equal to 1% relative to the weight of the composition, and preferably one or more additional alkaline agents, preferably selected among the mineral alkaline agents and/or alcanolamines. A method for dyeing keratin fibers using said composition and a multi-compartment device suitable for implementing said composition are also disclosed.
Description
CROSS REFERENCE TO RELATED APPLICATION

This is a national stage application of PCT/EP2019/066370, filed internationally on Jun. 20, 2019, which claims priority to French Application No. 1855426, filed on Jun. 20, 2018, both of which are incorporated by reference herein in their entireties.


The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising one or more oxidation dyes, one or more scleroglucan gums in a total weight content of greater than or equal to 0.5% relative to the total weight of the composition; one or more alkaline agents chosen from amino acids, said amino acid(s) being present in a total content of greater than or equal to 1% by weight relative to the weight of the composition, and preferably one or more additional alkaline agents, preferably chosen from mineral alkaline agents and/or alkanolamines.


The invention also relates to a dyeing process involving the application of said composition to keratin fibers, in particular human keratin fibers such as the hair, and also to a multi-compartment device that is suitable for implementing said dye composition.


The present invention relates to the field of dyeing keratin fibers and more particularly to the field of hair dyeing.


Among the methods for dyeing human keratin fibers, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. More particularly, this form of dyeing uses one or more oxidation dyes, usually one or more oxidation bases optionally combined with one or more couplers.


In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give access to colored species.


The shades obtained with these oxidation bases are quite often varied by combining them with one or more couplers, these couplers being notably chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.


The variety of molecules used as oxidation bases and couplers allows a wide range of colors to be obtained.


It is also possible to add to these compositions direct dyes, which are colored, and coloring molecules that have affinity for fibers. The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine and triarylmethane direct dyes. The presence of such compounds enables the coloring obtained to be further enriched with glints or enables the chromaticity of the coloring obtained to be increased.


Oxidation dyeing processes thus consist in using with these dye compositions a composition comprising at least one oxidizing agent, generally hydrogen peroxide, under alkaline pH conditions in the vast majority of cases. The role of this oxidizing agent is to reveal the coloring, via an oxidative condensation reaction between the oxidation dyes.


Oxidation dyeing must moreover satisfy a certain number of requirements. Thus, it must be free of toxicological drawbacks, it must enable shades to be obtained in the desired intensity and it must show a good wear property in the face of external attacking factors such as light, bad weather, washing, permanent waving, perspiration and rubbing.


The dyeing process must also make it possible to cover gray hair and, finally, must be as unselective as possible, i.e. it must make it possible to produce the smallest possible color differences along the same keratin fiber, which generally includes areas that are differently sensitized (i.e. damaged) from its end to its root, so as to obtain the most uniform possible coloring of the keratin fibers. Dye compositions must also make it possible to give good cosmetic properties to keratin fibers, in particular care, softness and/or hold, and must have good working qualities, in particular they must be easy to apply, while at the same time achieving visible (i.e. notably intense, chromatic), uniform and fast coloring results.


The compositions used in a dyeing process must also have good mixing and application properties on keratin fibers, and notably good rheological properties so as not to run down the face, onto the scalp or beyond the areas that it is proposed to dye, when they are applied; this notably allows uniform application from the roots to the ends.


The composition according to the invention also shows very good stability over time for several weeks.


In particular, it is sought to obtain dye compositions that are stable over time for several weeks. For the purposes of the present invention, the term “stable” in particular means that physical properties such as the appearance, the pH and/or the viscosity vary little or not at all over time, and in particular that the viscosity of the composition does not change or changes little during storage and/or that the composition does not undergo phase separation during storage.


Specifically, it is desirable for the dye compositions to be stable over time, in particular stable after 1 month at 45° C., or even after 2 months at 45° C.


It is also sought to obtain dye compositions that are stable over a wide pH range and in particular with respect to extreme pH values, for example to alkaline pH values ranging from 9 to 12. Finally, the dye compositions may occasionally be destabilized (undergo phase separation) by high contents of certain compounds, for instance on account of a high content of certain compounds such as oxidation dyes and/or cationic compounds such as cationic polymers, and it is thus desirable for these compositions to be stable under these conditions, in particular for them not to undergo phase separation.


Thus, one of the objects of the present invention is to propose compositions for dyeing keratin fibers, preferably human keratin fibers such as the hair, which do not have the drawbacks mentioned above, i.e. which are capable of giving very good dyeing performance qualities, notably in terms of intensity and/or color build-up, and also in terms of selectivity, chromaticity and/or resistance to external agents, having good working qualities in particular when applied to keratin fibers, and giving the fibers good cosmetic properties (softness, smoothness) while at the same time being stable (notably not undergoing phase separation and having a viscosity and/or pH which changes little or not at all over time).


These aims and others are achieved by the present invention, one subject of which is thus a composition (A) for dyeing keratin fibers, preferably human keratin fibers such as the hair, comprising:

    • one or more oxidation dyes;
    • one or more scleroglucan gums in a total content of greater than or equal to 0.5% by weight relative to the weight of the composition;
    • one or more alkaline agents chosen from amino acids, said amino acid(s) being present in a total content of greater than or equal to 1% by weight relative to the weight of the composition, and
    • preferably one or more additional alkaline agents, preferably chosen from mineral alkaline agents and/or alkanolamines.


Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, obtained after mixing a composition (A) comprising:

    • one or more oxidation dyes;
    • one or more scleroglucan gums in a total amount of greater than or equal to 0.5% by weight relative to the weight of the composition;
    • one or more alkaline agents chosen from amino acids, said amino acid(s) being present in a total content of greater than or equal to 1% by weight relative to the weight of composition (A), and
    • preferably one or more additional alkaline agents, preferably chosen from mineral alkaline agents and/or alkanolamines;


and a composition (B) comprising one or more chemical oxidizing agents.


For the purposes of the invention, the term “ready-to-use composition” refers to any composition that is intended to be applied immediately to keratin fibers.


The invention is also directed toward a process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, involving the application to the fibers of a dye composition (A) as defined previously, and of an oxidizing composition (B) comprising at least one chemical oxidizing agent, preferably chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide, preferably from hydrogen peroxide, the oxidizing composition (B) being mixed with the dye composition just before use (application to said fibers) (extemporaneously) or at the time of use, or alternatively the dye composition and oxidizing composition being applied sequentially without intermediate rinsing.


A subject of the invention is also a multi-compartment device (or “kit”) allowing the implementation of the composition for dyeing keratin fibers, preferably comprising at least two compartments, a first compartment containing the dye composition (A) as defined previously, and the second compartment containing at least one oxidizing composition (B) comprising at least one chemical oxidizing agent, preferably chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide, preferably from hydrogen peroxide, the compositions in the compartments being intended to be mixed before application, to give the formulation after mixing; in particular, the kit may be an aerosol device.


For the purposes of the present invention, the term “composition for dyeing” or “dye composition” means a composition intended to be applied to keratin fibers, preferably human keratin fibers and in particular the hair, optionally after mixing with an oxidizing composition comprising at least one chemical oxidizing agent. For the purposes of the present invention, the term “ready-to-use dye composition” or “ready-to-use composition” means a composition resulting from mixing a dye composition and an oxidizing composition. The ready-to-use dye composition may be prepared just before application to said keratin fibers.


The compositions according to the invention thus make it possible to give very good dyeing performance on keratin fibers, notably in terms of build-up, intensity, chromaticity and/or selectivity. They also afford compositions which have good rheological properties so as not to run down onto the face, the scalp or beyond the areas that it is proposed to dye, when they are applied.


The compositions according to the invention are stable. For the purposes of the present invention, the term “stable” in particular means that physical properties such as the appearance, the pH and/or the viscosity vary little or not at all over time, and in particular that the viscosity of the composition does not change or changes little during storage and/or that the composition does not undergo phase separation during storage. In particular, it is desirable for the dye compositions to be stable over time, in particular stable after 1 month at 45° C., or even after 2 months at 45° C.


Furthermore, the compositions according to the invention have the advantage of being stable (of not undergoing phase separation) independently of the pH and in particular with respect to extreme pH values (for example alkaline pH values ranging from 9 to 12). Finally, the compositions are preferably stable (do not undergo phase separation) even in the presence of a high content of certain compounds.


Moreover, the compositions of the invention are advantageously translucent, which gives them a visual appearance that the consumer finds esthetic and attractive. In particular, the compositions according to the invention afford very good dyeing properties while at the same time reducing the unpleasant odors when compared with conventional dye compositions.


Moreover, the compositions of the invention afford intense, chromatic and uniform dyeing of keratin fibers.


In particular, the compositions according to the invention afford very good dyeing properties while at the same time reducing the unpleasant odors when compared with conventional dye compositions.


Other features and advantages of the invention will emerge more clearly on reading the description and the examples that follow.


In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from . . . to . . . ”.


The keratin fibers are preferably human keratin fibers, preferably the hair.


The expression “at least one” is equivalent to the expression “one or more”.


Advantageously, composition (A) according to the invention has a thickened texture, and is in cream or gel form, preferably in gel form. Preferably, it is translucent.


Thus, the composition according to the invention generally has, at room temperature, a viscosity of greater than 50 cps, preferably between 200 and 100 000 cps, more preferentially between 500 and 50 000 cps, even more preferentially between 800 and 10 000 cps, and better still from 1000 to 8000 cps measured at 25° C. at a spin speed of 200 rpm using a rheometer such as a Rheomat RM 180 equipped with a No. 3 or 4 spindle, the measurement preferably being taken after 60 seconds of rotation of the spindle (after which time stabilization of the viscosity and of the spin speed of the spindle is observed).


Oxidation Dyes


The composition according to the invention comprises one or more oxidation dyes.


The oxidation dye precursors that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers.


The oxidation bases may preferably be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.


Preferentially, the oxidation base(s) of the invention are chosen from para-phenylenediamines and heterocyclic bases. Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-toluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.


Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine and 2-methoxymethyl-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.


Among the bis(phenyl)alkylenediamines, examples that may be mentioned include N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, 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-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.


Among the para-aminophenols, examples that may be mentioned include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.


Among the ortho-aminophenols, examples that may be mentioned include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and the addition salts thereof.


Among the heterocyclic bases, it is possible in particular pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.


Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino 3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.


Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308.


Examples that may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-β-hydroxyethoxy-3-aminopyrazolo[1,5-a]pyridine and 2-(4-dimethylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine, and also the addition salts thereof.


More particularly, the oxidation bases according to the invention are chosen from 3-aminopyrazolo[1,5-a]pyridines preferably substituted in position 2 with:


a) a (di)(C1-C6)(alkyl)amino group, the alkyl groups possibly being substituted with one or more hydroxyl, amino or imidazolium groups;


b) a cationic or non-cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (C1-C6)alkyl groups such as di(C1-C4)alkylpiperazinium;


c) a (C1-C6)alkoxy group optionally substituted with one or more hydroxyl groups, such as β-hydroxyalkoxy, and also the addition salts thereof.


Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88169571, JP 05-63124 and EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.


Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1-(β-hydroxyethyl)pyrazole. Use may also be made of 4,5-diamino-1-(β-methoxyethyl)pyrazole.


Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a salt thereof.


Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones and notably those described in patent application FR-A-2 886 136, such as the following compounds and the addition salts thereof. 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.


Use will preferably be made of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof.


As heterocyclic bases, use will preferentially be made of 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof.


The oxidation base(s) used in the context of the invention are generally present in an amount ranging from 0.0010% to 10% by weight approximately, and preferably ranging from 0.005% to 5%, relative to the total weight of the dye composition.


The additional couplers that are conventionally used for the dyeing of keratin fibers are preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.


Examples that may be mentioned include 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 1-hydroxy-3-aminobenzene, 2-methyl-5-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, thymol, 1-ß-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.


In general, the addition salts of the oxidation bases and couplers that may be used in the context of the invention are notably chosen from the addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.


In the context of the present invention, when they are present, the coupler(s) are generally present in a total amount ranging from 0.0010% to 10% by weight approximately relative to the total weight of the dye composition, and preferably ranging from 0.005% to 5% by weight relative to the total weight of the dye composition.


Preferably, the total content of oxidation dyes in the composition according to the invention is between 0.001% and 20% by weight, preferably between 0.001% and 10% by weight, preferably between 0.01% and 5% by weight, relative to the weight of the composition.


According to a particular embodiment, the composition of the invention comprises at least one oxidation base and at least one coupler.


Scleroglucan Gums


According to the invention, composition (A) comprises one or more scleroglucan gums in a total content of greater than or equal to 0.5% by weight relative to the weight of the composition.


Scleroglucan gums are polysaccharides of microbial origin produced by a fungus of Sclerotium type, in particular Sclerotium rolfsii. They are polysaccharides constituted solely of glucose units.


Scleroglucan gums may or may not be modified. Preferably, the scleroglucan gums used in the present invention are unmodified.


Examples of scleroglucan gums that may be used in the present invention are, in a nonlimiting manner, the products sold under the name Actigum CS, in particular Actigum CS 11, by the company Sanofi Bio Industries and under the name Amigum or Amigel by the company Alban Müller International.


Other scleroglucan gums, such as the gum treated with glyoxal described in French patent application No. 2 633 940, may also be used.


The scleroglucan gum(s) that may be used according to the invention preferably represent from 0.5% to 10% by weight, more preferentially from 0.5% to 5% by weight, even more preferentially from 0.5% to 3% by weight and even more preferentially from 0.5% to 2% by weight, relative to the total weight of composition (A).


Preferably, the scleroglucan gum(s) represent a total content ranging from 0.7% to 1.5% by weight relative to the total weight of composition (A).


According to one embodiment of the invention, the oxidizing composition (B) comprises one or more scleroglucan gums, preferably in a total content of greater than or equal to 0.5% by weight relative to the weight of the composition.


Preferably, according to this embodiment, the scleroglucan gum(s) that may be used according to the invention preferably represent from 0.5% to 10% by weight, more preferentially from 0.5% to 5% by weight, even more preferentially from 0.5% to 3% by weight, even more preferentially and even more preferentially from 0.5% to 2% by weight, relative to the total weight of the oxidizing composition (B).


Preferably, the scleroglucan gum(s) represent a total content ranging from 0.7% to 2% by weight relative to the total weight of composition (B).


Alkaline Agents of Amino Acid Type


The composition according to the invention comprises one or more alkaline agents chosen from amino acids, said amino acid(s) being present in a total content of greater than or equal to 1% by weight relative to the weight of the composition.


The “alkaline agents” may equivalently be referred to as “basifying agents”.


Preferably, the amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form, and include at least one acid function chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functions. The amino acids may be in neutral or ionic form.


The amino acids that may be used in the composition according to the present invention may be chosen from aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine, and mixtures thereof.


Advantageously, the amino acids are chosen from basic amino acids, notably comprising an additional amine function relative to the number of acid functions


optionally included in a ring or in a ureido function.


Preferably, the basic amino acids are preferably chosen from those corresponding to formula (XIII) below, and also salts thereof:

R—CH2—CH(NH2)—C(O)—OH  (XIII)


in which R represents a group chosen from imidazolyl, preferably imidazolyl-4-yl; aminopropyl; aminoethyl;

—(CH2)2N(H)—C(O)—NH2; and —(CH2)2—N(H)—C(NH)—NH2.


The basic amino acids (corresponding to formula (XIII)) are preferably histidine, lysine, arginine, ornithine and citrulline.


Preferably, the alkaline agent(s) chosen from amino acids are preferably arginine.


Preferably, the alkaline agent(s) chosen from amino acids are present in a total content ranging from 1% to 10% by weight, more preferentially from 1% to 8% by weight and better still from 2% to 7% by weight, relative to the total weight of composition (A).


Additional Alkaline Agents


The composition according to the invention preferably comprises one or more additional alkaline agents other than the amino acids mentioned previously.


Preferably, said the additional alkaline agent(s) are present in a total content ranging from 1% to 20% by weight, more preferentially from 3% to 15% by weight and better still from 5% to 15% by weight relative to the total weight of the composition.


According to a first advantageous embodiment of the invention, the composition comprises at least one additional alkaline agent chosen from mineral alkaline agents.


According to a preferred embodiment, the composition according to the invention also comprises at least one or more mineral alkaline agents and one or more alkaline agents chosen from alkanolamines.


The term “mineral alkaline agent” (also known as an inorganic alkaline agent) means an alkaline agent which is not organic.


The mineral alkaline agent(s) are preferably chosen from aqueous ammonia, also known as ammonium hydroxide (or ammonia precursors such as ammonium salts, for example ammonium halides and in particular ammonium chloride), alkali metal or alkaline-earth metal silicates, phosphates, carbonates or bicarbonates, such as alkali metal or alkaline-earth metal metasilicates, sodium or potassium carbonate or bicarbonate, sodium or potassium hydroxide, or mixtures thereof.


Preferably, the mineral alkaline agent(s) are chosen from aqueous ammonia (or ammonia precursors such as ammonium salts, for example ammonium halides and in particular ammonium chloride) and/or alkali metal or alkaline-earth metal metasilicates.


Preferably, the mineral alkaline agent(s) are present in a total content ranging from 0.10% to 10% by weight, more preferentially from 0.5% to 8% by weight and better still from 1% to 7% by weight, relative to the total weight of the composition.


When the composition comprises aqueous ammonia (ammonium hydroxide), its content preferably ranges from 0.1% to 10% by weight, more preferentially from 0.5% to 8% by weight and better still from 1% to 7% by weight, relative to the total weight of the composition.


According to another advantageous embodiment of the invention, the composition comprises at least one additional alkaline agent chosen from organic alkaline agents, other than the amino acids mentioned previously.


According to this embodiment, the additional organic alkaline agents are preferably chosen from organic amines.


In particular, the organic amines may be chosen from organic amines of heterocyclic type (other than histidine), amino acid dipeptides, organic amines including a guanidine function (other than arginine), and/or alkanolamines.


Preferably, the organic amines are chosen from:

    • the organic amines of heterocyclic type may be chosen from pyridine, piperidine, imidazole, triazole, tetrazole, benzimidazole, and mixtures thereof;
    • the amino acid dipeptides may be chosen from carnosine, anserine and balenine, and mixtures thereof;
    • the organic amines including a guanidine function may be chosen from creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid, and mixtures thereof;
    • alkanolamines, preferably monoethanolamine;
    • and mixtures thereof.


According to a preferred embodiment, the composition according to the invention comprises at least one additional alkaline agent chosen from alkanolamines.


The term “alkanolamine” means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C1 to C8 alkyl groups bearing one or more hydroxyl radicals.


Preferably, the organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising one to three identical or different C1 to C4 hydroxyalkyl radicals.


Preferably, the alkanolamines are preferably chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol and tris(hydroxymethyl)aminomethane, and mixtures thereof, preferably monoethanolamine (MEA).


Preferably, the alkanolamine(s) are present in a total content preferably ranging from 0.5% to 15% by weight, more preferentially from 1% to 12% by weight, better still from 2% to 10% by weight relative to the total weight of the composition, more preferentially from 2% to 8% by weight relative to the total weight of the composition.


The additional alkaline agents may also be chosen from salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.


Preferably, when the composition according to the invention comprises one or more additional alkaline agents, they are present in a total content ranging from 1% to 20% by weight, more preferentially from 3% to 15% by weight and better still from 5% to 15% by weight, relative to the total weight of the composition.


According to a particularly preferred embodiment of the invention, the composition according to the invention comprises one or more additional alkaline agents chosen from:

    • one or more mineral alkaline agents, preferably chosen from aqueous ammonia and/or alkali metal or alkaline-earth metal metasilicates, preferably aqueous ammonia; and
    • one or more organic alkaline agents, preferably chosen from alkanolamines and/or amino acids, preferably from alkanolamines, preferably monoethanolamine.


Associative Polymers


The composition according to the invention may also comprise one or more associative polymers. The associative polymers according to the invention are polymers comprising at least one C8-C30 fatty chain and of which the molecules are capable, in the formulation medium, of associating with each other or with molecules of other compounds.


Preferably, the fatty chain includes from 10 to 30 carbon atoms.


A particular case of associative polymers is amphiphilic polymers, i.e. polymers including one or more hydrophilic parts which make them water-soluble and one or more hydrophobic zones (comprising at least one fatty chain) via which the polymers interact and assemble with each other or with other molecules.


The associative polymers that may be used in the composition according to the invention may be chosen from nonionic, anionic, cationic and amphoteric associative polymers, and mixtures thereof, preferably nonionic associative polymers.


According to one embodiment of the invention, the associative polymer(s) are chosen from nonionic associative polymers.


The nonionic associative polymers are preferably chosen from:

    • (1) celluloses modified with groups including at least one


fatty chain;


preferably from:

    • hydroxyethylcelluloses modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, preferably such as the cetylhydroxyethylcellulose sold notably under the reference Natrosol Plus Grade 330 CS (C16 alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
    • hydroxyethylcelluloses modified with polyalkylene glycol ether alkyl phenol groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) ether of nonyl phenol) sold by the company Amerchol,
    • and mixtures thereof.
    • (2) hydroxypropyl guars modified with groups including at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia.


When they are present, the associative polymer(s), preferably nonionic associative polymer(s), are present in the composition in a total weight content preferably between 0.01% and 10%, even more preferentially between 0.05% and 5% relative to the total weight of the composition, better still between 0.1% and 2% by weight relative to the total weight of the composition.


Cationic Polymers


According to an advantageous embodiment of the invention, the composition comprises one or more cationic polymers other than the cationic associative polymers mentioned previously, preferably one or more nonassociative cationic polymers, i.e. polymers not comprising alkyl chains containing more than 10 carbon atoms, preferably more than 6 carbon atoms.


As cationic polymers that may be used in the compositions according to the invention, mention may be made in particular of:


(1) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to formula (I) or (II):




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in which

    • k and t are equal to 0 or 1, the sum k+t being equal to 1;
    • R12 denotes a hydrogen atom or a methyl radical;
    • R10 and R11, independently of each other, denote a C1-C6 alkyl group, a C1-C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl; R10 and R11, independently of each other, preferably denote a C1-C4 alkyl group;
    • Y is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.


Mention may be made more particularly of the dimethyldiallylammonium salt (for example chloride) homopolymer (Polyquaternium-6), for example sold under the name Merquat 100 by the company Nalco. Preferably, the polymers of family (1) are chosen from dialkyldiallylammonium homopolymers.


(2) quaternary diammonium polymers comprising repeating units of formula:




embedded image


in which:

    • R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals,


or else R13, R14, R15 and R16, together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non-nitrogen heteroatom;


or else R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or —CO—O—R17-D or —CO—NH—R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;

    • A1 and B1 represent linear or branched, saturated or unsaturated, divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
    • X denotes an anion derived from a mineral or organic acid;


it being understood that A1, R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;


in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC—(CH2)p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting:

    • a) a glycol residue of formula —O—Z—O—, in which Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: —(CH2CH2O)x-CH2CH2- and —[CH2CH(CH3)O]y-CH2CH(CH3)-, in which x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
    • b) a bis-secondary diamine residue, such as a piperazine derivative;
    • c) a bis-primary diamine residue of formula —NH—Y—NH—, in which Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical —CH2-CH2-S—S—CH2-CH2-;
    • d) a ureylene group of formula —NH—CO—NH—.


Preferably, X is an anion, such as chloride or bromide. These polymers have a number-average molar mass (Mn) generally of between 1000 and 100 000.


Mention may be made more particularly of cationic polymers that are constituted of repeating units corresponding to the formula:




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in which R1, R2, R3 and R4, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X− is an anion derived from a mineral or organic acid.


A particularly preferred compound of formula (IV) is the one for which R1, R2, R3 and R4 represent a methyl radical and n=3, p=6 and X=Cl, known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.


Preferably, the cationic polymer(s) are chosen from dialkyldiallylammonium homopolymers, in particular homopolymers of dimethyldiallylammonium salts, polymers constituted of repeating units corresponding to formula (IV) above, in particular poly(dimethyliminio)-1,3-propanediyl(dimethyliminio)-1,6-hexanediyl dichloride, the INCI name of which is hexadimethrine chloride, and mixtures thereof.


When they are present, the total content of cationic polymers (other than the associative polymers and the fixing polymers) in the composition according to the present invention may range from 0.01% to 10% by weight relative to the weight of the composition, preferably from 0.1% to 7% relative to the weight of the composition, even more advantageously from 0.5% to 5% by weight and better still from 0.5% to 3% by weight relative to the weight of the composition.


Carboxylic Acids


The dye composition (A) according to the invention may advantageously comprise one or more carboxylic acids, and/or addition salts thereof and/or solvates thereof, said carboxylic acid(s) being aliphatic compounds, comprising from 2 to 10 carbon atoms and preferably comprising at least two carboxylic groups.


Preferably, they are chosen from aliphatic dicarboxylic and/or tricarboxylic acids comprising from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, better still from 2 to 6 carbon atoms.


In particular, the carboxylic acid(s) are saturated or unsaturated, and substituted or unsubstituted.


Preferably, the carboxylic acids may be chosen from oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, citric acid, maleic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, and mixtures thereof.


Preferably, the carboxylic acid(s) comprise at least two carboxylic groups and are chosen from malonic acid, citric acid, maleic acid, glutaric acid, succinic acid, and mixtures thereof; preferably chosen from malonic acid, citric acid, maleic acid, and mixtures thereof.


More particularly preferably, the carboxylic acid is citric acid.


The total content of carboxylic acid(s) and/or addition salts thereof and/or solvates thereof preferably ranges from 0.1% to 20% by weight, relative to the total weight of composition (A).


Preferably, the total content of carboxylic acid(s) ranges from 0.1% to 20%, preferentially from 0.5% to 10% by weight, better still from 1% to 7% by weight, relative to the total weight of the composition, and even better still from 2% to 5% by weight relative to the total weight of composition (A).


Surfactants


Preferably, the composition according to the present invention also comprises one or more surfactants, which may be chosen from anionic surfactants, amphoteric or zwitterionic surfactants, nonionic surfactants and cationic surfactants, and mixtures thereof, preferably from nonionic surfactants, cationic surfactants, and mixtures thereof.


The term “anionic surfactant” means a surfactant including, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups: CO2H, CO2, SO3H, SO3, OSO3H, OSO3, H2PO3, HPO3, PO32−, H2PO2, HPO2, PO22−POH and PO.


According to one embodiment, the composition according to the invention comprises one or more nonionic surfactants.


The nonionic surfactants that may be used according to the invention may be chosen from:

    • alcohols, α-diols and (C1-C20)alkylphenols, these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or else these compounds comprising at least one fatty chain including from 8 to 40 carbon atoms and notably from 16 to 30 carbon atoms; in particular, oxyethylenated alcohols comprising at least one saturated or unsaturated, linear or branched C8 to C40 alkyl chain, comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and including one or two fatty chains;
    • condensates of ethylene oxide and propylene oxide with fatty alcohols;
    • polyethoxylated fatty amides preferably containing from 2 to 30 ethylene oxide units, polyglycerolated fatty amides including on average from 1 to 5 and in particular from 1.5 to 4 glycerol groups;
    • ethoxylated fatty acid esters of sorbitan, preferably containing from 2 to 40 ethylene oxide units;
    • fatty acid esters of sucrose;
    • polyoxyalkylenated, preferably polyoxyethylenated, fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated plant oils;
    • N—(C6-C24 alkyl)glucamine derivatives;
    • amine oxides such as (C10-C14 alkyl)amine oxides or N—(C10-C14 acyl)aminopropylmorpholine oxides;
    • and mixtures thereof.


Mention may also be made of nonionic surfactants of alkyl(poly)glycoside type, represented notably by the following general formula:

R1O—(R2O)t-(G)v


in which:

    • R1 represents a linear or branched alkyl or alkenyl radical including 6 to 24 carbon atoms and notably 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and notably 8 to 18 carbon atoms,
    • R2 represents an alkylene radical including 2 to 4 carbon atoms,
    • G represents a sugar unit including 5 to 6 carbon atoms,
    • t denotes a value ranging from 0 to 10 and preferably from 0 to 4,
    • v denotes a value ranging from 1 to 15 and preferably from 1 to 4.


Preferably, the alkyl(poly)glycoside surfactants are compounds of the formula described above in which:

    • R1 denotes a linear or branched, saturated or unsaturated alkyl radical including from 8 to 18 carbon atoms,
    • R2 represents an alkylene radical including 2 to 4 carbon atoms,
    • t denotes a value ranging from 0 to 3 and preferably equal to 0,
    • G denotes glucose, fructose or galactose, preferably glucose;
    • the degree of polymerization, i.e. the value of v, possibly ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.


The glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C8/C16-Alkyl(poly)glucosides 1,4, and notably decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred, preferably caprylyl/capryl glucosides.


Among the commercial products, mention may be made of the products sold by the company Cognis under the names Plantaren® (600 CS/U, 1200 and 2000) or Plantacare® (818, 1200 and 2000); the products sold by the company SEPPIC under the names Oramix CG 110 and Oramix®NS 10; the products sold by the company BASF under the name Lutensol GD 70, or the products sold by the company Chem Y under the name AG10 LK.


Preferably, use is made of C8/C16-alkyl (poly)glycosides 1,4, notably as an aqueous 53% solution, such as those sold by Cognis under the reference Plantacare® 818 UP.


Preferentially, the nonionic surfactants are chosen from:

    • saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols including at least one C8 to C40, notably C8-C20 and better still C10-C18 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide; and
    • (C6-C24 alkyl)(poly)glycosides, and more particularly (C8-C18 alkyl)(poly)glycosides;
    • and mixtures thereof;


and even more preferentially from (C6-C24 alkyl)(poly)glycosides, preferentially (C8-C18 alkyl)(poly)glycosides.


According to a preferred embodiment of the invention, the composition according to the invention comprises one or more nonionic surfactants preferably chosen from alkyl(poly)glycosides. Preferably, the composition according to the invention comprises one or more surfactants chosen from (C6-C24 alkyl)(poly)glycosides, more preferentially from (C8-C18 alkyl)(poly)glycosides, preferably from C8/C16-(poly)glucosides, preferably of 1,4 type, and preferably chosen from decyl glucosides and/or caprylyl/caprylyl glucosides, and cocoyl glucosides.


According to a first embodiment, the surfactant(s) are nonionic, preferably chosen from (C6-C24 alkyl)polyglycosides.


According to another embodiment, the composition according to the invention comprises at least one or more cationic surfactants.


Preferably, the cationic surfactant(s) are chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammoniumsalts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.


When the composition according to the invention contains one or more cationic surfactants, their content preferably ranges from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight and better still from 0.1% to 3% by weight, relative to the total weight of the composition.


The composition preferably comprises one or more cationic surfactants in a total content ranging from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and better still from 0.1% to 5% by weight, relative to the total weight of the composition.


The composition preferably comprises one or more nonionic surfactants in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight and better still from 0.1% to 3% by weight, relative to the total weight of the composition.


The composition preferably comprises one or more cationic surfactants in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight and better still from 0.1% to 3% by weight, relative to the total weight of the composition.


Preferably, the surfactant(s) are chosen from cationic or nonionic surfactants, and mixtures thereof, preferably cationic surfactants. Preferably, the composition according to the invention comprises at least one or more cationic surfactants and one or more nonionic surfactants.


Medium


The cosmetically acceptable medium that is suitable for dyeing keratin fibers, also known as a dye “support”, generally comprises water or a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water-soluble.


More particularly, the organic solvents are chosen from linear or branched and preferably saturated monoalcohols or diols, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; glycerol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether, butylene glycol or dipropylene glycol; and also diethylene glycol alkyl ethers, notably of C1-C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.


The common solvents described above, if they are present, usually represent from 1% to 40% by weight and more preferentially from 5% to 30% by weight, relative to the total weight of the composition.


The compositions used according to the invention generally comprise water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.


The composition according to the invention preferably comprises water.


Preferably, the water content ranges from 5% to 95% by weight, more preferentially from 10% to 90% by weight and better still from 20% to 80% by weight, relative to the total weight of the composition.


pH of the Medium


The pH of the composition according to the invention generally ranges from 1 to 12. Preferably, the pH of composition (A) according to the invention is basic.


For the purposes of the present invention, the term “basic pH” means a pH above 7.


Preferably, the pH of composition (A) according to the invention is above 8, and particularly ranges from 8.5 to 12.


Preferably, the pH of the composition is between 9 and 12.


pH Adjuster


The cosmetically acceptable medium may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibers, or alternatively using standard buffer systems.


Among the acidifying agents, examples that may be mentioned include mineral acids, for instance hydrochloric acid, (ortho)phosphoric acid, boric acid, nitric acid or sulfuric acid, or organic acids, for instance compounds comprising at least one sulfonic acid function, a phosphonic acid function or a phosphoric acid function, or compounds bearing a carboxylic acid function such as those mentioned previously.


Other Additives


The composition according to the invention may also contain various additives conventionally used in hair dye compositions, such as mineral thickeners, and in particular fillers such as clays or talc; organic thickeners other than scleroglucan gums; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers; fatty substances and/or additional direct dyes.


The above additives are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of the composition, and preferably between 0.10% and 20% by weight relative to the weight of the composition.


Needless to say, a person skilled in the art will take care to select this or these additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that are useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).


Dyeing Process


Another subject of the invention is a dyeing process using a dye composition (A) as described previously, with an oxidizing composition (B) comprising one or more chemical oxidizing agents.

    • In particular, the invention is also directed toward a process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, involving the application to the fibers of a dye composition (A) as defined previously, and of an oxidizing composition (B) comprising at least one chemical oxidizing agent, preferably chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide, preferably from hydrogen peroxide, the oxidizing composition (B) being mixed with the dye composition (A) just before use (i.e. application to said fibers) (extemporaneously) or at the time of use, or alternatively the dye composition and oxidizing composition being applied sequentially without intermediate rinsing.


Oxidizing Agents:


The oxidizing composition (B) used with the dye composition (A) according to the invention contains one or more chemical oxidizing agents, preferably chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide.


The term “chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.


Preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof, percarbonates of alkali metals or alkaline-earth metals, such as sodium carbonate peroxide, also known as sodium percarbonate and peracids and precursors thereof: alkali metal bromates or ferricyanides, solid hydrogen peroxide-generating chemical oxidizing agents such as urea peroxide and polymer complexes that can release hydrogen peroxide, notably those comprising a heterocyclic vinyl monomer such as polyvinylpyrrolidone/H2O2 complexes, in particular in powder form; oxidases that produce hydrogen peroxide in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase).


According to a preferred embodiment of the invention, the chemical oxidizing agent(s) are chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide chosen from a) urea peroxide, b) polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H2O2; c) oxidases; e) perborates and f) percarbonates; and mixtures thereof.


Preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, and mixtures of these compounds.


Particularly preferably, the chemical oxidizing agent is hydrogen peroxide.


Preferably, the chemical oxidizing agent(s) represent from 0.05% to 40% by weight, preferably from 0.5% to 30% by weight, more preferentially from 1% to 20% by weight and better still from 1.5% to 15% by weight relative to the total weight of the oxidizing composition (B).


Preferably, the oxidizing composition (B) according to the invention does not contain any peroxygenated salts.


As indicated previously, according to one embodiment of the invention, the oxidizing composition (B) comprises one or more scleroglucan gums, preferably in a total content of greater than or equal to 0.5% by weight relative to the weight of the composition.


Preferably, according to this embodiment, the scleroglucan gum(s) that may be used according to the invention preferably represent from 0.5% to 10% by weight, more preferentially from 0.5% to 5% by weight, even more preferentially from 0.5% to 3% by weight, even more preferentially and even more preferentially from 0.5% to 2% by weight and better still from 0.7% to 2% by weight relative to the total weight of the oxidizing composition (B).


The oxidizing composition (B) may also contain various additional compounds or various adjuvants conventionally used in compositions for dyeing the hair and notably as defined previously.


The oxidizing composition (B) is generally an aqueous composition. For the purposes of the invention, the term “aqueous composition” means a composition comprising more than 20% by weight of water, preferably more than 30% by weight of water and even more advantageously more than 40% by weight of water.


Preferably, the oxidizing composition (B) usually comprises water, which generally represents from 10% to 98% by weight, preferably from 20% to 96% by weight, preferably from 50% to 95% by weight, relative to the total weight of the composition.


This oxidizing composition (B) may also comprise one or more water-soluble organic solvents as described previously. It may also comprise one or more acidifying agents.


Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.


Usually, the pH of composition (B) is less than 7.


The pH of composition (B) of the invention is advantageously between 1 and 7, preferably between 1 and 4 and more preferentially from 1.5 to 3.5.


Finally, the oxidizing composition (B) is in various forms, for instance a solution, an emulsion or a gel.


Dyeing Process


The process of the invention may be performed by applying the dye composition (A) as defined previously and the oxidizing composition (B) successively and without intermediate rinsing, the order being irrelevant.


Preferably, a ready-to-use composition obtained by extemporaneous mixing, at the time of use, of the dye composition (A) as defined previously and of the oxidizing composition (B) is applied to wet or dry keratin fibers. According to this embodiment, preferably, the weight ratio R of the amounts of (A)/(B) ranges from 0.1 to 10, preferably from 0.2 to 2 and better still from 0.3 to 1.


In addition, independently of the variant used, the application of the ready-to-use composition to the keratin materials (resulting either from the extemporaneous mixing of the dye composition (A) and the oxidizing composition (B) or from the partial or total successive application thereof) is left in place for a time generally from about 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.


The temperature during the process is conventionally between room temperature (between 15 and 25° C.) and 80° C. and preferably between room temperature and 60° C.


After the treatment, the keratin materials are optionally rinsed with water, optionally subjected to washing followed by rinsing with water, and are then dried or left to dry.


Preferably, the keratin fibers are human keratin fibers, preferably human hair.


A subject of the invention is also a ready-to-use composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, obtained by extemporaneous mixing, at the time of use, of a composition (A) comprising:

    • one or more oxidation dyes;
    • one or more scleroglucan gums in a total amount of greater than or equal to 0.5% by weight relative to the weight of the composition;
    • one or more alkaline agents chosen from amino acids, in a total content of greater than or equal to 1% by weight relative to the weight of the composition, and
    • preferably one or more additional alkaline agents, preferably chosen from mineral alkaline agents and/or alkanolamines.


and a composition (B) comprising

    • one or more chemical oxidizing agents, preferably hydrogen peroxide.


The term “extemporaneous” notably means less than 30 minutes, preferably less than 15 minutes, before application to the keratin fibers, preferably less than 5 minutes. In particular, the mixture is applied immediately after having been prepared.


According to a particular embodiment of the invention, the chemical oxidizing agent(s) preferably represent a total content ranging from 0.10% to 20% by weight, preferably from 0.5% to 15% by weight or even more preferentially from 1% to 10% by weight, relative to the total weight of the ready-to-use composition.


Finally, the invention relates to a multi-compartment device comprising, in a first compartment, a dye composition (A) as described previously, and, in a second, an oxidizing composition (B) comprising one or more oxidizing agents, these compositions having been described previously.


In particular, a subject of the invention is also a multi-compartment device (or “kit”) allowing the implementation of the composition for dyeing keratin fibers, preferably comprising at least two compartments, a first compartment containing the dye composition (A) as defined previously, and the second compartment containing at least one oxidizing composition (B) comprising at least one chemical oxidizing agent, preferably chosen from hydrogen peroxide and/or one or more systems for generating hydrogen peroxide, preferably from hydrogen peroxide, the compositions in the compartments being intended to be mixed before application, to give the formulation after mixing; in particular, the kit may be an aerosol device.


The examples that follow serve to illustrate the invention without, however, being limiting in nature.


In particular, the dyeing of the keratin fibers obtained in these examples may advantageously be evaluated in the CIE L* a* b* system, using a Datacolor Spectraflash SF600X spectrocolorimeter.


In this L* a* b* system, the three parameters respectively denote the intensity of the color (L*), the green/red color axis (a*) and the blue/yellow color axis (b*). The higher the value of L*, the lighter the color. The higher the value of a*, the redder the color and the higher the value of b*, the yellower the color.


The variation (or extent) of the dyeing between untreated locks of hair and locks of hair after treatment is defined by the parameter DE* and is calculated according to the following equation:

DE*=√{square root over ((L*−Lo*)2+(a*−ao*)2+(b*−bo*)2)}  (i)


In this equation, the parameters L*, a* and b* represent the values measured on locks of hair after dyeing and the parameters L0*, a0* and b0* represent the values measured on untreated locks of hair. The higher the value of DE*, the belier the dyeing of the keratin fibers.


In the CIE L*, a*, b* system, the chromaticity is calculated according to the following equation:

C*=√{square root over (a*2+b*2)}


The higher the value of C*, the more chromatic the coloring.







EXAMPLE 1

The following compositions were prepared from the following ingredients in the following proportions indicated in grams:















Comparative
Composition A2



composition
according to the



A1
invention

















Ammonium hydroxide
1.23
1.23


Arginine
0.5
3


Ethanolamine
5
5


EDTA
0.2
0.2


Sodium sulfite
0.5
0.5


Citric acid
3.3
3.3


Sodium metasilicate
2
2


Toluene-2,5-diamine
0.16
0.16


4-Amino-2-hydroxytoluene
0.92
0.92


5-Amino-6-chloro-o-cresol
0.2
0.2


1-Hydroxyethyl 4,5-diaminopyrazole
1.44
1.44


sulfate




p-Aminophenol
0.12
0.12


Fragance
qs
qs


Polyquaternium-11
1.84
1.84


Hexadimethrine chloride
1.2
1.2


Polyquaternium-6
0.8
0.8


Cetylhydroxyethylcellulose
0.2
0.2


Sclerotium gum
1
1


Water
qs 100
qs 100


Glycerol
10
10


Cetrimonium chloride
0.25
0.25


Caprylyl/capryl glucoside
0.6
0.6


Ascorbic acid
0.4
0.4









Visual Evaluation of the Stability of the Compositions


The stability of the dye compositions was evaluated by observing them at T0 and then after 48 h at room temperature (25° C.) and then after 2 months of storage at 45° C.















Composition A1
Composition A2







Observation at T0 (immediately
Translucent gel
Translucent gel


after preparation) at room
Homogeneous (no
Homogeneous(no


temperature (25° C.)
phase separation)
phase separation)


Observation after 2 months at
Translucent gel
Translucent gel


45° C.
Homogeneous (no
Homogeneous (no



phase separation)
phase separation)









It is observed that composition A1 (comparative) and composition A2 according to the invention are homogeneous and form a translucent gel at T0. After 2 months at 45° C., compositions A1 and A2 according to the invention are stable and in gel form; they are homogeneous and translucent. Comparative composition C5 in which the scleroglucan gum has been replaced weight-for-weight with another thickener, hydroxypropylcellulose, is not stable, and is liquid. Thus, it is not homogeneous; phase separation of these compositions is observed as early as T0.


EXAMPLE 2

Compositions A1 and A2 of example 1 were mixed with 1 times their weight of 20-volumes oxidizing agent (6 g % of H2O2 AM); the mixture thus obtained was applied to locks of natural hair containing 90% white hairs.


The “mixture/lock” bath ratio is, respectively, 10/1 (g/g).


The leave-on time is 30 minutes, on a hotplate set at 27° C. On conclusion of the leave-on time, the locks are rinsed and then dried under a drying hood at 40° C.


The color of the locks was evaluated in the CIE L* a* b* system, using a Minolta CM3600D spectrocolorimeter



















a*
b*
C*





















Coloring obtained with the
18.32
8.12
20.04



mixture of composition A1 +






oxidizing agent (outside the






invention)






Coloring obtained with the
21.40
10.03
23.63



mixture of composition A2 +






oxidizing agent (according to






the invention)










The mixture obtained using composition A2 according to the invention gives a higher C* value, and thus better chromaticity than the mixture obtained using the comparative composition A1.

Claims
  • 1. A composition for dyeing keratin fibers, comprising: at least one oxidation dye;at least one scleroglucan gum present in a total amount of greater than or equal to 0.5% by weight, relative to the total weight of the composition; andat least one alkaline agent chosen from amino acids, wherein the at least one alkaline agent chosen from amino acids is present in a total amount of greater than or equal to 1% by weight, relative to the weight of the composition.
  • 2. The composition of claim 1, wherein the at least one scleroglucan gum is present in an amount ranging from 0.5% to 10% by weight, relative to the total weight of the composition.
  • 3. The composition of claim 1, wherein the at least one oxidation dye is chosen from benzene-based oxidation bases, or salts thereof; wherein the at least one oxidation dye is optionally combined with at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, salts thereof, or mixtures thereof.
  • 4. The composition of claim 1, wherein the at least one oxidation dye is chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, salts thereof, or mixtures thereof.
  • 5. The composition of claim 1, wherein the at least one alkaline agent chosen from amino acids is present in a total amount ranging from 1% to 10% by weight, relative to the total weight of the composition.
  • 6. The composition of claim 1, wherein the at least one alkaline agent chosen from amino acids is chosen from aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine, valine, or mixtures thereof.
  • 7. The composition of claim 1, wherein the at least one alkaline agent chosen from amino acids is chosen from basic amino acids.
  • 8. The composition of claim 1, further comprising at least one additional alkaline agent chosen from mineral alkaline agents and/or alkanolamines.
  • 9. The composition of claim 7, wherein the at least one additional alkaline agent chosen from alkanolamines is chosen from monoalkanolamines, dialkanolamines, trialkanolamines, or mixtures thereof, comprising one to three identical or different C1 to C4 hydroxyalkyl radicals.
  • 10. The composition of claim 9, wherein the at least one additional alkaline agent chosen from alkanolamines is chosen from monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethyl)aminomethane, or mixtures thereof.
  • 11. The composition of claim 1, further comprising at least one cationic surfactant chosen from cetyltrimethylammonium salts, behenyltrimethylammonium salts, dipalmitoylethylhydroxyethylmethylammonium salts, or mixtures thereof.
  • 12. The composition of claim 1, further comprising at least one nonionic surfactant chosen from: saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols including at least one C8 to C40 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide;alkyl(poly)glycosides; ormixtures thereof.
  • 13. The composition of claim 1, further comprising at least one associative polymer present in a total amount ranging from 0.01% to 10% by weight, relative to the total weight of the composition.
  • 14. The composition of claim 13, wherein the at least one associative polymer is nonionic, and is chosen from celluloses modified with groups including at least one fatty chain.
  • 15. The composition of claim 1, further comprising at least one cationic polymer chosen from: (1) dialkyldiallylammonium homopolymers; and/or(2) cationic polymers that are constituted of repeating units corresponding to formula (IV):
  • 16. The composition of claim 1, further comprising at east one carboxylic acid chosen from oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, citric acid, maleic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, or mixtures thereof.
  • 17. The composition of claim 1, further comprising at least one chemical oxidizing agent.
  • 18. The composition of claim 17, wherein the at least one chemical oxidizing agent is chosen from hydrogen peroxide and/or at least one system generating hydrogen peroxide.
  • 19. A method for dyeing keratin fibers comprising: applying to the keratin fibers a dye composition (A) and an oxidizing composition (B);wherein the dye composition (A) comprises: at least one oxidation dye;at least one scleroglucan gum present in a total amount of greater than or equal to 0.5% by weight, relative to the total weight of the dye composition (A); andat least one alkaline agent chosen from amino acids. wherein the at least one alkaline agent chosen from amino acids is present in a total amount of greater than or equal to 1% by weight, relative to the weight of the dye composition (A);wherein the oxidizing composition (B) comprises at least one chemical oxidizing agent; andwherein the oxidizing composition (B) is extemporaneously mixed with the dye composition (A) just before being applied to the keratin fibers, or alternatively, the dye composition (A) and the oxidizing composition (B) are applied sequentially to the keratin fibers without intermediate rinsing.
  • 20. The method of claim 19, wherein the at least one chemical oxidizing agent is chosen from hydrogen peroxide and/or at least one system generating hydrogen peroxide.
Priority Claims (1)
Number Date Country Kind
1855426 Jun 2018 FR national
PCT Information
Filing Document Filing Date Country Kind
PCT/EP2019/066370 6/20/2019 WO 00
Publishing Document Publishing Date Country Kind
WO2019/243513 12/26/2019 WO A
US Referenced Citations (81)
Number Name Date Kind
2261002 Ritter Oct 1941 A
2271378 Searle Jan 1942 A
2273780 Dittmar Feb 1942 A
2375853 Kirby et al. May 1945 A
2388614 Kirby et al. Nov 1945 A
2454547 Bock et al. Nov 1948 A
2961347 Floyd Nov 1960 A
3206462 McCarty Sep 1965 A
3227615 Korden Jan 1966 A
3472840 Stone et al. Oct 1969 A
3589978 Kamal et al. Jun 1971 A
3632559 Matter et al. Jan 1972 A
3874870 Green et al. Apr 1975 A
3910862 Barabas et al. Oct 1975 A
3912808 Sokol Oct 1975 A
3917817 Vanlerberghe et al. Nov 1975 A
3929990 Green et al. Dec 1975 A
3966904 Green et al. Jun 1976 A
4001432 Green et al. Jan 1977 A
4005193 Green et al. Jan 1977 A
4025617 Green et al. May 1977 A
4025627 Green et al. May 1977 A
4025653 Green et al. May 1977 A
4026945 Green et al. May 1977 A
4027020 Green et al. May 1977 A
4031307 DeMartino et al. Jun 1977 A
4075136 Schaper Feb 1978 A
4131576 Iovine et al. Dec 1978 A
4137180 Naik et al. Jan 1979 A
4157388 Christiansen Jun 1979 A
4165367 Chakrabarti Aug 1979 A
4172887 Vanlerberghe et al. Oct 1979 A
4217914 Jacquet et al. Aug 1980 A
4240450 Grollier et al. Dec 1980 A
4349532 Vanlerberghe et al. Sep 1982 A
4381919 Jacquet et al. May 1983 A
4591610 Grollier May 1986 A
4702906 Jacquet et al. Oct 1987 A
4719282 Nadolsky et al. Jan 1988 A
4761273 Grollier et al. Aug 1988 A
4839166 Grollier et al. Jun 1989 A
4874554 Lange et al. Oct 1989 A
4996059 Grollier et al. Feb 1991 A
5061289 Clausen et al. Oct 1991 A
5089252 Grollier et al. Feb 1992 A
5180397 Grollier et al. Jan 1993 A
5180399 Grollier et al. Jan 1993 A
5380340 Neunhoeffer et al. Jan 1995 A
5534267 Neunhoeffer et al. Jul 1996 A
5663366 Neunhoeffer et al. Sep 1997 A
5766576 Löwe et al. Jun 1998 A
6099592 Vidal et al. Aug 2000 A
20030229948 Desenne et al. Dec 2003 A1
20040034946 Legrand et al. Feb 2004 A1
20040060125 Audouset Apr 2004 A1
20040064901 Kleen et al. Apr 2004 A1
20040133993 Cottard et al. Jul 2004 A1
20040172771 Cottard et al. Sep 2004 A1
20040221401 Desenne et al. Nov 2004 A1
20050039270 Legrand et al. Feb 2005 A1
20060117493 Bureiko et al. Jun 2006 A1
20060182697 Lalleman et al. Aug 2006 A1
20080282481 De Boni et al. Nov 2008 A1
20100175202 Simonet et al. Jul 2010 A1
20100192969 DeGeorge et al. Aug 2010 A1
20100199441 Hercouet et al. Aug 2010 A1
20110117037 Legrand May 2011 A1
20110150797 Legrand Jun 2011 A1
20110203605 Allard et al. Aug 2011 A1
20110203606 Recchion et al. Aug 2011 A1
20110209720 DeGeorge et al. Sep 2011 A1
20120076930 Miller Mar 2012 A1
20120210523 Lalleman et al. Aug 2012 A1
20130042883 DeGeorge et al. Feb 2013 A1
20130167862 Lopez et al. Jul 2013 A1
20140082855 Rapold et al. Mar 2014 A1
20140305464 DeGeorge et al. Oct 2014 A1
20140326270 DeGeorge et al. Nov 2014 A1
20160279036 Schoepgens et al. Sep 2016 A1
20170172901 Kerl et al. Jun 2017 A1
20170354584 Lalleman et al. Dec 2017 A1
Foreign Referenced Citations (51)
Number Date Country
2359399 Jun 1975 DE
3843892 Jun 1990 DE
4133957 Apr 1993 DE
19543988 May 1997 DE
0080976 Jun 1983 EP
0122324 Oct 1984 EP
0337354 Oct 1989 EP
0770375 May 1997 EP
1492597 Aug 1967 FR
1583363 Oct 1969 FR
2077143 Oct 1971 FR
2080759 Nov 1971 FR
2162025 Jul 1973 FR
2190406 Feb 1974 FR
2252840 Jun 1975 FR
2270846 Dec 1975 FR
2280361 Feb 1976 FR
2316271 Jan 1977 FR
2320330 Mar 1977 FR
2336434 Jul 1977 FR
2368508 May 1978 FR
2383660 Oct 1978 FR
2393573 Jan 1979 FR
2413907 Aug 1979 FR
2470596 Jun 1981 FR
2505348 Nov 1982 FR
2519863 Jul 1983 FR
2542997 Sep 1984 FR
2598611 Nov 1987 FR
2618070 Jan 1989 FR
2633940 Jul 1991 FR
2733749 Nov 1996 FR
2801308 May 2001 FR
2886136 Dec 2006 FR
3008615 Jan 2015 FR
1026978 Apr 1966 GB
1153196 May 1969 GB
1546809 May 1979 GB
2207443 Feb 1989 GB
02-019576 Jan 1990 JP
05-163124 Jun 1993 JP
9408969 Apr 1994 WO
9408970 Apr 1994 WO
9615765 May 1996 WO
2016091816 Jun 2016 WO
2018056235 Mar 2018 WO
2019243505 Dec 2019 WO
2019243507 Dec 2019 WO
2019243508 Dec 2019 WO
2019243509 Dec 2019 WO
2019243511 Dec 2019 WO
Non-Patent Literature Citations (17)
Entry
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066365, dated Aug. 13, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066368, dated Sep. 3, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066363, dated Sep. 2, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066369, dated Aug. 22, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066364, dated Sep. 11, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066361, dated Aug. 22, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/EP2019/066370, dated Sep. 11, 2019.
Mintel, “Root Vanish,” Kazumi, ID 3319563, XP055562798, dated Feb. 27, 2015.
Mintel, “Colourant Cream,” LG Household and Health Care, ID 1533817, , XP055547325, dated May 11, 2011.
Mintel, “Hair Colourant,” Garnier, ID 644332, XP055547333, dated Jan. 16, 2007.
Non-Final Office Action for copending U.S. Appl. No. 17/252,856, dated Aug. 16, 2021.
Non-Final Office Action for copending U.S. Appl. No. 17/252,883, dated Aug. 18, 2021.
Non-Final Office Action for copending U.S. Appl. No. 17/253,007, dated Aug. 25, 2021.
Non-Final Office Action for copending U.S. Appl. No. 17/252,870, dated Sep. 10, 2021.
Non-Final Office Action for copending U.S. Appl. No. 17/252,974, dated Sep. 20, 2021.
Non-Final Office Action for copending U.S. Appl. No. 17/253,019, dated Sep. 24, 2021.
Final Office Action for copending U.S. Appl. No. 17/252,974, dated Dec. 29, 2021.
Related Publications (1)
Number Date Country
20210275428 A1 Sep 2021 US