WO2025043537A1

WO2025043537A1 - Kit for dyeing keratin fibers

Info

Publication number: WO2025043537A1
Application number: PCT/CN2023/115774
Authority: WO
Inventors: Jingmiao MA; Yanan WU; Zhibing Liu
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2023-08-30
Filing date: 2023-08-30
Publication date: 2025-03-06
Anticipated expiration: 2026-02-28
Also published as: FR3152389A3; FR3152389B3

Abstract

A kit for dyeing keratin fibers, in particular hairs, is provided, comprising: A) a colorant composition comprising: (i) at least one oxidative dye chosen from oxidation bases, optionally in combination with one or more couplers; (ii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers; (iii) at least one polar oil; and (iv) at least one surfactant; and B) a developer composition comprising: I) at least one oxidizing agent; and II) at least one associative polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymer comprising one or more acrylic and/or methacrylic units, and a mixture thereof. A process for dyeing keratin fibers is also provided.

Description

KIT FOR DYEING KERATIN FIBERS

TECHNICAL FIELD

The present invention relates to a cosmetic composition. In particular, the present invention relates to a kit for dyeing keratin fibers and to a process for dyeing keratin fibers.

BACKGROUND

Many people have for a long time sought to modify the color of their hair, and especially to dye it, for example, to mask their grey hair.

The dyeing product can comprise both at least one colorant composition and at least one developer composition. For better use, the colorant composition and the developer composition may be placed respectively in a multi-compartment package, and are mixed together immediately before use.

When using hair dyeing products, especially for home use, consumers often expect application easiness, especially for the dyeing products in which the colorant composition and/or the developer composition are in the form of cream.

It is desired that after a colorant composition and a developer composition is mixed, the mixture can be pumped out without dripping issue.

Therefore, there is need for dyeing products with which can be easily pumped out and applied without dripping issue, even for the dyeing products in which the colorant composition and/or the developer composition are in the form of cream.

SUMMARY OF THE INVENTION

One aim of the present application is to provide a dyeing product which can be easily pumped out and applied without dripping issue.

Another aim of the present application is to provide a process for dyeing the hair.

According to a first aspect, the present invention relates to a kit for dyeing keratin fibers, in particular hairs, comprising:

A) a colorant composition comprising:

(i) at least one oxidative dye chosen from oxidation bases, optionally in combination with one or more couplers;

(ii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers;

(iii) at least one polar oil; and

(iv) at least one surfactant; and

B) a developer composition comprising:

I) at least one oxidizing agent; and

II) at least one associative polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymer comprising one or more acrylic and/or methacrylic units, and a mixture thereof.

According to a second aspect, the present invention relates to a process for dyeing keratin fibers, comprising:

mixing the colorant composition and the developer composition immediately before use;

applying the resulted mixture onto the keratin fibers; and

rinsing off the mixture on the keratin fibers with water, optionally washing the keratin fibers with a shampoo before rinsing the keratin fibers with water.

Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the detailed description and the examples that follow.

DETAILED DESCRIPTION OF THE INVENTION

In that which follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "of between" and "ranging from... to... " .

The articles "a" and "an" , as used herein, mean one or more when applied to any feature in embodiments of the present invention described in the specification and claims. The use of "a" and "an" does not limit the meaning to a single feature unless such a limit is specifically stated. Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more" .

Throughout the present application, the expression “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones. As used herein, the use of the term “comprising” also discloses the embodiment wherein no material features or even no features other than the specifically mentioned features are present (such as “consisting essentially of” and “consisting of” ) . In the case of “consisting essentially of, ” any additional compositions, materials, and/or components that materially affect the basic and novel characteristics are excluded from such an embodiment, but any compositions, materials and/or components that do not materially affect the basic and novel characteristics can be included in the embodiment.

The term “about” denoting a certain value is intended to denote a range within±5%of the value. As one example, the phrase “about 100” denotes a range of 100±5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the disclosure can be obtained within a range of±5%of the indicated value.

The term “keratin fiber (s) ” , as used herein, means hairs, eyelashes, eyebrows, or body hairs. Preferably, the keratin fiber (s) means hairs.

According to the first aspect, the kit for dyeing keratin fibers according to the present invention comprises a colorant composition and a developer composition.

Colorant composition

The colorant composition according to the present invention comprises at least one oxidative dye, at least one hydrophilic gelling polymer, at least one polar oil, and at least one surfactant.

Oxidative dyes

The oxidative dye of the present invention is generally chosen from oxidation bases, optionally combined with one or more couplers.

Preferentially, the oxidative dye comprises one or more oxidation bases.

The oxidation bases may be chosen especially from p-phenylenediamines, bis (phenyl) alkylenediamines, p-aminophenols, o-aminophenols, heterocyclic bases, and the addition salts thereof, and mixtures thereof.

Among the p-phenylenediamines, examples that may be mentioned include p-phenylenediamine, p-tolylenediamine, 2-chloro-p-phenylenediamine, 2-methyl-p-phenylenediamine (CI 76042) , 3-methyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 4-methyl-p-phenylenediamine, 2, 3-dimethyl-p-phenylenediamine, 2, 6-dimethyl-p-phenylenediamine, 2, 6-diethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (-hydroxyethyl) amino-2-chloroaniline, 2-hydroxyethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl-hydroxyethyl) -p-phenylenediamine, N- (, -dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-hydroxyethyloxy-p-phenylenediamine, 2-acetylaminoethyloxy-p-phenylenediamine, N- (-methoxyethyl) -p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1- (4'-aminophenyl) pyrrolidine, and the addition salts thereof with an acid.

Among the p-phenylenediamines mentioned above, p-phenylenediamine, p-tolylenediamine, 2-isopropyl-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, 2-hydroxyethyloxy-p-phenylenediamine, 2, 6-dimethyl-p-phenylenediamine, 2, 6-diethyl-p-phenylenediamine, 2, 3-dimethyl-p-phenylenediamine, N, N-bis (-hydroxyethyl) -p-phenylenediamine, 2-chloro-p-phenylenediamine and 2-acetylaminoethyloxy-p-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 (-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diaminopropanol, N, N'-bis (-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (-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, 1, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane and the addition salts thereof.

Among the p-aminophenols, examples that may be mentioned include p-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- (-hydroxyethyl-aminomethyl) phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

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

Among the heterocyclic bases, examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1026978 and GB1153196, 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 the addition salts thereof described, for example, in patent application FR 2801308. Examples that may be mentioned include pyrazolo [1, 5-a] pyrid-3-ylamine, 2- (acetylamino) pyrazolo [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 and the addition salts thereof.

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in the patents DE 2359399; JP 88-169571; JP 05-63124; 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 that may be mentioned are 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- (2-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- (2-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- (-hydroxyethyl) amino-1-methylpyrazole, and the addition salts thereof. 4, 5-Diamino-1- (2-methoxyethyl) pyrazole may also be used.

Preferably, a4, 5-diaminopyrazole, and more preferably 4, 5-diamino-1- (2-hydroxyethyl) pyrazole and/or a salt thereof is used.

Pyrazole derivatives that may also be mentioned include diamino-N, N-dihydropyrazolopyrazolones and especially 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-bis (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 or 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 one of its salts.

Heterocyclic bases that will preferentially be used include 4, 5-diamino-1- (2- 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 oxidative dye may also comprise one or more couplers, which may be chosen from those conventionally used for the dyeing of keratin fibers.

Among these couplers, mention may be made especially of m-phenylenediamines, m-aminophenols, m-diphenols, naphthalene-based couplers, heterocyclic couplers, and also the addition salts thereof, and mixtures thereof.

Examples that may be mentioned include 1, 3-dihydroxybenzene, 1, 3-dihydroxy-2-methylbenzene, 4-chloro-1, 3-dihydroxybenzene, 2, 4-diamino-1- (2-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, 1-β-hydroxyethylamino-3, 4-methylenedioxybenzene, -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, hydroxyethyl-3, 4-methylenedioxyaniline, 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, such as chlorhydrate or dichlorhydrate thereof, e.g., 1-β-hydroxyethyloxy-2, 4-diamino-benzene dichlorhydrate (2, 4-diaminophenoxyethanol HCl) .

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

Advantageously, the oxidation base is present in an amount ranging from 0.1 wt. %to 15.0 wt. %, or from 0.15 wt. %to 14.0 wt. %, or from 0.2 wt. %to 13.0 wt. %, preferably from 0.25 wt. %to 12.0 wt. %, or from 0.3 wt. %to 11.0 wt. %, or from 0.35 wt. %to 10.0 wt. %, more preferably from 0.4 wt. %to 9.0 wt. %, or from 0.45 wt. %to 8.0 wt. %, or from 0.5 wt. %to 7.0 wt. %, or from 0.55 wt. %to 6.0 wt. %, from 0.6 wt. %to 5.0 wt. %, relative to the total weight of the colorant composition.

Advantageously, the coupler, if presents, is present in an amount ranging from 0.1 wt. %to 15.0 wt. %, preferably from 0.3 wt. %to 10.0 wt. %, more preferably from 0.5 wt. %to 5.0 wt. %, relative to the total weight of the colorant composition.

Hydrophilic gelling polymers

According to the present invention, the term "hydrophilic gelling polymer" means a polymer that is capable of thickening an aqueous medium. Preferably, the thickening polymer has, at 1%in water or a 50/50 water/alcohol mixture by weight at 25℃, a viscosity of greater than 100 centipoise at a shear rate of 1 s^-1. The viscosity can be measured using in particular viscometers or rheometers having cone-plate geometry.

The hydrophilic gelling polymer is chosen from anionic acrylic copolymers.

For the purposes of the present invention, the term "acrylic copolymer" means a polymer resulting from the copolymerization of at least two chemically different monomers, at least one of which is selected from unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid.

According to a particular embodiment of the invention, the anionic acrylic copolymer (s) are selected from:

- anionic copolymers derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms;

- anionic associative acrylic copolymers, and

- mixtures thereof.

As used herein, the term "associative acrylic copolymer" means an amphiphilic acrylic copolymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally comprises, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.

The term "hydrophobic group" means a group or a polymer bearing a saturated or unsaturated and linear or branched hydrocarbon-based chain. When it denotes a hydrocarbon-based group, the hydrophobic group comprises at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, from 12 to 24 carbon atoms and preferentially from 16 to 22 carbon atoms. Preferentially, the hydrocarbon-based hydrophobic group originates from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or else from a polyalkylenated fatty alcohol, such as steareth-50.

In the context of the invention, the anionic copolymer (s) derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms are different from the anionic associative acrylic copolymer (s) .

The anionic copolymer (s) derived from at least one unsaturated carboxylic acid and at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms are copolymers comprising, among their monomers, one or more unsaturated carboxylic acids, which are more particularly α, β-monoethylenically unsaturated, and one or more esters of an unsaturated carboxylic acid, which are more particularly α, β-monoethylenically unsaturated, and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

More particularly, the unsaturated carboxylic acid, which is in particular α, β-monoethylenically unsaturated, is a monomer corresponding to formula (I) below:

in which R¹ denotes H or CH₃ or C₂H₅, which corresponds to acrylic acid, methacrylic acid or ethacrylic acid units.

Preferably, the other monomeric ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms is a monomer of formula (II) below:

in which R¹ denotes H or CH₃ or C₂H₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units) , and R² denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

As esters of an unsaturated carboxylic acid and of a fatty monoalcohol comprising from 1 to 6 carbon atoms according to formula (II) , mention may be made more particularly of methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, and the corresponding methacrylates, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

According to one embodiment, these anionic copolymers may be crosslinked, for example, with a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate or methylenebisacrylamide.

Among anionic copolymers of this type, use will more particularly be made of the polymers constituted of the following monomers:

i) of an unsaturated carboxylic acid, which is in particular α, β-monoethylenically unsaturated, corresponding to formula (I) below:

in which R¹ denotes H or CH₃ or C₂H₅, which corresponds to acrylic acid, methacrylic acid or ethacrylic acid units;

(ii) of an ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, of formula (II) below:

in which R¹denotes H or CH₃or C₂H₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units) , and R²denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms,

(iii) and optionally a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate or methylenebisacrylamide.

Examples of anionic copolymers as defined above are the crosslinked copolymer of acrylic acid and of ethyl acrylate sold under the trade name Aculyn 33 by the company Rohm&Haas, which is in aqueous dispersion containing28%by weight of active material, the methacrylic acid/ethyl acrylate crosslinked copolymer in the form of an aqueous dispersion at30%by weight (INCI name: Acrylates Copolymer) sold under the name Carbopol Aqua SF-1 Polymer by the company Lubrizol, and the copolymer of (meth) acrylic acid and of a C₁-C₄ alkyl (meth) acrylate sold under the name Synthalen W400 by the company 3V Sigma, at 30%by weight of active material in water.

Preferably, these anionic copolymers are selected from crosslinked copolymers of (meth) acrylic acid and of a C₁-C₄ alkyl (meth) acrylate, and better still from crosslinked copolymers of (meth) acrylic acid and of ethyl (meth) acrylate.

Among the anionic associative acrylic copolymers that may be used in the context of the invention, mention may be made of:

(1) copolymers derived from the polymerization of:

(i) (meth) acrylic acid and/or its C₁-C₄alkyl ester,

(ii) a monomer of formula (III) below:
CH₂=CR' CH₂O B_nR (III)

in which R’ denotes H or CH₃, B denotes the ethyleneoxy group (-CH₂-CH₂-O-) , n is zero or denotes an integer ranging from 1 to 100 (especially from 5 to 15) and R denotes a hydrocarbon-based group selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl groups comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms and even more particularly from 16 to 20 carbon atoms.

A monomer of formula (III) that is more particularly preferred is a monomer in which R' denotes H, n is equal to 10 and R denotes a stearyl (C18) group.

Such anionic associative polymers are described in patent EP-0 216 479.

Among these anionic associative polymers, the ones that are particularly preferred are polymers formed from 20%to 60%by weight of (meth) acrylic acid, from 5%to 60%by weight of C₁-C₄alkyl (meth) acrylate, from 2%to 50%by weight of monomer of formula (III) , and from 0 to 1%by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the latter polymers, preference is given most particularly to terpolymers of methacrylic acid, ethyl acrylate and polyoxyethylenated stearyl alcohol allyl ether containing 10 mol of ethylene oxide (INCI name: Steareth-10 allyl ether/acrylates copolymer) , especially in 40/50/10 respective weight proportions, such as the product sold under the name Salcare SC 80 by the company Ciba;

(2) associative polymers comprising at least one hydrophilic unit of unsaturated ethylenic carboxylic acid type and at least one hydrophobic unit of (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid type.

Preferably, these polymers are selected from copolymers of (i) a monomer of formula (IV) below:

in which R¹denotes H or CH₃ or C₂H₅, and of (ii) monomer of the following formula (V) (monomer of (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid type) :
H₂C=CR¹-COOR³ (V)

in which R¹ denotes H or CH₃ or C₂H₅ and preferably H or CH₃, R³ denotes a C₁₀-C₃₀ and preferably C₁₂-C₂₂ alkyl group.

In this polymer, the monomer (IV) constitutes the hydrophilic unit and the monomer (V) constitutes the hydrophobic unit.

(C₁₀-C₃₀) alkyl esters of unsaturated carboxylic acids comprise, for example, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate and dodecyl (meth) acrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949.

Among the anionic associative polymers of this type that will be used more particularly are polymers formed from a monomer mixture comprising:

(i) acrylic acid,

(ii) an ester of formula (V) described above in which R¹ denotes H or CH₃ and R³ denotes an alkyl group containing from 12 to 22 carbon atoms,

Among the anionic associative polymers of this type, use will be made more particularly of:

those constituted of 95%to 60%by weight of acrylic acid, 4%to 40%by weight of a C₁₀-C₃₀alkyl acrylate and 0 to 6%by weight of a crosslinking polymerizable monomer, or alternatively those constituted of 98%to 96%by weight of acrylic acid, 1%to 4%by weight of a C₁₀-C₃₀ alkyl acrylate and 0.1%to 0.6%by weight of a crosslinking polymerizable monomer, such as those described previously.

Among the abovementioned polymers, the ones that are most particularly preferred are the products sold by the company Lubrizol under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382, Carbopol ETD 2020, Carbopol Ultrez 20 and Carbopol Ultrez 21 (INCI name: Acrylates/C_10-30 alkyl acrylate crosspolymer) , and even more preferentially Pemulen TR1 and Carbopol 1382;

(3) acrylic terpolymers comprising:

(a) from 19.5%to 70%by weight of an α, β-monoethylenically unsaturated carboxylic acid containing from 3 to 5 carbon atoms,

(b) from 20%to 80%by weight of C₁-C₄ alkyl (meth) acrylates,

(c) from 0.5%to 60%by weight of a nonionic urethane macromonomer of formula (VI) below:

in which p ranges from 6 to 150 and R2 is selected from linear alkyl radicals comprising from 18 to 26 and preferably from 20 to 24 carbon atoms. Preferably, the radical R2 is a behenyl radical.

Such terpolymers are described especially in patent application EP-A-0173109.

The α, β-monoethylenically unsaturated carboxylic acid (a) may be selected from acrylic acid, methacrylic acid and crotonic acid. It is preferably (meth) acrylic acid. Preferentially, the monomer (a) is methacrylic acid.

The terpolymer contains a monomer (b) selected from C₁-C₄ alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. The monomer (b) is preferably selected from methyl acrylate and ethyl acrylate.

Such terpolymers are generally in the form of an aqueous dispersion.

Use is preferentially made of a terpolymer of methacrylic acid/methyl acrylate/condensate of dimethyl m-isopropenyl benzyl isocyanate and of polyoxyethylenated (40 OE) behenyl alcohol (INCI name: Polyacrylate-3) , such as the product sold in the form of an aqueous dispersion at 25%by weight, under the name Viscophobe DB 1000 by the company The Dow Chemical Company;

(4) copolymers of an α, β-monoethylenically unsaturated carboxylic acid and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C₁₂-C₃₀ fatty alcohol, especially with 10 to 50 ethylene oxide units, and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol.

Examples of such copolymers that may be mentioned include:

- polymers of acrylic acid, of methyl acrylate and of 20 OE polyoxyethylenated stearyl methacrylate crosslinked with pentaerythrityl allyl ether or trimethylolpropane allyl ether (INCI name: Acrylates/steareth-20 methacrylate crosspolymer) sold under the name Aculyn 88 Polymer by the company The Dow Chemical Company,

- crosslinked polymers of acrylic acid, of methyl acrylate and of 25 OE polyoxyethylenated behenyl methacrylate (INCI name: Acrylates/beheneth-25 methacrylate copolymer) , such as the product sold under the name Novethix L-10 Polymer by the company Lubrizol Advanced Materials, Inc.,

- polymers of acrylic acid, of methyl acrylate and of 25 OE polyoxyethylenated C₁₂-C₂₄ alkyl methacrylate (INCI name: Acrylates/palmeth-25 acrylate copolymer) , such as the product sold under the name Synthalen W2000 L by the company 3V Group,

- polymers of methacrylic acid, of ethyl methacrylate, of polyethylene glycol C₁₆-C₂₂ alkyl ether methacrylate containing 25 ethylene glycol units, of the ether of 2- (6, 6-dimethylbicyclo [3.1.1] hept-2-en-2-yl) ethyl methacrylate and of polypropylene glycol containing 5 propylene glycol units and of polyethylene glycol containing 25 ethylene glycol units (INCI name: Polyacrylate-33) , such as the product sold under the name 33 by the company Rhodia Novecare.

- the polyoxyethylenated (20 OE) terpolymer of acrylic acid/ethyl acrylate/stearyl methacrylate (INCI name: Acrylates/steareth-20 methacrylate copolymer) sold especially under the name Aculyn 22 by the company The Dow Chemical Company,

- the polyoxyethylenated (25 OE) terpolymer of acrylic acid/ethyl acrylate/behenyl methacrylate (INCI name: Acrylates/beheneth-25 methacrylate copolymer) sold especially under the name Aculyn 28 Polymer by the company The Dow Chemical Company;

(5) copolymers of (meth) acrylic acid, of crosslinked C₁-C₄ alkyl (meth) acrylate, of polyethylene glycol C₁₀-C₃₀ alkyl ether methacrylate containing 25 mol of ethylene oxide and of polyethylene glycol allyl ether containing 20 ethylene oxide units/polypropylene glycol containing 5 propylene oxide units, such as the product sold under the name Plus Polymer by the company Lubrizol (INCI name: Polyacrylate-14) .

According to one particular embodiment, the associative polymers as described above have a weight-average molecular weight of less than 500 000 and even more preferentially of less than 100 000, preferably ranging from 5000 to 80 000, which may be measured via the methods known to those skilled in the art.

Preferably, the anionic acrylic copolymers are selected from

- anionic copolymers derived from at least one α, β-monoethylenically unsaturated carboxylic acid and at least one ester of an α, β-monoethylenically unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, and especially Acrylates Copolymer;

- anionic associative acrylic copolymers, which are preferably selected from copolymers of an α, β-monoethylenically unsaturated carboxylic acid, of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C₁₂-C₃₀ fatty alcohol, especially with 10 to 50 ethylene oxide units, and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol; and especially Acrylates/steareth-20 methacrylate copolymer and Acrylates/beheneth-25 methacrylate copolymer; and

- mixtures thereof.

More preferably, the anionic acrylic copolymer (s) are selected from anionic copolymers derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, and especially acrylates Copolymer.

Advantageously, the hydrophilic gelling polymer chosen from anionic acrylic copolymers is present in an amount ranging from 0.4 wt. %to 4.8 wt. %, or from 0.5 wt. %to 4.5 wt. %, preferably from 0.6 wt. %to 4.2 wt. %, or from 0.7 wt. %to 3.9 wt. %, and more preferably from 0.8 wt. %to 3.6 wt. %, from 0.9 wt. %to 3.3 wt. %, or from 1.0 wt. %to 3.0 wt. %, relative to the total weight of the colorant composition.

Polar oils

The term “oil” means a fatty substance that is liquid at normal temperature (25℃) and at atmospheric pressure (760 mmHg) .

The term “fatty substance” means an organic compound insoluble in water at normal temperature (25℃) and at atmospheric pressure (750 mmHg) . Insoluble means the solubility below 5%and such as below 1%and further such as below 0.1%.

Oils have in their structure a chain of at least two siloxane groups or at least one hydrocarbon chain having at least 6 carbon atoms.

Preferably, the polar oil has a polarity index value of less than 26 mN/m. The term “polarity index” means the polarity or surface tension (in 10^-3 Newton/meter) , as measured by the ring method using a ring tensiometer at 20℃ against air.

The polar oil is, for example, selected from fatty alcohols, esters of fatty acids and fatty alcohols, silicones; and mixtures thereof.

Examples of the polar oil that can be mentioned include, but not be limited to, isopropyl palmitate (25.2 mN/m) , octyldodecanol (24.8 mN/m) , isopropyl myristate (24.2 mN/m) , ethylhexyl palmitate (23.1 mN/m) , disiloxane (22.7 mN/m) , isopropyl stearate (21.9 mN/m) , caprylic/capric triglyceride (21.3 mN/m) , isopropyl isostearate (21.2 mN/m) , Jojoba Seed Oil (20.8 mN/m) , Peanut Oil (20.5 mN/m) , Sweet Almond Oil (20.3 mN/m) , Sunflower Seed Oil (19.3 mN/m) , Decyl Oleate (18.7 mN/m) , Avocado Oil (18.3 mN/m) , Olive Fruit Oil (16.9 mN/m) , Castor Seed Oil (13.7 mN/m) , Calendula Officinalis Flower Oil (11.1 mN/m) , Wheat Germ Oil (8.3 mN/m) , and mixtures thereof.

Preferably, the polar oil is selected from esters of fatty acid containing 7 to 19 carbon atoms and fatty alcohols containing 3 to 20 carbon atoms, wherein the total number of carbon atoms is between 10 and 30.

More preferably, the polar oil is isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof.

Advantageously, the polar oil is present in an amount ranging from 10 wt. %to 65 wt. %, preferably from 15 wt. %to 55 wt. %, more preferably from 20 wt. %to 45 wt. %, relative to the total weight of the colorant composition.

Surfactants

Preferably, the surfactant is selected from the group consisting of nonionic surfactants, amphoteric surfactants, anionic surfactants and mixtures thereof.

Preferably, the surfactant system comprises at least one nonionic surfactant, at least one amphoteric surfactant, and at least one anionic surfactant.

Amphoteric surfactants

Useful amphoteric surfactants include betaines, alkyl sultaines, alkyl amphoacetates and alkyl amphodiacetates, alkyl amphoproprionates, and mixtures thereof. Non-limiting examples of useful amphoteric surfactants are provided below.

(a) Betaines

Useful betaines include those of the following formulae (VIIa-VIId) :

wherein R₁₀ is an alkyl group having 8-18 carbon atoms; and n is an integer from 1 to 3.

Particularly useful betaines include, for example, coco-betaine, cocamidopropyl betaine, lauryl betaine, laurylhydroxy sulfobetaine, lauryldimethyl betaine, cocamidopropyl hydroxysultaine, behenyl betaine, capryl/capramidopropyl betaine, lauryl hydroxysultaine, stearyl betaine, and mixtures thereof. Typically, at least one betaine compound is selected from coco betaine, behenyl betaine, capryl/capramidopropyl betaine, and lauryl betaine, and mixtures thereof. Particularly preferred betaines include coco betaine and cocamidopropyl betaine.

(b) Alkyl Sultaines

Non-limiting examples of alkyl sultaines include hydroxyl sultaines of formula (VIII)

wherein R is an alkyl group having 8-18 carbon atoms. More specific examples include, but are not limited to cocamidopropyl hydroxysultaine, lauryl hydroxysultaine, and mixtures thereof.

(c) Alkyl Amphoacetates and Alkyl Amphodiacetates

Useful alkyl amphoacetates and alkyl amphodiacetates include those of Formula (IX) and (X) :

wherein R is an alkyl group having 8-18 carbon atoms. Sodium is shown as the cation in the above formulae but the cation may be an alkali metal ion such as sodium or potassium, ammonium ions, or alkanolammonium ions such as monoethanolammonium or triethanolammonium ions. A more specific, but non-limiting example, is sodium lauroamphoacetate.

(d) Alkyl Amphopropionates

Non-limiting examples of amphopropionates include cocoamphopropionate, caprylamphopropionate, cornamphopropionate, caproamphopropionate, oleoamphopropionate, isostearoamphopropionate, stearoamphopropionate, lauroamphopropionate, salts thereof, and mixtures thereof.

Advantageously, the amphoteric surfactant, if presents, is present in an amount ranging from 1 wt. %to 9 wt. %, preferably from 2 wt. %to 7 wt. %, more preferably from 3 wt. %to 5 wt. %, relative to the total weight of the colorant composition.

Anionic Surfactants

The anionic surfactants may be, for example, sulfate, sulfonate, carboxylic (or carboxylate) surfactants, or mixtures thereof. The sulfate, sulfonate, or carboxylic (or carboxylate) surfactants may, in various embodiments, comprise saturated or unsaturated hydrocarbon chains. The anionic surfactants may optionally be in salt form, or in the form of alkali metal or alkaline-earth metal, ammonium, or amino alcohol salts.

Sulfate anionic surfactants comprise at least one sulfate function. The sulfate anionic surfactants that may be used comprise at least one sulfate function (-OSO₃H or-OSO₃) . They may be chosen from, by way of non-limiting example, alkyl or alkenyl sulfates, alkyl or alkenyl ether sulfates, alkylamido or alkenylamido ether sulfates, alkylaryl or alkenylaryl polyether sulfates, monoglyceride sulfates, and salts of these compounds. In various embodiments, the alkyl or alkenyl groups of these compounds comprise up to 30 carbon atoms, such as, for example from 6 to 30 carbon atoms, such as from 8 to 28, from 8 to 22 or from 8 to 18 carbon atoms, and the aryl group may optionally denote a phenyl or benzyl group. In at least some embodiments, these compounds may optionally be polyoxyalkylenated, especially polyoxyethylenated, for example comprising from 1 to 50 ethylene oxide units, such as from 2 to 10 ethylene oxide units.

In certain embodiments, sulfate anionic surfactants are chosen from alkyl or alkenyl sulfates, such as C₆-C₂₄ alkyl or alkenyl sulfates or C₁₂-C₂₀ alkyl or alkenyl sulfates, or from alkyl or alkenyl ether sulfates, optionally having from 2 to 20 ethylene oxide units, such as C₆-C₂₄ alkyl or alkenyl ether sulfates, or C₁₂-C₂₀ alkyl or alkenyl ether sulfates.

Sulfonate anionic surfactants comprise at least one sulfonate function (-SO₃H or-SO₃ ^-) and may optionally also comprise one or more sulfate functions.

The sulfonate anionic surfactants that may be used comprise at least one sulfonate function (-SO₃H or-SO₃ ^-) . They may be chosen from the following compounds: alkylsulfonates, alkenylsulfonates, alkylamidesulfonates, alkenylamidesulfonates, alkylarylsulfonates, alkenylarylsulfonates, α-olefinsulfonates, paraffin sulfonates, alkylsulfosuccinates, alkenylsulfosuccinates, alkyl or alkenyl ether sulfosuccinates, alkylamidesulfosuccinates, alkenylamidesulfosuccinates, alkylsulfoacetates, alkenylsulfoacetates, N-acyltaurates, acylisethionates, alkylsulfolaurates, alkenylsulfolaurates, and salts of these compounds; the alkyl or alkenyl groups of these compounds comprising up to 30 carbon atoms, such as, for example, from 6 to 30 carbon atoms, such as from 8 to 28, from 8 to 22 or from 8 to 18 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

In certain embodiments, sulfonate anionic surfactants are chosen from those having up to 30 carbon atoms, such as from 6 to 30, from 8 to 28, from 8 to 22 or from 8 to 18 carbon atoms, for example alkyl or alkenyl sulfosuccinates, such as C₆-C₂₄alkyl or alkenyl sulfosuccinates or C₈-C₁₈alkyl or alkenyl sulfosuccinates, alkyl or alkenyl ether sulfosuccinates, such as C₆-C₂₄alkyl or alkenyl ether sulfosuccinates or C₈-C₁₈alkyl or alkenyl ether sulfosuccinates, or acylisethionates, such as such as C₆-C₂₄acylisethionates or C₈-C₁₈acylisethionates. In certain embodiments, the anionic surfactant is chosen from laurylsulfosuccinates.

Carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-OOH or-COO^-) and may optionally also comprise one or more sulfate and/or sulfonate functions. The carboxylic anionic surfactants that may be used thus comprise at least one carboxylic or carboxylate function (-OOH or-COO^-) . They may be chosen from the following compounds: acylglycinates, acyllactylates, acylsarcosinates, acylglutamates, alkyl-D-galactosideuronic acids, alkyl or alkenyl ether carboxylic acids, alkyl (C_6-30) or alkenyl aryl ether carboxylic acids, alkylamido or alkenylamido ether carboxylic acids; and also the salts of these compounds; the alkyl, alkenyl and/or acyl groups of these compounds comprising up to 30 carbon atoms, such as from 6 to 30 carbon atoms, especially from 8 to 28, better still from 8 to 22 or even from 8 to 18 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

In certain embodiments, C₆-C₂₄or C₈-C₁₈alkyl or alkenyl monoesters of polyglycosidepolycarboxylic acids, such as C₆-C₂₄or C₈-C₁₈alkyl or alkenyl polyglycoside-citrates, C₆-C₂₄or C₈-C₁₈alkyl polyglycoside-tartrates, C₆-C₂₄or C₈-C₁₈ alkyl or alkenyl polyglycoside-sulfosuccinates, and salts thereof, may be chosen.

In further embodiments, polyoxyalkylenated alkyl (amido) or alkenyl (amido) ether carboxylic acids and salts thereof, in particular those comprising from 2 to 50 alkylene oxide and in particular ethylene oxide groups, such as the compounds sold by the company Kao under the name Akypo, may be chosen. For example, polyoxyalkylenated alkyl (amido) or alkenyl (amido) ether carboxylic acids of formula (XI) may be chosen:
R₁- (OC₂H₄) _n-OCH₂COOA (XI)

wherein:

R₁ represents a linear, branched, or cyclic C₅-C₂₄ alkyl or alkenyl radical, optionally substituted, an alkyl (C₈-C₉) phenyl radical, a radical R₂CONH-CH₂-CH₂-with R₂ denoting a linear or branched C₉-C₂₁ alkyl or alkenyl radical, preferably, R₁ is a C₈-C₂₀ and preferably C₈-C₁₈ alkyl radical, and aryl preferably denotes phenyl;

n is an integer or decimal number (average value) ranging from 2 to 24 and preferably from 2 to 10; and

A denotes H, ammonium, Na, K, Li, Mg, or a monoethanolamine or triethanolamine residue.

In certain embodiments, the polyoxyalkylenated alkyl (amido) or alkenyl (amido) ether carboxylic acids of formula (XI) may be those where R₁ is chosen from a C₁₂-C₁₄ alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical; A is chosen from a hydrogen or sodium atom, and n ranges from 2 to 20, preferably 2 to 10. In further embodiments, the polyoxyalkylenated alkyl (amido) or alkenyl (amido) ether carboxylic acids of formula (XI) may be those where R₁ is chosen from a C₁₂ alkyl radical; A is chosen from a hydrogen or sodium atom, and n ranges from 2 to 10.

In certain embodiments, the carboxylic anionic surfactant may be chosen from acylglutamates, especially of C₆-C₂₄ or even C₁₂-C₂₀, such as stearoylglutamates, and in particular disodium stearoylglutamate, acylsarcosinates, especially of C₆-C₂₄ or even C₁₂-C₂₀, such as palmitoylsarcosinates, and in particular sodium palmitoylsarcosinate, acyllactylates, especially of C₁₂-C₂₈ or even C₁₄-C₂₄, such as behenoyllactylates, and in particular sodium behenoyllactylate, C₆-C₂₄ and especially C₁₂-C₂₀ acylglycinates, (C₆-C₂₄) alkyl ether carboxylates and especially (C₁₂-C₂₀) alkyl ether carboxylates, and polyoxyalkylenated (C₆-C₂₄) alkyl (amido) ether carboxylic acids, in particular those comprising from 2 to 50 ethylene oxide groups.

As noted herein, the anionic surfactant may optionally be in salt form. In that case, the salt may, for example, be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magnesium salt. In preferred embodiments, alkali metal or alkaline-earth metal salts may be chosen.

Advantageously, the anionic surfactant, if presents, is present in an amount ranging from 0.05 wt. %to 7 wt. %, preferably from 0.25 wt. %to 4 wt. %, more preferably from 0.5 wt. %to 1 wt. %, relative to the total weight of the colorant composition.

Nonionic surfactants

The nonionic surfactant selected from the group consisting of polyoxyalkylenated and polyglycerolated nonionic surfactants are particularly useful. For example, useful nonionic surfactants include hydrogenated castor oil (e.g., PEG-25 hydrogenated castor oil, PEG-30 hydrogenated castor oil, PEG-35 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-45 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-54 hydrogenated castor oil, PEG-55 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-65 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-100 hydrogenated castor oil, and PEG-200 hydrogenated castor oil) , esters of polyols with fatty acids or alkoxylated derivatives thereof (e.g., glyceryl distearate, glyceryl hydroxystearate, glyceryl laurate, glyceryl linoleate, glyceryl myristate, glyceryl oleate, glyceryl stearate, an ethoxylated derivate thereof, or a mixture thereof) , and ethoxylated fatty alcohols (or C₈-C₃₀ alcohols) .

In some instances, the one or more nonionic surfactants may include PEG-40 hydrogenated castor oil, oleth-5, polysorbate 80, or a mixture thereof.

The nonionic surfactant can be, for example, selected from alcohols, alpha-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non-limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils from plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C₆-C₂₄) alkylpolyglycosides; N- (C₆-C₂₄) alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄) alkylamine oxides or N- (C₁₀-C₁₄) acylaminopropyl-morpholine oxides; and mixtures thereof.

Examples of oxyalkylenated nonionic surfactants that may be mentioned include: oxyalkylenated (C₈-C₂₄) alkylphenols, saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃₀ alcohols, saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃₀ amides, esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of polyethylene glycols, polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of sorbitol, saturated or unsaturated, oxyalkylenated plant oils, condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

As examples of polyglycerolated nonionic surfactants, polyglycerolated C₈-C₄₀ alcohols may be used. In particular, the polyglycerolated C₈-C₄₀ alcohols correspond to the following formula XII:
RO- [CH₂-CH (CH₂OH) -O] _m-H or RO- [CH
(CH₂OH) -CH₂O] _m-H (XII)

in which R represents a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

As examples of compounds that are suitable in the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether) , lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether) , oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether) , cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture.

The nonionic surfactants may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100, such as glyceryl esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; polyethylene glycol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; sorbitol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; sugar (sucrose, glucose, alkylglycose) esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and alkoxylated derivatives thereof, preferably with a number of alkyleneoxide of from 10 to 200, and more preferably from 10 to 100; ethers of fatty alcohols; ethers of sugar and a C₈-C₂₄, preferably C₁₂-C₂₂, fatty alcohol or alcohols; and mixtures thereof.

Examples of ethoxylated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene groups, such as the compounds with the INCI names: PEG-9 to PEG-50 laurate; PEG-9 to PEG-50 palmitate; PEG-9 to PEG-50 stearate; PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate; and the compound polyethylene glycol 100 EO monostearate (INCI name: PEG-100 stearate) ; and mixtures thereof.

As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di-and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate and mixtures thereof can in particular be cited.

As glyceryl esters of C₈-C₂₄ alkoxylated fatty acids, polyethoxylated glyceryl stearate (glyceryl mono-, di-and/or tristearate) such as PEG-20 glyceryl stearate can for example be cited.

The sorbitol esters of C₈-C₂₄ fatty acids and alkoxylated derivatives thereof can be selected from sorbitan palmitate, sorbitan trioleate and esters of fatty acids and alkoxylated sorbitan containing for example from 20 to 100 EO, such as for example polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Ubiqema.

As esters of fatty acids and glucose or alkylglucose, in particular glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters and more specifically the diester of methylglucoside and oleic acid (INCI name: Methyl glucose dioleate) , the mixed ester of methylglucoside and the mixture oleic acid/hydroxystearic acid (INCI name: Methyl glucose dioleate/hydroxystearate) , the ester of methylglucoside and isostearic acid (INCI name: Methyl glucose isostearate) , the ester of methylglucoside and lauric acid (INCI name: Methyl glucose laurate) , the mixture of monoester and diester of methylglucoside and isostearic acid (INCI name: Methyl glucose sesqui-isostearate) , the mixture of monoester and diester of methylglucoside and stearic acid (INCI name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (INCI name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (INCI name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can for example be cited.

As sucrose esters, saccharose palmito-stearate, saccharose stearate and saccharose monolaurate can for example be cited.

As sugar ethers, alkylpolyglucosides can be used, and for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818/UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Advantageously, the nonionic surfactant, if presents, is present in an amount ranging from 0.05 wt. %to 3.5 wt. %, preferably from 0.25 wt. %to 2.5 wt. %, more preferably from 0.5 wt. %to 1.5 wt. %, relative to the total weight of the colorant composition.

Advantageously, the surfactant system, comprising at least one surfactant selected from the group consisting of nonionic surfactants, amphoteric surfactants, anionic surfactants and mixtures thereof may be present in an amount ranging from 0.1 wt. %to 30 wt. %, or 0.3 wt. %to 25 wt. %, preferably from 0.5 wt. %to 20 wt. %, or 0.8 wt. %to 18 wt. %, or from 1 wt. %to 15 wt. %, more preferably 1.5 wt. %to 12 wt. %, or from 2 wt. %to 10 wt. %relative to the total weight of the colorant composition.

Hydrous phase

The colorant composition of the present invention may comprise a hydrous phase.

Preferably, the hydrous phase comprises water.

The hydrous phase may also comprise one or more water-miscible or at least partially water-miscible compounds (at room temperature of 20-25℃) , for instance C₂-C₈ lower polyols, monoalcohols, or polyol ethers (especially containing from 3 to 16 carbon atoms) . The solvent of the colorant composition of the present invention may include water, or even consist essentially of water.

Advantageously, the hydrous phase is present in an amount ranging from 15 wt. %to 80 wt. %, preferably from 20 wt. %to 70 wt. %, more preferably from 25 wt. %to 60 wt. %, relative to the total weight of the colorant composition.

Advantageously, water is present in an amount ranging from 15 wt. %to 80 wt. %, preferably from 20 wt. %to 70 wt. %, more preferably from 25 wt. %to 60 wt. %, relative to the total weight of the colorant composition.

Other ingredients

The colorant composition according to the present invention may also comprise other ingredients, known previously elsewhere in cosmetic compositions, such as alkalizing agents, antioxidants, fragrances, and so on.

The skilled person in the art can adjust the amounts of the other ingredients so as not to adversely impact the final use of the colorant composition according to the present invention.

Developer composition

The developer composition according to the present invention comprises at least one oxidizing agent and at least one associative polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymer comprising one or more acrylic and/or methacrylic units, and a mixture thereof.

Oxidizing agents

The oxidizing agent according to the present invention is chosen from hydrogen peroxide and/or hydrogen peroxide-generating systems.

Specifically, the oxidizing agent is selected from the group consisting of hydrogen peroxide, persalts such as persulphates, percarbonates and perborates, urea peroxide, and mixtures thereof. Preferably, the oxidizing agent is hydrogen peroxide.

Advantageously, the oxidizing agent is present in an amount ranging from 0.1 wt. %to 25 wt. %, or from 0.5 wt. %to 24 wt. %, or from 0.9 wt. %to 23 wt. %, preferably from 1.3 wt. %to 22 wt. %, or from 1.7 wt. %to 21 wt. %, or from 2.1 wt. %to 20 wt. %, from 2.5 wt. %to 19 wt. %, or from 3 wt. %to 18 wt. %, more preferably from 3.5 wt. %to 17 wt. %, or from 4 wt. %to 16 wt. %, or from 4.5 wt. %to 15 wt. %, from 5 wt. %to 13 wt. %, relative to the total weight of the developer composition.

Associative polymers

As used herein, the associative polymer is selected from nonionic associative polyurethane polyethers, associative acrylic polymers comprising one or more acrylic and/or methacrylic units, and a mixture thereof.

As used herein, the term "associative polymer" means an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally comprises, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.

Nonionic associative polyurethane polyethers

The nonionic associative polyurethane polyethers generally comprise, in their chain, both hydrophilic blocks, usually of polyoxyethylene nature, and hydrophobic blocks that may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.

Preferably, these polyurethane polyethers comprise at least two lipophilic hydrocarbon chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer) . These same polymers may also be graft polymers or star polymers.

The nonionic associative polyurethane polyethers comprising a fatty chain may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups.

The nonionic associative polyurethane polyethers comprise a urethane linkage between the hydrophilic blocks, whence arises the name.

By extension, also included among the nonionic associative polyurethane polyethers comprising a hydrophobic chain are those in which the hydrophilic blocks are linked to the hydrophobic blocks via other chemical bonds.

As examples of nonionic associative polyurethane polyethers comprising a hydrophobic chain that may be used in the invention, it is also possible to use Rheolatecontaining a urea functional group, sold by the company Rheox, or208, 204 or 212, and also Acrysol RM

Mention may also be made of the product Elfacoscontaining a C₁₂-C₁₄alkyl chain, and the product Elfacoscontaining a C₁₈alkyl chain, from Akzo.

The product DWfrom Rohm&Haas containing a C₂₀alkyl chain and a urethane linkage, sold at a solids content of 20%in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in aqueous/alcoholic medium. Examples of such polymers that may be mentioned are 255, 278 and244 sold by the company Rheox. The products DW 1206F and DW 1206J, sold by the company Rohm&Haas, may also be used.

The polyurethane polyethers that may be used according to the invention may also be chosen from those described in the paper by G. Fonnum, J. Bakke and Fk. Hansen, Colloid Polym. Sci., 271, 380-389 (1993) .

According to a specific form of the invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) a polyoxyethylenated stearyl alcohol comprising 100 mol of ethylene oxide, and (iii) a diisocyanate.

Such polyurethane polyethers are sold especially by the company Elementis under the name Rheolate FXwhich is a polycondensate of polyethylene glycol containing 136 mol of ethylene oxide, of stearyl alcohol polyoxyethylenated with 100 mol of ethylene oxide and of hexamethylene diisocyanate (HDI) with a weight-average molecular weight of 30000 (INCI name: PEG-136/Steareth-100/HDI Copolymer) .

According to another specific form of the invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold in particular by the company Rohm&Haas under the names Aculynand Aculyn

Aculynhaving the INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer, is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis (4-cyclohexyl isocyanate) (SMDI) at 15%by weight in a matrix of maltodextrin (4%) and water (81%) (INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer) .

Aculyn (PEG-150/Decyl Alcohol/SMDI Copolymer) is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis (4-cyclohexyl isocyanate) (SMDI) at 35%by weight in a mixture of propylene glycol (39%) and water (26%) (INCI name: PEG-150/Decyl Alcohol/SMDI Copolymer) .

Advantageously, the nonionic associate polyurethane polyether, if presents, is present in an amount ranging from 0.2 wt. %to 3.5 wt. %, preferably from 0.4 wt. %to 2.5 wt. %, more preferably from 0.8 wt. %to 1.5 wt. %, relative to the total weight of the developer composition.

Associative acrylic polymers comprising one or more acrylic and/or methacrylic units

Preferably, the associative acrylic polymer is selected from copolymers of an α, β-monoethylenically unsaturated carboxylic acid and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C₁₂-C₃₀ fatty alcohol, especially with 10 to 50 ethylene oxide units, and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol.

More preferably, the associative acrylic polymer is selected from

-polymers of acrylic acid, of methyl acrylate and of 25 OE polyoxyethylenated C₁₂-C₂₄ alkyl methacrylate (INCI name: Acrylates/palmeth-25 acrylate copolymer) , such as the product sold under the name Synthalen W2000 L by the company 3V Group,

- the polyoxyethylenated (25 OE) terpolymer of acrylic acid/ethyl acrylate/behenyl methacrylate (INCI name: Acrylates/beheneth-25 methacrylate copolymer) sold especially under the name Aculyn 28 Polymer by the company The Dow Chemical Company.

Advantageously, the associative acrylic polymer, if presents, is present in an amount ranging from 0.2 wt. %to 3.5 wt. %, preferably from 0.4 wt. %to 2.5 wt. %, more preferably from 0.8 wt. %to 1.5 wt. %, relative to the total weight of the colorant composition.

Advantageously, the associate polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymers, and a mixture thereof, is present in an amount ranging from 0.2 wt. %to 3.5 wt. %, or from 0.3 wt. %to 3.0 wt. %, preferably from 0.4 wt. %to 2.5 wt. %, or from 0.6 wt. %to 2 wt. %, more preferably from 0.8 wt. %to 1.5 wt. %, relative to the total weight of the developer composition.

Nonionic surfactants

The developer composition may comprise a nonionic surfactant.

Preferably, the nonionic surfactant may be chosen from fatty alcohol-based compounds, fatty amide-based compounds, and mixtures thereof.

The term "fatty alcohol-based compounds" according to the present invention includes fatty alcohols, oxyalkylenated fatty alcohols, and mixtures thereof. The term "fatty alcohol" means a long-chain aliphatic alcohol comprising from 8 to 30 carbon atoms and comprising at least one hydroxyl group OH.

Examples of the fatty alcohol-based compounds that can be mentioned include, but not limit to cetearyl alcohol, which is a mixture of cetyl alcohol and stearyl alcohol, stearyl alcohol 20 OE (CTFA name steareth-20) , cetearyl alcohol 25 OE (CTFA name ceteareth-25) and mixtures thereof.

The fatty amide-based compounds according to the present invention are chosen from oxyalkylenated fatty amides, which are chosen from the compounds of formula (XIII) below:
R-CO-N (R') - (Alk-O) _nH (XIII)

wherein:

R denotes an optionally substituted C₈-C₃₀, preferably C₁₀-C₂₄ and better still C₁₂-C₂₂ alkyl or alkenyl radical,

R' denotes a hydrogen atom or an (Alk-O) _mH radical, and preferably a hydrogen atom,

Alk denotes a divalent alkylene radical comprising from 1 to 8 carbon atoms, preferably 2 or 3 carbon atoms,

n, m denote, independently of one another, a number ranging from 1 to 50, preferably from 1 to 20, better still from 1 to 10.

One non-limiting example of fatty amide-based compounds that can be mentioned is the compound having the INCI name PEG-4 rapeseedamide, sold in particular under the nameby the company Kao.

According to the present invention, the nonionic surfactant is present in an amount ranging from about 0.1 wt. %to about 20 wt. %, preferably from about 0.5 wt. %to about 15 wt. %, or from about 1 wt. %to about 10 wt. %, relative to the total weight of the developer composition.

Hydrous phase

The developer composition according to the invention may comprise a hydrous phase.

The hydrous phase can comprise ingredients as defined for the hydrous phase of the above colorant composition.

Advantageously, the hydrous phase is present in an amount ranging from 30 wt. %to 95 wt. %, preferably from 40 wt. %to 90 wt. %, relative to the total weight of the developer composition.

Advantageously, water is present in an amount ranging from 15 wt. %to 95 wt. %, preferably from 20 wt. %to 90 wt. %, more preferably from 25 wt. %to 85 wt. %, relative to the total weight of the developer composition.

Other ingredients

The developer composition according to the present invention may also comprise other ingredients, known previously elsewhere in cosmetic compositions, such as chelating agents, preservatives, pH adjusting agents, fragrances, and so on.

The skilled person in the art can adjust the amounts of the other ingredients so as not to adversely impact the final use of the developer composition according to the present invention.

The colorant composition and/or the developer composition of the present invention are in the form of cream. In one embodiment, both the colorant composition and the developer composition of the present invention are in the form of cream.

Conventionally, cream products show good color performance, while foam products in the market are convenient to use.

By means of the specific colorant composition comprising the above oxidative dye, hydrophilic gelling polymer, surfactant system, and polar oil of the present invention, even in the form of cream, the mixture from the colorant composition and the developer composition of the present invention can provide easy application similar with foam products and as good color performance as traditional cream products.

In one embodiment, both the colorant composition and the developer composition of the present invention are ammonia-free compositions, i.e. they do not comprise the ingredients which can generate ammonia, e.g. ammonium hydroxide, ammonium bicarbonate, and ammonium persulfate, such that the mixture from the colorant composition and the developer composition of the present invention would not generate unpleasant smell when being applied.

In one embodiment, the colorant composition and the developer composition of the present invention are disposed in two different compartments respectively. For example, the colorant composition and the developer composition are disposed in two different pouches or bottles for the dye kit of the present invention.

In one embodiment, the dye kit of the present invention is equipped with means allowing the delivery to the hair of the mixture of the colorant composition and the developer composition, for example, the device described in patent FR 2 586 913.

Process

According to the second aspect, the present invention relates to a process for dyeing keratin fibers, comprising:

applying the resulted mixture onto the keratin fibers; and

In one embodiment, the colorant composition of the present invention is put into a container or palm together with the developer composition as described above, with or without stirring them.

The mixture of the colorant composition and the developer composition is usually left in place on the keratin fibers for a time generally ranging from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process is conventionally between 20 and 80℃and preferably between 20 and 60℃. After the treatment, the human keratin fibers are advantageously rinsed with water. They may optionally be further washed with a shampoo, followed by rinsing with water, before being dried or left to dry.

The process may be repeated several times in order to obtain the desired coloration.

EXAMPLES

The present invention is illustrated in greater detail by the examples described below, which are given as non-limiting illustrations.

Main raw materials used, trade names and supplier thereof were listed in Table 1.

Table 1

Invention Examples (IE) 1-3 and Comparative Examples (CE) 1-5

The developer compositions according to invention examples 1-2 and comparative examples 1-3 were prepared with the ingredients listed in Table 2 (the contents were expressed as weight percentages of ingredients with regard to the total weight of each developer composition, unless otherwise indicated) :

Table 2

Developer compositions of invention examples 1-2 are developer compositions according to the present invention.

Developer compositions of comparative examples 1-3 do not comprise at least one associative polymer selected from nonionic associative polyurethane polyethers and associative acrylic polymer comprising one or more acrylic and/or methacrylic units.

The developer compositions were prepared as follows:

1) . adding 80%of the water, cetearyl alcohol, PEG-4 rapeseedamide, tetrasodium etidronate, and into a first main kettle and stirring and heating the mixture to the temperature of 75℃ at the speed of 200-300 rpm; after the temperature reached 75℃, stirring and emulsifying the mixture at the speed of 300-600 rpm for 15 minutes, and then cooling the mixture to 45℃;

2) . adding the rest of water (20%) into the first main kettle, stirring the mixture at the speed of 400-600 rpm for 10 minutes, and then cooling the mixture to 35℃;

3) . adding hydrogen peroxide into the first main kettle, cooling to room temperature and stirring the mixture at the speed of 400-600 rpm for 5-10 minutes until the mixture was uniform;

4) adding acrylates/beheneth-25 methacrylate copolymer or PEG-150/decyl alcohol/SMDI copolymer or hydroxyethylcellulose or xanthan gum (ifpresent) into the first main kettle and stirring the mixture at the speed of 600 rpm for 15 minutes until the mixture was uniform and then adjusting the mixture to the pH value of 2.2+-0.2 using phosphoric acid.

Colorant compositions according to invention example 3 and comparative examples 4-5 were prepared with the ingredients listed in Table 3 (the contents were expressed as weight percentages of ingredients with regard to the total weight of the colorant composition, unless otherwise indicated) .

Table 3

Colorant composition of invention example 3 is colorant composition according to the present invention.

Colorant composition of comparative example 4 does not comprise at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers.

Colorant composition of comparative example 5 does not comprise at least one polar oil.

Preparation procedure (taking IE. 3 for example) :

The colorant composition of IE. 3 was prepared as follows:

1) . adding water and acrylates copolymer into a second main kettle and stirring the mixture obtained at room temperature at the speed of 150-200 rpm for 5 minutes until the mixture was uniform;

2) . adding sodium lauryl sulfate, cocamidopropyl betaine, and PEG-40 hydrogenated castor oil into the second main kettle and stirring the mixture at room temperature at the speed of 200-300 rpm for 15 minutes until the mixture was uniform;

3) . adding ethanolamine into the second main kettle and stirring the mixture at room temperature at the speed of 200-300 rpm for 5-10 minutes until the mixture was uniform;

4) . adding ethylhexyl palmitate into the second main kettle and stirring the mixture at room temperature at the speed of 600-1000 rpm for 15-20 minutes to emulsify the mixture; and

5) . adding ascorbic Acid, sodium metabisulfite, hydroxybenzomorpholine, m-Aminophenol, 2-Methoxymethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate, and 2, 4-diaminophenoxyethanol HCl into the second main kettle and stirring the mixture at room temperature at the speed of 600-1000 rpm for 15 minutes until the mixture was uniform.

Evaluation

Viscosity, pumping ratio and stability of each of colorant compositions and developer compositions obtained were evaluated.

Viscosity

The viscosity of each colorant or developer composition was measured in order to check ifthe composition is acceptable for pumping out and application.

Viscosity was measured by a Mettler RM 180 Rheomat with spindle#2 (for developer compositions) or#3 (for colorant compositions) at 25℃ to check ifthe viscosity of the developer composition is within a range of 100-400 mPa. s, and ifthe viscosity of the colorant composition is within a range of 600-1500 mPa. s.

Pumping ability

110g of a colorant or developer composition was filled in a bi-pump package, 10 packages were prepared for each composition. For each package, the colorant or developer composition was pumped out with hand into a bowl until no composition can be pump out, then the composition in the bowl was weighted as M (g) . The pumping ratio is calculated as M/110 (%) . and then all the results for 10 packages were calculated, also the average results of 10 packages were recorded for both colorant and developer. The target average pumping ratio is above 85%for the 10 packages.

Stability

The stability of each colorant or developer composition was evaluated as follows:

The composition was prepared and aged for 24 hours at room temperature, then contained in a cosmetic bottle, then put into an oven or a refrigerator for storage for a period of time:

45℃: 1 month or 2 months;

Room temperature (20℃-25℃) : 1 month or 2 months;

4℃: 1 month.

Then whether the appearance was visibly changed was checked.

If there is no phase separation after storage, then the composition is considered stable.

If there is phase separation after storage, then the composition is considered instable.

Viscosity, pumping ratio and stability of each developer composition and colorant composition were summarized in Table 4.

Table 4

Application property, dripping issue, and viscosity of mixtures obtained by mixing a colorant composition and a developer composition were evaluated.

Application property

Each of developer compositions of invention examples 1-2 and comparative examples 1-3 as shown in Table 2 and colorant compositions of invention examples 3 and comparative examples 4-5 as shown in Table 3 were mixed at a ratio of 1: 1 by weight. The time T consumed to evenly apply the mixtures on half mannequin head by hands were recorded and compared, wherein each mixture was applied twice by different internal hair experts, and then the average time were calculated and the scores were given according to the following standard.

10: T<100 seconds;

9: 100≤T<110 seconds;

8: 110≤T<120 seconds;

7: 120≤T<130 seconds;

6: 130≤T<120 seconds;

5: 140≤T<150 seconds;

4: 150≤T<160 seconds;

3: 160≤T<170 seconds;

2: 170≤T<180 seconds;

1: ≥180 seconds.

Dripping issue

Whether there is dripping issue during the application of the mixtures obtained was observed by the experts.

Viscosity

In addition, viscosities of the mixtures obtained were measured by a Mettler RM 180 Rheomat with spindle#3 at 25℃ to check ifthe viscosity of each mixture is within the range of 600-1500 mPa. s.

The results on application property, dripping issue, and viscosity were summarized in Tables 5 and 6.

Table 5

Table 6

It can be also seen from Table 4 that compositions of invention examples 1-3 are stable and have suitable viscosities for pumping.

It can be also seen from Table 4 that compositions of comparative examples 2-5 are not desired due to too high viscosity or poor stability.

It can be seen from Tables 5 and 6 that mixtures obtained from kits according to the present invention have suitable viscosity, and can be easily pumped out and applied, meanwhile there is no dripping issue during application. And the mixtures obtained with developer composition of comparative examples 1 and 3 have too low viscosities and might cause dripping issue during application.

Claims

A kit for dyeing keratin fibers, comprising:

A) a colorant composition comprising:

(i) at least one oxidative dye chosen from oxidation bases, optionally in combination with one or more couplers;

(ii) at least one hydrophilic gelling polymer chosen from anionic acrylic copolymers;

(iii) at least one polar oil; and

(iv) at least one surfactant; and

B) a developer composition comprising:

I) at least one oxidizing agent; and

II) at least one associative polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymer comprising one or more acrylic and/or methacrylic units, and a mixture thereof.
The kit according to claim 1, wherein the colorant composition and/or the developer composition is in the form of cream; and/or the surfactant is selected from nonionic surfactants, amphoteric surfactants, anionic surfactants and mixture thereof, preferably the colorant composition comprises at least one amphoteric surfactant, at least one anionic surfactant and at least one nonionic surfactant.
The kit according to claim 1 or 2, wherein the oxidation bases are chosen from p-phenylenediamines, bis (phenyl) alkylenediamines, p-aminophenols, o-aminophenols, heterocyclic bases, and the addition salts thereof, and mixtures thereof, and preferably chosen from p-aminophenol, 2-methoxymethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, and the addition salts thereof, and mixtures thereof, and/or

the couplers are chosen from m-phenylenediamines, m-aminophenols, m-diphenols, naphthalene-based couplers, heterocyclic couplers, and also the addition salts thereof, and mixtures thereof, and preferably chosen from m-aminophenol, 6-hydroxybenzomorpholine, hydroxyethyl-3, 4-methylenedioxyaniline, 2, 4-diaminophenoxyethanol, and the addition salts thereof, and mixtures thereof.
The kit according any of claims 1-3, wherein

wherein the oxidation base is present in an amount ranging 0.1 wt. %to 15.0 wt. %, or from 0.15 wt. %to 14.0 wt. %, or from 0.2 wt. %to 13.0 wt. %, preferably from 0.25 wt. %to 12.0 wt. %, or from 0.3 wt. %to 11.0 wt. %, or from 0.35 wt. %to 10.0 wt. %, more preferably from 0.4 wt. %to 9.0 wt. %, or from 0.45 wt. %to 8.0 wt. %, or from 0.5 wt. %to 7.0 wt. %, or from 0.55 wt. %to 6.0 wt. %, from 0.6 wt. %to 5.0 wt. %, relative to the total weight of the colorant composition, and/or

the coupler is present in an amount ranging from 0.1 wt. %to 15.0 wt. %, preferably from 0.3 wt. %to 10.0 wt. %, more preferably from 0.5 wt. %to 5.0 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-4, wherein

the anionic acrylic copolymers are selected from

- anionic copolymers derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms;

- anionic associative acrylic copolymers; and

- mixtures thereof;

preferably, the anionic acrylic copolymers are selected from

- anionic copolymers derived from at least one α, β-monoethylenically unsaturated carboxylic acid and at least one ester of an α, β-monoethylenically unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms;

- copolymers of an α, β-monoethylenically unsaturated carboxylic acid, of an ester of an α, β-monoethylenically unsaturated carboxylic acid and a polyoxyethylenated C₁₂-C₃₀ fatty alcohol, especially with 10 to 50 ethylene oxide units, and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol; and

- mixtures thereof.
The kit according to any of claims 1-5, wherein the hydrophilic gelling polymer is present in an amount ranging from 0.4 wt. %to 4.8 wt. %, or from 0.5 wt. %to 4.5 wt. %, preferably from 0.6 wt. %to 4.2 wt. %, or from 0.7 wt. %to 3.9 wt. %, and more preferably from 0.8 wt. %to 3.6 wt. %, from 0.9 wt. %to 3.3 wt. %, or from 1.0 wt. %to 3.0 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-6, wherein the polar oil has a polarity index value of less than 26 mN/m, preferably the polar oil is chosen from fatty alcohols, esters of fatty acids and fatty alcohols, silicones and mixtures thereof; more preferably is chosen from esters of fatty acid containing 7 to 19 carbon atoms and fatty alcohols containing 3 to 20 carbon atoms, wherein the total number of carbon atoms is between 10 and 30; even more preferably is chosen from isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate and mixtures thereof, preferably the polar oil is present in an amount ranging from 10 wt. %to 65 wt. %, preferably from 15 wt. %to 55 wt. %, more preferably from 20 wt. %to 45 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-7, wherein

the amphoteric surfactant is chosen from betaines, alkyl sultaines, alkyl amphoacetates, alkyl amphoproprionates, and mixtures thereof, and preferably chosen from coco-betaine, cocamidopropyl betaine, and mixtures thereof;

the anionic surfactant is chosen from sulfate, sulfonate, carboxylic (or carboxylate) surfactants, and mixtures thereof, and preferably chosen from sodium laureth sulfate, sodium lauryl sulfate, and mixtures thereof; and/or

the nonionic surfactant is chosen from polyoxyalkylenated and polyglycerolated hydrogenated castor oils, glyceryl esters of fatty acids, glyceryl esters of C₈-C₂₄ alkoxylated fatty acids, esters of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and glucose or alkylglucose, alkylpolyglucosides, and mixtures thereof, and preferably chosen from PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, caprylyl/capryl glucoside, and mixtures thereof.
The kit according to any of claims 1-8, wherein

the amphoteric surfactant is present in an amount ranging from 1 wt. %to 9 wt. %, preferably from 2 wt. %to 7 wt. %, more preferably from 3 wt. %to 5 wt. %, relative to the total weight of the colorant composition;

the anionic surfactant is present in an amount ranging from 0.05 wt. %to 7 wt. %, preferably from 0.25 wt. %to 4 wt. %, more preferably from 0.5 wt. %to 1 wt. %, relative to the total weight of the colorant composition; and/or

the nonionic surfactant is present in an amount ranging from 0.05 wt. %to 3.5 wt. %, preferably from 0.25 wt. %to 2.5 wt. %, more preferably from 0.5 wt. %to 1.5 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-9, wherein the colorant composition further comprises water, which is present in an amount ranging from 15 wt. %to 95 wt. %, preferably from 20 wt. %to 90 wt. %, more preferably from 25 wt. %to 85 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-10, wherein the oxidizing agent is chosen from hydrogen peroxide and/or hydrogen peroxide-generating systems, and preferably is hydrogen peroxide, preferably the oxidizing agent is present in an amount ranging from 0.1 wt. %to 25 wt. %, or from 0.5 wt. %to 24 wt. %, or from 0.9 wt. %to 23 wt. %, preferably from 1.3 wt. %to 22 wt. %, or from 1.7 wt. %to 21 wt. %, or from 2.1 wt. %to 20 wt. %, from 2.5 wt. %to 19 wt. %, or from 3 wt. %to 18 wt. %, more preferably from 3.5 wt. %to 17 wt. %, or from 4 wt. %to 16 wt. %, or from 4.5 wt. %to 15 wt. %, from 5 wt. %to 13 wt. %, relative to the total weight of the developer composition.
The kit according to any of claims 1-11, wherein

the associative polymer is selected from nonionic associative polyurethane polyethers obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) a polyoxyethylenated stearyl alcohol comprising 100 mol of ethylene oxide, and (iii) a diisocyanate, anionic associative acrylic copolymers, and a mixture thereof;

preferably, the associate polymer is selected from nonionic associative polyurethane polyether obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate, copolymers of an α, β-monoethylenically unsaturated carboxylic acid and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a polyoxyethylenated C₁₂-C₃₀ fatty alcohol, especially with 10 to 50 ethylene oxide units, and of an ester of an α, β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol, and a mixture thereof;

more preferably, the associate polymer is selected from PEG-150/Stearyl Alcohol/SMDI copolymer, PEG-150/Decyl Alcohol/SMDI copolymer, PEG-136/Steareth-100/HDI copolymer, Acrylates/steareth-20 methacrylate crosspolymer, Acrylates/beheneth-25 methacrylate copolymer, Acrylates/palmeth-25 acrylate copolymer, Polyacrylate-33, Acrylates/steareth-20 methacrylate copolymer, and a mixture thereof.
The kit according to any of claims 1-12, wherein the associate polymer selected from nonionic associative polyurethane polyethers, associative acrylic polymers, and a mixture thereof, is present in an amount ranging from 0.2 wt. %to 3.5 wt. %, or from 0.3 wt. %to 3.0 wt. %, preferably from 0.4 wt. %to 2.5 wt. %, or from 0.6 wt. %to 2 wt. %, more preferably from 0.8 wt. %to 1.5 wt. %, relative to the total weight of the colorant composition.
The kit according to any of claims 1-13, wherein the developer composition further comprises at least one nonionic surfactant chosen from fatty alcohol-based compounds, fatty amide-based compounds, and mixtures thereof; and is present in an amount ranging from 0.1 wt. %to 20 wt. %, preferably from 0.5 wt. %to 15 wt. %, or from 1 wt. %to 10 wt. %, relative to the total weight of the developer composition.
A process for dyeing keratin fibers, comprising

mixing the colorant composition and developer composition as defined in any one of claims 1-16 immediately before use;

applying the resulted mixture onto the keratin fibers; and

rinsing off the mixture on the keratin fibers with water, optionally washing the keratin fibers with a shampoo before rinsing the keratin fibers with water.