Combination for dyeing keratinous fibers and its use

Abstract

Combination for Dyeing Keratin Fibers and its Use. The present invention relates to a dye combination comprising: A) a dye composition a), comprising: I) a coloring composition i), comprising: i) at least one oxidizing dye; wherein the oxidizing dye comprises one or more oxidizing bases selected from the group consisting of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, meta-aminophenols, ortho-aminophenols, and addition salts thereof, and mixtures thereof; and / or wherein the oxidizing dye comprises one or more couplers selected from the group consisting of meta-phenylenediamines, meta-aminophenols, and addition salts thereof, and mixtures thereof; and B) a pyrazolidine-3,5-dione compound of formula (1): (1). Figure for abstract: None

Description

Title of the invention: Combination for dyeing keratinous fibers and its use technical field

[0001] The present invention relates to a combination for dyeing keratinous fibers, in particular human keratinous fibers, for example hair. Background

[0002] For a long time, many people have sought to change the color of their hair, and in particular to dye it in order, for example, to cover their white hair.

[0003] “Permanent” dyeing processes, also called oxidative dyeing, which use dye compositions containing oxidizing dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds, have been developed to dye human keratin fibers permanently. These oxidation bases are colorless or weakly colored compounds that, when combined with oxidizing agents, can give rise to colored compounds through an oxidative condensation process.

[0004] The dyeing product may comprise at least one oxidizing dye and at least one oxidant. For best results, the oxidizing dye and the oxidant may be placed in a multi-compartment package and mixed together immediately before use.

[0005] Consumers wish to use dyes to color only the target area. However, in many cases, for example when dyeing hair, other areas may be undesirably dyed (stained), such as the hands, face, ears, and the like. Consumers must be more careful to avoid unwanted areas and have sought products to help them remedy unwanted dyeing. Summary of the invention

[0006] The inventors have now discovered that the use of a specific retarder in conjunction with an oxidative dye makes it possible to obtain a composition for the oxidative dyeing of keratinous fibers, which can overcome the above disadvantages, in particular by reducing or even substantially avoiding undesirable staining by the dye in an untargeted area.

[0007] An object of the present invention is therefore a dye combination for the oxidative dyeing of keratinous fibers, comprising:

[0008] A) a dye composition a), comprising:

[0009] I) a colouring composition I), comprising:

[0010] i) at least one oxidizing tint;

[0011] wherein the oxidizing tint comprises one or more oxidation bases chosen from the group consisting of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, and the addition salts of these, and mixtures of these;

[0012] and / or

[0013] wherein the oxidizing tint comprises one or more couplers selected from the group consisting of meta-phenylenediamines, meta-aminophenols, and their addition salts, and mixtures thereof; and

[0014] B) a pyrazolidine-3,5-dione compound of formula (1):

[0015] Ri., 'N R / "'

[0016] wherein Ri and R2 are each independently H, a hydroxyl, an unsubstituted or substituted Ci-C30 alkyl, an unsubstituted or substituted C2-C30 alkenyl, a cycloalkyl, an unsaturated heterocyclic group, a heterocyclic group or an epoxyalkyl such as a Ci-Cio alkyl or a halogen-substituted Ci-Cio alkyl, preferably a Ci-C6 alkyl or a halogen-substituted Ci-C6 alkyl, a C3-Cio alkenyl, a C3-Cio cycloalkyl, an unsaturated C3-Cio heterocyclic group, a C3-CiO heterocyclic alkyl or a C3-CiO alkoxy; and R3 is H, or a Ci-Cio alkyl, a C3-CiO cycloalkyl, a C3-CiO heterocyclic alkyl or a C3-CiO alkoxy, unsubstituted or substituted with a halogen, such as a Ci-C6 alkyl or a Ci-C4 alkyl, preferably H, the halogen preferably being F, Cl or Br.

[0017] Optionally, the pyrazolidine-3,5-dione compound of formula (1) is placed jointly with the dye composition a), or in a separate chamber from the dye composition a).

[0018] According to one embodiment of the invention, the dye composition a) may in turn comprise:

[0019] II) a developer composition II), comprising:

[0020] ii) at least one developer.

[0021] Optionally, the compound pyrazolidine-3,5-dione of formula (1) is placed in composition I).

[0022] The present invention therefore provides for the use of a pyrazolidine-3,5-dione compound of formula (1), used as a retarder, to slow down the reactions of a tint or intermediates thereof.

[0023] The present invention also provides for the use of a pyrazolidine-3,5-dione compound of formula (1) to reduce the colouring of a shade.

[0024] The present invention also provides for the use of a composition to reduce the colouring of a shade, wherein the composition comprises a pyra-zolidine-3,5-dione compound of formula (1).

[0025] The present invention also relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as hair, using the dye composition a) according to the invention.

[0026] The present invention also relates to a process for reducing dye stains on keratinous fibers such as hair, using the dye composition a) according to the invention.

[0027] The present invention also relates to a process for slowing down the reactions of the dye or its intermediates, characterized by mixing a pyrazolidine-3,5-dione compound of formula (1) with the dye. Preferably, the pyrazolidine-3,5-dione compound of formula (1) is mixed with the dye before the dye is applied, or the pyrazolidine-3,5-dione compound of formula (1) is applied to the area where the dye was applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes. Description of the drawings

[0028] [Fig-1] Fig. 1 shows the retarding performance of the mixtures according to Example 4. Embodiments of the invention

[0029] Throughout the description, including in the claims, the expression "comprising one" shall be understood as synonymous with "comprising at least one", unless otherwise stated. Furthermore, the expression "at least one" used in this description is equivalent to the expression "one or more".

[0030] Throughout the description, including the claims, an embodiment defined by "comprising" or similar should be understood as encompassing a preferred embodiment defined by "consisting substantially of" and a preferred embodiment defined by "consisting of".

[0031] Throughout the description, including the claims, the "keratinous fiber" according to the present invention is hair, eyelashes, eyebrows, or body hair. Preferably, the keratinous fiber according to the present invention is hair.

[0032] In the application, unless specifically stated otherwise, the contents, parts and for- Percentages are expressed on a weight basis.

[0033] Throughout the description, including the claims, the term "retarder" means an agent capable of slowing down reactions of the tint or intermediates thereof, such as reactions with the developer, for example an oxidation reaction between them.

[0034] According to the present invention, "stain reduction" refers to the reduction of staining occurring in unwanted areas, such as the hands, face, scalp, ears, rinse water, towels, floor, and the like. Preferably, the effect lasts at least 5 minutes after hair dyeing, more particularly 10 minutes, or preferably 15 or 20 minutes.

[0035] An object of the present invention is to provide a dye combination for the oxidative dyeing of keratinous fibers, comprising:

[0036] A) a dye composition a), comprising:

[0037] I) a coloring composition I), comprising the components of:

[0038] i) at least one oxidizing tint; and

[0039] II) a developer composition II), comprising the components of:

[0040] ii) at least one oxidant;

[0041] and

[0042] B) a pyrazolidine-3,5-dione compound of formula (1):

[0043] .9 (1) >1-^ / b

[0044] wherein Riet R2 are each independently H, a hydroxyl, an unsubstituted or substituted Ci-C30 alkyl, an unsubstituted or substituted C2-C30 alkenyl, a cycloalkyl, an unsaturated heterocyclic group, a heterocyclic group or an epoxyalkyl such as a Ci-Cio alkyl or a halogen-substituted Ci-Cio alkyl, preferably a Ci-C6 alkyl or a halogen-substituted Ci-C6 alkyl, a C3-Ci0 alkenyl, a C3-Ci0 cycloalkyl, an unsaturated C3-Ci0 heterocyclic group, a C3-Ci0 heterocyclic alkyl or a C3-Ci0 alkoxy; and R3 is H, or a Ci-Cio alkyl, a C3-CiO cycloalkyl, a C3-CiO heterocyclic alkyl or a C3-CiO alkoxy, unsubstituted or substituted with a halogen, such as a Ci-C6 alkyl or a Ci-C4 alkyl, preferably H, the halogen preferably being F, Cl or Br.

[0045] The color combination of the invention is intended to be used in a dyeing process for keratinous fibers.

[0046] An object of the invention is therefore a process for dyeing keratinous fibers, which consists of mixing the coloring composition I) with the composition II) of the dye composition a) immediately before use to obtain a dye mixture, optionally adding a pyrazolidine-3,5-dione compound of formula (1) to the dye mixture, and applying the dye combination of the invention to the keratinous fibers.

[0047] In an embodiment varying according to the present invention, a pyra-zolidine-3,5-dione compound of formula (1) can be added directly into the coloring composition I).

[0048] Other features and advantages of the invention will become more apparent from the description and examples that follow.

[0049] Except for the examples of operation, or where otherwise indicated, all numbers expressing quantities of components and / or reaction conditions shall be understood as being modified in all cases by the term "approximately", with the meaning conventionally known in the art, for example, within 10% of the number indicated (such as "approximately 10%" means 9% to 11% and "approximately 2%" means 1.8% to 2.2%). Dye composition a)

[0050] The dye composition a) in the combination according to the present invention may comprise a dye composition I) and a developer composition II).

[0051] According to one embodiment of the present invention, the colorant composition I) and the developer composition II) can be used in a weight ratio of 1:3 to 3:1, preferably 1:2 to 2:1, or preferably 2:3 to 1:1. Colouring composition I)

[0052] The dye composition a) in the combination according to the present invention comprises a dye composition I).

[0053] The colouring composition I) of the composition a) according to the present invention may comprise at least one oxidizing tint. Oxidizing tint

[0054] As previously stated, the colour composition I) according to the invention comprises one or more oxidizing tints usable as component i).

[0055] The oxidizing tints that can be used in the present invention are generally chosen from oxidation bases, preferably associated with one or more couplers.

[0056] Preferably, the oxidizing tint(s) comprises one or more oxidation bases.

[0057] The oxidation bases can be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, hetero-bases cyclics, and addition salts thereof and mixtures thereof; preferably among para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and mixtures thereof; more preferably among para-aminophenols, ortho-aminophenols and mixtures thereof.

[0058] Among the paraphenylenediamines, preference is given to an unsubstituted paraphenylenediamine or a paraphenylenediamine substituted by 1 or 2 alkyls in Ci-C4. Other examples may include para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-methyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine. Other paraphenylenediamines can also be used, for example 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([3-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(P-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(P-hydroxyethyl)amino-2-chloroaniline, 2-[3-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-([3-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-Dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-[3-hydroxyethyl)-para-phenylenediamine, N-([3,Y-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-[3-hydroxyethyloxy-para-phenylenediamine, 2-P-acetylaminoethyloxy-para-phenylenediamine, N-(|3-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-[3-hydroxyethylamino-5-aminotoluene and 3-hydroxy-l-(4'-aminophenyl)pyrrolidine, as well as the addition salts of these with an acid.

[0059] Examples of bis(phenyl)alkylenediamines may include N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(P-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.

[0060] Among the para-aminophenols, an unsubstituted para-aminophenol or a para-aminophenol substituted with 1 or 2 alkyl groups in the C1-C4 group. Other examples include para-aminophenol, 4-amino-3-methylphenol, and 4-amino-2-methylphenol. Other para-phenylenediamines can also be used, for example, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-([3-hydroxyethyl-aminomethyl)phenol, and 4-amino-2-fluorophenol, as well as their acid salts.

[0061] Examples of ortho-aminophenols include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, as well as their addition salts.

[0062] Among heterocyclic bases, examples that can be mentioned include pyridine derivatives and pyrimidine derivatives. According to one embodiment of the present invention, it is further preferred that no pyrazole derivative be used as an oxidizing dye.

[0063] Among the pyridine derivatives that can be mentioned, we can cite the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for example 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts of these.

[0064] Among the derivatives of pyrimidine, we may cite the compounds described, for example, in 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, where a tautomeric equilibrium exists.

[0065] The oxidizing dye(s) may also include one or more couplers, which may be chosen from those classically used for dyeing keratinous fibers.

[0066] Among these couplers, we may mention in particular meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, as well as their addition salts and mixtures thereof. In particular, preferably, unsubstituted meta-aminophenol or a meta-aminophenol substituted with 1 or 2 alkyls in C1-C4, unsubstituted meta-diphenol or a meta-diphenol substituted with 1 or 2 alkyls in C1-C4, diaminophenols, or unsubstituted hydroxyindoles, an amino-substituted hydroxypyridine, or hydroxybenzomorpholine may be used.

[0067] Examples that can be mentioned include l-hydroxy-3-aminobenzene, l-methyl-2-hydroxy-4-aminobenzene, 1,3-dihydroxybenzene, 1,3-Dihydroxy-2-methylbenzene, 5-amino-6-chloro-o-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-l-([3-hydroxyethyloxy)benzene, 2-amino-4-([3-hydroxyethylamino)-l-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-l-dimethylaminobenzene, sesamol, lP-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphtol, 2-methyl-l-naphtol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1N-(P-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis([3-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, the addition salts of these with an acid, and mixtures of these, such as the hydrochloride or dihydrochloride of these, for example, the dihydrochloride of 1-beta-hydroxyethyloxy-2,4-diaminobenzene (2,4-diaminophenoxyethanol HCl).

[0068] Generally, the addition salts of the oxidation bases and of the couplers that can be used in the context of the invention are in particular chosen from among the addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

[0069] In a first exemplary embodiment for the oxidation base, examples include unsubstituted para-phenylenediamine or para-phenylenediamine substituted by 1 or 2 alkyls in Ci-C4.

[0070] In a second exemplary embodiment of the oxidation base, examples include an unsubstituted para-aminophenol or a para-aminophenol substituted by 1 or 2 alkyls in Ci-C4, in particular an unsubstituted para-aminophenol.

[0071] For the oxidation base, unsubstituted para-aminophenol or para-aminophenol substituted by 1 or 2 alkyls in CrC4 is particularly mentioned.

[0072] In particular, for the coupler, preferably one can use unsubstituted meta-aminophenol or a meta-aminophenol substituted by 1 or 2 alkyls in CrC4, unsubstituted meta-diphenol or a meta-diphenol substituted by 1 or 2 alkyls in CrC4, diaminophenols, or unsubstituted hydroxyindoles, an amino-substituted hydroxypyridine, or hydroxybenzomorpholine.

[0073] When unsubstituted hydroxyindoles, an amino-substituted hydroxypyridine or a hydroxybenzomorpholine are used as a coupler, they are preferably used in combination with the oxidation base according to the second exemplary embodiment.

[0074] When an oxidation base according to the third exemplary embodiment for oxidation base is used, it is preferably used in combination with a substituted amino hydroxypyridine as a coupler.

[0075] In addition, the combination of 2-amino-3-hydroxypyridine as a coupler with the oxidation base according to the second exemplary embodiment, or the combination of 5-amino-6-chloro-o-methylphenol as a coupler with the oxidation base according to the second exemplary embodiment, may be mentioned individually.

[0076] Without being limited by any known theory, it is thought that when used in combination with component B), an aminophenol is preferably used. More particularly, a meta-aminophenol is preferably used, which can give a particularly desirable stainless result when used in combination with component B) according to the present invention.

[0077] The oxidation base(s) may advantageously represent from 0.0001% to 20% by weight, preferably from 0.01% to 10% by weight and even better from 0.1% to 5% by weight, relative to the total weight of composition I).

[0078] The coupler(s), if present, may advantageously represent from 0.0001% to 20% by weight, and preferably from 0.001% to 10% by weight, or from 0.01% to 5% by weight, relative to the total weight of composition I). Antioxidant

[0079] The colouring composition I) may optionally include an antioxidant.

[0080] The antioxidants used may include natural exogenous phytochemical antioxidants such as phenols and carotenoids.

[0081] The antioxidant may include flavonoids. Flavonoids constitute a large class of over 5,000 polyphenolic phytochemicals with antioxidant properties that act by directly scavenging free radicals. Flavonoids have anti-inflammatory, antibacterial, antiviral, anti-allergic, antimutagenic, antithrombotic, antitumor, and vasodilatory effects, and these mechanisms of action can also be used to prevent, mitigate, or eliminate oxidative damage caused by dental instruments. Flavonoids also exhibit chelating properties with metal ions and can mitigate oxidative damage caused by metal ions by chelating the ions. The formation and stability of the flavonoid-metal chelate depend on the function of the structure.Flavonoids with a catechol moiety and a hydrogen bond between the hydroxyl groups at positions 5 and 3 have chelating properties.

[0082] Vitamin C and its derivatives may be used, including ascorbic acid, erythorbic acid, or derivatives thereof, for example, sodium ascorbate / erythorbate and the fat-soluble ester of tetrahexyl decyl ascorbate / erythorbate and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, ascorbyl acetate, and the like. Furthermore, it is also possible to use plants derived from a large amount of vitamin C, such as extracts of Myrciaria dubia, acerola, emblica officinalis, and bioflavonoids from rosehips and citrus fruits, including water-soluble bioflavonoids such as hesperidin methyl chalcone.

[0083] Sesamum indicum or lignans may also be added. Sesame and its lignans (fibrous compounds associated with sesame) act as antioxidants. Sesame seed lignans significantly increase the activity of vitamin E.

[0084] Other antioxidants that can be incorporated into the compositions of the present invention include tocopherols (e.g., d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol, d-delta-tocopherol), tocotrienol phenol (e.g., da-tocotrienol, d-[3-tocotrienol], dy-tocotrienol, d-δ-tocotrienol), and vitamin E (α-tocopheryl acetate). These compounds can be isolated from natural sources, prepared synthetically, or blended. The tocotrienol-rich vitamin E preparation can be obtained by fractionating the vitamin E preparation to remove a portion of the biophenol and recover the more concentrated tocotrienol product. Useful tocotrienols are natural products isolated, for example, from wheat germ oil, grain oil or palm oil by high-performance liquid chromatography or from barley, distillers' grains or oats by alcoholic extraction and / or molecular distillation.The term "tocotrienol" as used here includes a tocotrienol-rich fraction obtained from these natural products as well as a pure compound. Increased glutathione peroxidase activity protects the skin from oxidative damage.

[0085] In addition, carotenoids, particularly lutein-type carotenoids, are also useful antioxidants that can be utilized. Lutein-type carotenoids include molecules such as lutein, canthaxanthin, cryptoxanthin, zeaxanthin, and astaxanthin. Lutein compounds protect compounds such as vitamin A, vitamin E, and other carotenoids.

[0086] The flavonoid may be a flavanone (a derivative of 2,3-dihydro-2-phenylbenzopyran-4-one). Flavanones include: scutellarin, eriodictin, hesperetin, hesperidin, sylvestre, isosakuranetin, naringenin, naringin, pinocine, tangrin (poncirin), sakuranetin, sakura glycosides and 7-O-methyl er-gophenol (sterubine).

[0087] The flavonoid may be a dihydroflavonol (a derivative of 3-hydroxy-2,3-dihydro-2-phenylbenzopyran-4-one). Flavanols include: taxifolin, aromadrin, chrysandroside A, chrysandroside B, xeractinol, astilbine, and flavonol.

[0088] The flavonoid may be a flavonoid (a derivative of 2-phenylbenzopyran-4-one). Flavonoids include: apigenin, luteolin, tangeritin, chrysin, baicalein, wild baicalein, wogonin, synthetic flavonoids: diosmin and flavonoid ester.

[0089] The flavonoid may be a flavonol (a derivative of 3-hydroxy-2-phenylbenzopyran-4-one). Flavonols include: 3-hydroxyflavone, rhodoxanthin, quercetin, galangin, cotton dermatan, kaempferol, isorhamnetin, blackberry pigment, myricetin, naringin (natsudaidaine), muskyl flavonol (pachypodol), quercetin, methyl rhamnosine, rhamnetin, azalein, hyperoside, isoquercetin, suede glycosides, robinin, rutin, spirea, xanthorhamnine, amurensin, icariin, and tracuridine.

[0090] The flavonoid may be a flavan-3-ol (a derivative of 2-phenyl-3,4-dihydro-2H-benzopyran-3-ol). Flavan-3-ols include: catechin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, epiafzelin, fisetinidol, guibourtinidol, mesquitol, and robinetinidol.

[0091] The flavonoid may be a flavan-4-ol (a derivative of 2-phenylchroman-4-ol). Flavan-4-ols include: apiforol and luteoforol.

[0092] The flavonoid may be an isoflavone (a derivative of 3-phenylbenzopyran-4-one). Isoflavones include: genistein, daidzein, garbanin A, formononetin and equol metabolites of daidzein.

[0093] The antioxidant may be an anthocyanin (a derivative of the 2-phenylbenzopyranoside cation). Anthocyanins include: aurantinidin, cyanidin, del-phinidin, europinidin, luteolinidin, pelargonidin, malvidin, peonidin, morning glory pigment (petunidin), rose pigment (rosinidin), and xanthone.

[0094] The antioxidant may be a dihydrochalcone (a derivative of the 1,3-diphenyl-l-propanone). Dihydrochalcone includes: phloretin, dihydrochalcone phloridine cisplatin, aspalathin, naringin dihydrochalcone, neohesperidin dihydrochalcone, and nothofagin. The mode of action of the present invention is not limited, but dihydrochalcone may exert an antioxidant effect by reducing reactive radicals such as reactive oxygen species and reactive nitrogen species.

[0095] The antioxidant can be an anthocyanin. Anthocyanins and their derivatives are antioxidants. Anthocyanins comprise a class of flavonoid compounds responsible for the red, purple, and blue colors of many fruits, vegetables, grains, and flowers, which are natural water-soluble compounds. In addition, anthocyanins are collagenase inhibitors. Inhibiting collagenase helps prevent and reduce wrinkles caused by the reduction of skin collagen, increase skin elasticity, and so on. Anthocyanins can be obtained from any part of a variety of plant sources, such as the solid parts, flowers, stems, leaves, roots, bark, or seeds. Those skilled in the art will understand that certain portions of the plant These fractions may contain naturally higher levels of anthocyanins, and therefore they are used to obtain the desired anthocyanins. In some cases, the antioxidant may include one or more betaines. Betaine, similar to anthocyanins, is available from natural sources and is an antioxidant.

[0096] The antioxidant may be a phenylpropanoid (a derivative of cinnamic acid). Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including its antioxidant pharmacokinetic, 2,6-dihydroxyacetophenomenon), 5-hydroxyferric acid, sinapic acid, coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, chavicol, baicein, p-coumaric acid, and sinapinic acid. Without limiting the mode of action of the present invention, phenylpropanoids may neutralize free radicals.

[0097] The antioxidant may be a chalcone (a derivative of 1,3-diphenyl-2-propen-1-one). Chalcones include: zirconia, okanin, safflower, marein, sophoradine, xanthohumol, flavokavaine A, flavokavaine B, flavokavaine C, and synthetic safalcone.

[0098] The antioxidant may be a curcuminoid. Curcuminoids include: curcumin, demethoxycurcumin, bis-demethoxycurcumin, and tetrahydrocurcumin. Curcumin and tetrahydrocurcumin may be derived from the turmeric rhizome. Tetrahydrocurcumin, a metabolite of curcumin, has been shown to be a more potent and stable antioxidant than curcumin.

[0099] The antioxidant may be a tannin. Tannins include: tannins, terflavin B, glu-cogallin, D-gallic acid and quercitannic acid.

[0100] The antioxidant may be a stilbenoid. Stilbenoids include: resveratrol, red sandalwood, and paclitaxel. Resveratrol may include, but is not limited to, 3,5,4'-trihydroxyindole, 3,4,3',5'-tetrahydroxyindole (cetotriol), 2,3',4,5'-tetrahydroxyindole (oxidized resveratrol), 4,4'-dihydroxyindole, and its alpha and beta glucoside, galactoside, and mannoside derivatives.

[0101] The antioxidant may be a coumarin (a derivative of 2H-benzopyran-2-one). Coumarins include: 4-hydroxycoumarin, umbelliferone, aesculetin, hemiarin, auraptene, and dicoumarin.

[0102] The antioxidant may be a carotenoid. Carotenoids include: beta-carotene, alpha-carotene, gamma-carotene, beta-cryptoxanthin, lycopene, lutein and idebenone.

[0103] The antioxidant may be a vitamin or a derivative thereof. Vitamins include: retinol, ascorbic acid or erythorbic acid, L-ascorbic acid, tocopherol, tocotrienol and vitamin cofactor: coenzyme Q10.

[0104] The antioxidant may be: xanthone, butylated hydroxytoluene, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, gallic acid, eugenol, uric acid, alpha-lipoic acid, ellagic acid, cichoric acid, chlorogenic acid, rosmarinic acid, salicylic acid, acetylcysteine, S-allylcysteine, pyridone (Barbigerone), che- bulagic acid, edaravone, ethoxyquin, glutathione, hydroxytyrosol, idebenone, melatonin, N-acetylserotonin, nordihydroguaiaretic acid, oleotanthal, oleuropein, paradol, paclitaxel, probucol, propyl gallate, protocatechuic acid, pyrithione, rutin, linseed lignan diglucoside, sesamin, sesame phenol, silybin, silymarin, theaflavins, theaflavin digallate, thymoquinone, Trolox, tyrosol, polyunsaturated fatty acids, and sulfur-based antioxidants such as methionine or lipoic acid. Reducer

[0105] The colouring composition I) may include a reducer for use as an antioxidant.

[0106] According to the present invention, useful reducing agents may include sodium thiosulfate, sodium metabisulfite, ammonium thiourea sulfite, thioglycolic acid (TGA), thiolactic acid, ammonium thiolactate, mono-carbothioic acid diglycidyl ester, carbothioic ammonium acetate, thioglycerol, dithio glycolic acid, diammonium carbothioic strontium acetate, thio glycolate, isooctyl carbothioic acid, cysteine, cysteamine, homocysteine, glutathione peptide, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiodiglycol, 2-mercaptoethanol, dithiothreitol, thioxanthine, thiosalicylic acid, thiopropionic acid, lipoic acid, N-acetylcysteine ​​and its salts; ammonium thioglycolate, glycerol monothioglycolate, or a mixture of these.

[0107] Examples of preferred reducing agents that may be mentioned include thioglycolic acid, dithioglycolic acid, thiolactic acid, thiomalic acid, salts thereof or a mixture thereof.

[0108] The antioxidant, including the reducer, described above is preferably used according to the invention in an amount ranging from 0.001 to 10% by weight, preferably from 0.1 to 7% by weight, or preferably from 0.5 to 5% by weight, relative to the total weight of the colouring composition I). Surfactant

[0109] The colouring composition I) according to the invention may comprise one or more surfactants, for example, in particular an anionic surfactant and / or a non-ionic surfactant. Anionic surfactant

[0110] The colouring composition I) according to the invention may further comprise one or more anionic surfactants.

[0111] The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably selected from the following groups:

[0112] -COOH, -COO, -SO3H, -SO3, -OSO3H, -OSO3, -PO2H2, -PO2H, -PO?, -P(OH)2, =P(O)OH, -P(OH)O, =P(0)0, =POH, =P0, the anionic parts comprising a cationic counter-ion such as an alkali metal, an alkaline earth metal or an ammonium.

[0113] By way of examples of anionic surfactants that can be used in the colorant composition I) according to the invention, alkyl sulfates, alkyl ethers sulfates, alkylamidoethersulfates, alkylaryl polyethersulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosucinamates, acylisethionates and N-acyltaurates, polycarboxylic acid salts and alkyl monoester of polyglycoside, acyl lactylates, salts of acids Uronic D-galactoside, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts, and the corresponding non-salted forms of all these compounds;The alkyl and acyl groups of all these compounds comprise from 6 to 40 carbon atoms, and the aryl group designates a phenyl group.

[0114] These compounds can be oxyethylated and then preferably comprise from 1 to 50 units of ethylene oxide.

[0115] The salts of the C6-C24 alkyl monoesters of polyglycoside-polycarbyl acids can be selected from C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglycoside-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates.

[0116] When the anionic surfactant(s) is / are in salt form, it / they may be chosen from alkali metal salts such as sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular amino alcohol salts, alkaline earth metal salts such as magnesium salts.

[0117] Examples of amino alcohol salts that may be cited include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-l-propanol salts, 2-amino-2-methyl-l,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

[0118] Salts of alkali or alkaline-earth metals, and in particular sodium or magnesium salts, are preferably used.

[0119] Preferred anionic surfactants are selected from C6-C3O alkyl sulfates, C6-C3O alkyl ethers sulfates, C6-C3O alkylamido ethers sulfates, alkylaryl polyethers sulfates and monoglyceride sulfates, all of these compounds optionally comprising 1 to 20 units of ethylene oxide; or preferably from alkyl sulfates C12-C20 and C12-C20 alkyl ether sulfates containing 2 to 20 units of ethylene oxide, for example, 1 to 4 units of ethylene oxide, particularly in the form of alkali metal, ammonium, amino alcohol, and alkaline earth metal salts, or a mixture of these compounds. Better still, a polyoxyethylenated sodium lauryl ether sulfate is preferred, such as sodium lauryl ether sulfate containing 2 or 2.2 moles of ethylene oxide.

[0120] Preferably, the anionic surfactants of the invention are sulfates, more particularly selected from alkyl sulfates (in C6-C30), alkyl ether sulfates (in C6-C30), alkylamido ether sulfates (in C6-C30), alkylaryl polyether sulfates and monoglyceride sulfates, their salts such as alkali salts, such as sodium, and mixtures thereof.

[0121] Or preferably, the anionic surfactants of the invention are selected from alkyl (C6-C30) sulfates, alkyl (C6-C30) ether sulfates, in particular alkyl (C6-C30) ether sulfates such as lauryl ether sulfate, their salts, such as sodium laureth sulfate.

[0122] The quantity of said anionic surfactant(s) in the colorant composition I according to the invention is from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, or preferably from 0.1 to 8% by weight, relative to the total weight of composition I). Nonionic surfactant

[0123] The colouring composition I) according to the invention may further contain one or more non-ionic surfactants.

[0124] The non-ionic surfactant(s) that may be used in the compositions is / are described, for example, in the Handbook of Surfactants by MR Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178.

[0125] Examples of nonionic surfactants that may be mentioned include the following nonionic surfactants:

[0126] - alkyl (C8-C24) oxyalkylated phenols;

[0127] - C8-C30 fatty acid amides, saturated or unsaturated, linear or branched, oxy alkylated;

[0128] - fatty alcohols in the C8 to C40 range, particularly in the C8-C2O range and even better in the C10-C18 range, saturated or unsaturated, linear or branched, oxyethylenated comprising from 1 to 100 moles of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 moles, or even from 3 to 20 moles of ethylene oxide;

[0129] - C8-C30 acid esters, saturated or unsaturated, linear or branched, and poly ethylene glycols;

[0130] - C8-C30 acid esters, saturated or unsaturated, linear or branched, and of sorbitol, preferably oxygenated;

[0131] - fatty acid esters of sucrose;

[0132] - C8-C30 alkyl (poly)glucosides, C8-C30 alkenyl (poly)glucosides, optionally oxyalkylated (0 to 10 oxyalkylene units) and comprising 1 to 15 glucose units, the C8-C30 alkyl (poly)glucoside esters;

[0133] - saturated or unsaturated, oxygenated vegetable oils;

[0134] - ethylene oxide and / or propylene oxide condensates, among others, alone or in a mixture;

[0135] - N-alkyl (C8-C30) glucamine and N-acyl (C8-C30) methyl- derivatives glucamine;

[0136] - aldobionamides;

[0137] - amine oxides;

[0138] - oxyethylenated and / or oxypropylenated silicones;

[0139] - and mixtures thereof.

[0140] The terms "oxyalkylated", "oxyethylated", "oxypropylated" and "glycerolated" cover, respectively, mono- or poly-oxyalkylated, oxyethylated, oxypropylated and glycerolated compounds, unless otherwise specified.

[0141] The oxyalkylene units are more particularly oxyethylenated or oxy-propylene units, or a combination thereof, preferably oxyethylenated units.

[0142] The number of moles of ethylene oxide and / or propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol particularly ranges from 1 to 50 and better still from 1 to 10.

[0143] Advantageously, the non-ionic surfactants according to the invention do not have oxypropylene motifs.

[0144] Examples may include, but are not limited to, lauryl alcohol containing 4 moles of ethylene oxide (INCI name: Laureth-4) and lauryl alcohol containing 12 moles of ethylene oxide (INCI name: Laureth-12). Other examples may include OLETH-10, OLETH-30, DECETH-3, DECETH-5 and the like.

[0145] As examples of nonionic glycerolated surfactants, preferably monoglycerolated or polyglycerolated C8-C40 alcohols are used, comprising from 1 to 50 moles of glycerol and preferably from 1 to 10 moles of glycerol.

[0146] Examples of compounds of this type include lauryl alcohol containing 4 moles 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, oleyl / cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

[0147] Among glycerol alcohols, it is particularly preferred to use the C8 / C10 alcohol containing 1 mole of glycerol, the C10 / C12 alcohol containing 1 mole of glycerol and C12 alcohol containing 1.5 moles of glycerol.

[0148] The non-ionic surfactant(s), when present in the colour composition I) according to the invention, is (are) preferably present in a total quantity ranging from 0.01 to 1% by weight, relative to the total weight of the composition. Solvent

[0149] The colouring composition I) according to the invention may advantageously comprise one or more solvents, for example water and / or an organic solvent. Water

[0150] The colouring composition I) according to the invention advantageously comprises water, in a content less than or equal to 40% by weight relative to the total weight of composition I).

[0151] The water content in the colouring composition I) according to the invention is preferably from 10% to 40% by weight, more preferably from 15% to 35% by weight, or from 20% to 30% by weight, relative to the total weight of composition I). Organic solvent

[0152] The colouring composition I) according to the invention may also include one or more water-soluble organic solvents (solubility greater than or equal to 5% in water at 25°C and atmospheric pressure).

[0153] Examples of water-soluble organic solvents that may be cited include linear or branched monoalcohols or diols, preferably saturated, comprising 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, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; ethers of polyols, for example monomethyl, monoethyl and monobutyl ether of ethylene glycol, propylene glycol or ethers thereof, for example monomethyl ether of propylene glycol; as well as diethylene glycol alkyl ethers, in particular C1-C4 alkyl ethers, for example diethylene glycol monoethyl ether or diethylene glycol monobutyl ether, alone or in mixtures.

[0154] Water-soluble organic solvents, when present, generally represent between 1% and 20% by weight relative to the total weight of the colour composition I) according to the invention, and preferably between 3% and 15% by weight, or between 4% and 10% by weight. Alkaline agent

[0155] The colouring composition I) according to the invention may further comprise one or more alkaline agents.

[0156] The alkali agent(s) may in particular be chosen from aqueous ammonia, carbonates or bicarbonates of alkali metals, organic amines whose pKb at 25 °C is less than 12, in particular less than 10 and even more advantageously less than 6; from the salts of the amines mentioned above with acids such as carbonic acid or hydrochloric acid: it should be noted that this is the pKb corresponding to the function of strongest basicity.

[0157] Preferably, composition I) according to the present invention can be free or substantially free of aqueous ammonia.

[0158] Preferably, the amines are chosen from alkanolamines, including in particular a primary, secondary or tertiary amine function, and one or more linear or branched CrC8 alkyl groups bearing one or more hydroxyl radicals; from oxyethylenated and / or oxypropylenated ethylenediamines, and from amino acids and compounds having the following formula:

[0159] Rx^ zRz zN WN Ry xRt

[0160] wherein W is a Ci-C6 alkylene residue optionally substituted by a hydroxyl group or a Ci-C6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a Ci-C6 alkyl radical, a Ci-C6 hydroxyalkyl radical or a Ci-C6 aminoalkyl radical.

[0161] According to one embodiment of the invention, the colouring composition I) according to the invention comprises at least one alkanolamine and / or at least one basic amino acid, more advantageously at least one alkanolamine, such as ethanolamine, or mixtures thereof.

[0162] Advantageously, the content of alkali agent(s) ranges from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, or from 1% to 10% or 5% by weight relative to the total weight of composition I). It should be noted that this content is expressed as NH3 when the alkali agent is aqueous ammonia.

[0163] The pH of composition I) of the invention is preferably from 6 to 11.

[0164] The pH can be adjusted by adding acidifying agents, such as hydrochloric acid, (Ortho)phosphoric acid, sulfuric acid, boric acid, as well as carboxylic acids, for example acetic acid, lactic acid or citric acid, or sulfonic acids. Alkaline agents such as those mentioned above may also be used. Fatty phase

[0165] The colouring composition I) according to the invention may further comprise a cosmetically acceptable fatty substance.

[0166] According to a particular embodiment, the fat body is free of groups carboxylic acids.

[0167] The term "fats" refers to organic compounds insoluble in water at room temperature (25°C) and atmospheric pressure (760 mmHg) (solubility less than 5%, preferably 1%, and even more preferably 0.1%). They may preferably have in their structure a sequence of at least two siloxane groups or at least one hydrocarbon chain comprising at least six carbon atoms. Furthermore, fats are generally soluble in organic solvents under the same conditions of temperature and pressure, for example, chloroform, ethanol, benzene, or decamethylcyclopentasiloxane.

[0168] Fatty substances are in particular selected from among lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, oils, in particular non-siliconized mineral, vegetable, animal or synthetic oils, non-siliconized waxes, silicones.

[0169] It is recalled that, within the scope of the invention, fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched hydrocarbon groups, saturated or unsaturated, comprising 6 to 30 carbon atoms, which is (are) optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may contain one to three conjugated or non-conjugated carbon-carbon double bonds.

[0170] As regards lower alkanes, these alkanes comprise from 6 to 16 carbon atoms and are linear or branched, optionally cyclic. By way of example, alkanes may be chosen from hexane and dodecane, isoparaffins such as isohexadecane and isodecane.

[0171] Examples of non-siliconized oils that may be used in the composition of the invention include:

[0172] - hydrocarbon oils of animal origin, such as perhydrosqualene;

[0173] - vegetable hydrocarbon oils, such as liquid triglycerides fatty acids containing 6 to 30 carbon atoms, for example heptanoic or octanoic acid triglycerides, or, for example, sunflower oil, corn oil, soybean oil, bone marrow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic / capric acid triglycerides, for example those sold by Stéarineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel, jojoba oil and shea butter oil;

[0174] - linear or branched hydrocarbons of more than 16 carbon atoms and of origin mineral or synthetic, such as liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam®;

[0175] - fluorinated oils, for example perfluoromethylcyclopentane and perfluoro- 1,3-Dimethylcyclohexane, sold under the names Flutec® PCI and Flutec® PC3 by the BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by 3M, or bromoperfluorooctyl sold under the name Foralkyl® by Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by 3M.

[0176] The fatty alcohols that may be used in the composition of the invention are not oxyalkylated. They are saturated or unsaturated, linear or branched, and comprise from 6 to 30 carbon atoms, and more particularly from 8 to 30 carbon atoms. Examples include cetyl alcohol, stearyl alcohol and mixtures thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol, and linoleyl alcohol.

[0177] The useful esters are the esters of Ci-C26 aliphatic mono- or polyacids, saturated or unsaturated, linear or branched, and of Ci-C26 aliphatic mono- or polyalcohols, saturated or unsaturated, linear or branched, the total number of carbons of the esters being more particularly greater than or equal to 10.

[0178] Among the monoesters, the following may be mentioned: dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyle stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate;Ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyle or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

[0179] Still within the framework of this variant, esters of dicarboxylic or tricarboxylic acids in C4-C22 and of alcohols in Ci-C22, as well as esters of mono-, di- or tricarboxylic acids and of di-, tri-, tetra- or pentahydroxyalcohols in C2-C26, can also be used.

[0180] Examples include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoylstearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; tetraoctanoate pentaerythrityl; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; ethylene glycol distearate; diethylene glycol distearate and polyethylene glycol distearate.

[0181] The composition may also include, as a fatty acid ester, sugar esters and diesters of C6-C30 fatty acids and preferably of C2-C22 fatty acids. It is recalled that the term "sugar" refers to oxygenated hydrocarbon compounds having several alcohol functional groups, with or without aldehyde or ketone functional groups, and comprising at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.

[0182] Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, including alkyl derivatives, such as methyl derivatives, for example methylglucose.

[0183] Sugar esters of fatty acids may be selected in particular from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched fatty acids, saturated or unsaturated, in C6-C3o and preferably in Ci2-C22. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.

[0184] The esters according to this variant can also be chosen from mono, di, tri, tetraesters and polyesters, and mixtures thereof.

[0185] These esters may be selected, for example, from oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, mixed oleo-palmitate, oleo-stearate and palmito-stearate esters.

[0186] It is particularly preferred to use monoesters and diesters and in particular mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methyl-glucose.

[0187] Advantageously, the fat content ranges from 0.01% to 45% by weight, preferably from 0.1% to 30% by weight, or from 1% to 15% by weight relative to the total weight of composition I). Adjuvants

[0188] The colouring composition I) according to the invention may also include one or more cosmetic adjuvants.

[0189] For example, composition I) may include one or more additives well known in the art, such as anionic, nonionic, amphoteric polymers or mixtures of These include hair loss prevention agents, vitamins and provitamins including panthenol, derivatives of these vitamins (notably esters) and their mixtures; sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifiers, opacifiers, hydroxy acids, pearlescent agents, perfumes and preservatives.

[0190] It goes without saying that a person skilled in the art will take care to select these additional (optional) compound(s) in such a way that the advantageous properties intrinsically associated with the invention are not, or are not substantially, negatively affected by the envisaged addition(s).

[0191] The aforementioned adjuvants can generally be present in an amount, for each of them, of between 0 and 20% by weight, or between 0 and 10% by weight, relative to the total weight of composition I).

[0192] Composition I) according to the invention may be in the form of fluid or thickened liquids, gels or creams, preferably cream. Developer composition II)

[0193] The dye composition a) in the combination according to the present invention may comprise a developer composition II).

[0194] According to one embodiment of the present invention, the developer composition II) is placed separately from the colorant composition I). Oxidizing

[0195] Composition II) of composition a) according to the present invention comprises at least one oxidant.

[0196] The developer composition II) of the present invention may comprise one or more oxidants for general use as one of the active components of composition II). The term "oxidant" means an oxidant other than atmospheric oxygen. More particularly, the oxidant is selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromates, peroxy salts such as persulfates or perborates, peracids and their precursors, and alkali or alkaline earth metals; or a polymer-type complex capable of releasing hydrogen peroxide.

[0197] Advantageously, the oxidant is hydrogen peroxide.

[0198] The concentration of the oxidant may be from 0.1% by weight to 50% by weight, or preferably from 0.5% by weight to 20% by weight, or from 1% by weight to 15% by weight, relative to the weight of composition II). Solvent

[0199] The developer composition II) of the present invention may comprise one or more solvents, for example water and / or an organic solvent. The useful solvent can be chosen from those discussed for the "solvent" of composition I) above.

[0200] Compositions I) and II) of the dye composition a) may independently use identical or different solvents, respectively.

[0201] When water is used as a solvent in developer composition II) according to the invention, it is more preferably in a range of 40% to 95% by weight, more preferably from 50% to 90% by weight, or from 60% to 85% by weight, relative to the total weight of composition II).

[0202] Examples of water-soluble organic solvents that may be cited include polyols containing more than two hydroxyl functions, such as glycerol.

[0203] Water-soluble organic solvents, when present, generally represent between 0.01% and 10% by weight relative to the total weight of the colour composition I) according to the invention, and preferably between 0.1% and 5% by weight, or between 0.5% and 1% by weight. Surfactant

[0204] The developer composition II) according to the invention may comprise one or more surfactants, for example, in particular, an anionic surfactant and / or a nonionic surfactant, preferably a nonionic surfactant. The useful surfactant may be chosen from those discussed for the "surfactant" of composition I) above. Chelating agent

[0205] The colouring composition I) and / or the developer composition II) of the dye composition a) according to the present invention may comprise at least one chelating agent.

[0206] According to the present invention, the useful chelating agent comprises aminocarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, and in particular the alkali metal salt thereof, for example, N,N-bis(carboxymethyl)glutamic acid, tetrasodium EDTA, tetrasodium salt of N,N-bis(carboxymethyl)glutamic acid (diacetic glutamic acid, GLDA); hydroxycarboxylic acids, for example, citric acid, tartaric acid, glucuronic acid, succinic acid, ethylenediaminedisuccinic acid (EDDS), and in particular the alkali metal salt thereof; hydroxylaminocarboxylic acids, for example, hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DEG), and in particular the alkali metal salt thereof; polyphosphonic acid, and in particular the alkali metal salt thereof;other organic acids containing phosphorus, for example, phytic acid, and in particular the alkali metal salt thereof, for example, sodium phytate, potassium phytate, polycarboxylic acid, for example, polyacrylic acid, poly-; methacrylic, and in particular the alkali metal salt thereof.

[0207] In one embodiment, the at least one water-soluble chelating agent is an alkali metal hydroxyl polycarboxylate represented by an alkane containing 1 to 4 carbon atoms, preferably containing 2 or 3 carbon atoms, substituted by 1, 2 or 3 hydroxyl groups (-OH), preferably by one (1) hydroxyl group, and further substituted by 2, 3, 4 or 5 carboxylate groups (-C00M), preferably by 2 or 3 carboxylate groups (-C00M), where the multiple M groups independently represent H or an alkali metal, provided that at least one of the M groups represents an alkali metal, such as Na, K or Li, preferably all the M groups represent an alkali metal, such as Na, K or Li, preferably Na.More specifically, at least one alkali metal hydroxyl polycarboxylate may be selected from sodium tartrates, sodium citrates, potassium tartrates, potassium citrates, and hydrates thereof, preferably sodium citrates, in particular trisodium citrate. In this document, sodium citrates are used to refer to monosodium citrate, disodium citrate, and trisodium citrate, and other alkali metal hydroxyl polycarboxylates may be understood similarly.

[0208] Among others, the alkali metal mentioned above is preferably sodium or potassium, particularly sodium. Accordingly, preferred chelating agents may include sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, or a mixture thereof.

[0209] In particular, composition I) and / or composition II) of the present invention may include at least one water-soluble chelating agent in a range of 0.01% to 1% by weight, in particular 0.1% to 0.4% by weight, relative to the total weight of the second composition.

[0210] Component B), pvrazolidine-3.5-dione compound of formula (1)

[0211] In addition to the dye composition a) comprising the colorant composition I) and the developer composition II), the dye combination according to the present invention may also comprise a pyrazolidine-3,5-dione compound of formula (1):

[0213] wherein Ri and R2 are each independently H, a hydroxyl, an unsubstituted or substituted Ci-C30 alkyl, an unsubstituted or substituted C2-C30 alkenyl, a cycloalkyl, an unsaturated heterocyclic group, a heterocyclic group, or an epoxyalkyl such as a Ci-CiO alkyl or a Ci-CiO alkyl substituted by a halogen, preferably a Ci-C6 alkyl or a halogen-substituted Ci-C6 alkyl, a C3-CiO alkenyl, a C3-CiO cycloalkyl, a C3-CiO unsaturated heterocyclic group, a C3-CiO heterocyclic alkyl or a C3-CiO alkoxy; and R3 is H, or a Ci-Cio alkyl, a C3-CiO cycloalkyl, a C3-CiO heterocyclic alkyl or a C3-CiO alkoxy unsubstituted or substituted with a halogen, such as a Ci-C6 alkyl or a C1-C4 alkyl, preferably H, the halogen preferably being F, Cl or Br.

[0214] According to a preferred embodiment of the present invention, Ri and R2 are each a lower alkyl group, such as a C1-C6 alkyl group, or a C1-C4 alkyl group. For example, Ri and R2 may be the same alkyl group, such as each being methyl, ethyl, propyl, or butyl. According to one embodiment, R3 may be H. Therefore, examples of pyrazolidine-3,5-dione compounds of formula (1) may include 1,2-dimethyl-pyrazolidine-3,5-dione, 1,2-diethyl-pyrazolidine-3,5-dione, 1,2-dipropyl-pyrazolidine-3,5-dione, and 1,2-dibutyl-pyrazolidine-3,5-dione.

[0215] The pyrazolidine-3,5-dione compounds of formula (1) according to the invention are generally present in amounts ranging from 0.001% to 25% by weight, or from 0.0001% to 10% by weight, preferably from 0.005% to 5% by weight, in particular from 0.01% to 3% by weight, relative to the total weight of the combination.

[0216] Addition form of the compound pyrazolidine-3.5-dione of formula fl)

[0217] As stated above, the inventor has discovered surprisingly that the compound pyrazolidine-3,5-dione of formula (1) can be used as a retarder to slow down the reactions of the tint or intermediates thereof, for example, the oxidizing tint i) useful in composition I).

[0218] That is to say, the pyrazolidine-3,5-dione compound of formula (1) acts mainly on the dye reaction. Therefore, for the dye combination, the pyrazolidine-3,5-dione compound of formula (1) can be added directly to the dye composition a), for example, as a mixture with the dye composition I); or can be added in a separate chamber, for example, as a pyrazolidine-3,5-dione composition comprising the pyrazolidine-3,5-dione compound of formula (1), separate from the dye composition a).

[0219] For use as a pyrazolidine-3,5-dione composition independently of the tincture composition a), the pyrazolidine-3,5-dione composition may include any component known in the cosmetic field benefiting from the stability of the pyrazolidine-3,5-dione compound of formula (1).

[0220] Consequently, the present invention can advantageously provide a dye combination, comprising:

[0221] a dye composition a) according to the present invention placed in enclosure 1; And

[0222] a pyrazolidine-3,5-dione composition comprising the pyrazolidine-3,5-dione compound of formula (1) according to the present invention placed in chamber 2 separated from chamber 1.

[0223] As stated above, the AMPS polymer can be used to slow down the reactions of the tint or intermediates thereof, for example the oxidizing tint i) useful in composition I). Without being limited by any known theory, it is thought that the use of the compound pyrazolidine-3,5-dione of formula (1) in combination with the AMPS polymer above may provide a synergistic effect as a retarder. Method and use

[0224] A subject of the invention is a process for dyeing human keratinous fibers, in particular hair, using the dye combination as described above.

[0225] Another subject of the invention is a process for reducing the colouring of a tint composition, using the tint combination as described above.

[0226] Another object of the invention is a process for slowing down the reactions of the tint or intermediates, using the tint combination as described above.

[0227] The invention also relates to the use of the shade combination as described above for dyeing keratinous fibers, in particular hair.

[0228] The invention also relates to the use of the tint combination as described above to reduce the coloring of the tint combination.

[0229] The invention also relates to the use of a tint combination as described above to slow down the reactions of the tint or intermediates, using the tint combination as described above.

[0230] In particular, the invention relates to a process for slowing down the reactions of the dye or intermediates thereof, characterized by mixing a py-razolidine-3,5-dione compound of formula (1) comprising phenyl methyl pyrazolone with the dye.

[0231] Preferably, the pyrazolidine-3,5-dione compound of formula (1) is mixed with the tint before the tint is applied, or the pyrazolidine-3,5-dione compound of formula (1) is applied to the area where the tint was applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes.

[0232] The present invention also relates to the use of a pyrazolidine-3,5-dione compound of formula (1) comprising phenylmethylpyrazolone to reduce the colouring of a shade.

[0233] According to another aspect, the present invention relates to the use of a composition for dyeing keratinous fibers, while reducing staining in areas other than keratinous fibers, wherein the composition comprises a pyra-zolidine-3,5-dione compound of formula (1) comprising phenyl methyl pyrazolone.

[0234] According to a preferred embodiment, the dyeing process of the invention comprises mixing the dye composition I) and composition II) immediately before use, and applying the resulting mixture as described above to the keratinous fibers.

[0235] More particularly, by "mixture" or a variant thereof, we mean the action of putting the colour composition I) of the present invention into a container or a palm, together with the developer composition II) as described above, with or without agitation of the latter.

[0236] According to a preferred variant of the preferred embodiment, the coloring composition I) of the present invention is placed in a container or palm jointly with the developer composition II) as described above, without shaking them.

[0237] Regardless of the process used and the number of compositions used, the composition(s) described above, optionally mixed beforehand, is / are applied to wet or dry keratinous fibers.

[0238] As indicated above in the section "Form of addition of the pyrazolidine-3,5-dione compound of formula (1)", the pyrazolidine-3,5-dione compound of formula (1) can be supplied in various forms for use with the colorant composition (I) and the developer composition (II), so as to slow down the tint reaction. In particular, if a pyrazolidine-3,5-dione compound of formula (1) is placed in chamber 2, separate from chamber 1, for the tint combination described according to the present invention:

[0239] - if the user does not want to slow down the dyeing process, or if the stain caused by the dye is irrelevant no, room 2 may not be used;

[0240] - if the user wishes to avoid any staining, he can mix chamber 2 with the room 1 before dyeing;

[0241] - if the user wishes to determine whether or not to use chamber 2 depending on Upon the appearance of an actual stain, one can initially use only chamber 1, and when the dye composition adheres to the hand or any other area, chamber 2 can be applied immediately; and

[0242] - If the user wants to avoid stains and desires a quick dyeing, he can apply pre-treat room 2 on areas where stains are most likely to occur but should be avoided, for example the hand.

[0243] Alternatively, if a pyrazolidine-3,5-dione compound of formula (1) is supplied jointly with the dye composition I), for example, by being added directly into composition I), the dyeing process is still slowed down, compared with the same dyeing process except in the absence of any pyrazolidine-3,5-dione compound of formula (1).

[0244] The mixed compositions, including the colouring composition I) and the composition of developer II), and optionally the compound pyrazolidine-3,5-dione of formula (1), are generally left in place on the fibers for a period generally ranging from 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.

[0245] The temperature during the process is classically between 20 and 80°C and preferably between 20 and 60°C. After treatment, the human keratin fibers are advantageously rinsed with water. They may optionally be washed again with shampoo, followed by rinsing with water, before being dried or left to dry.

[0246] The process can be repeated several times to obtain the desired colouring.

[0247] The aforementioned combination of shades can also be equipped with means for delivering the desired mixture to the hair, such as the device described in patent FR 2 586 913.

[0248] The following examples are given purely for illustrative purposes of the present invention. EXAMPLES

[0249] The quantities / concentrations of the ingredients in the compositions / formulas described below are expressed as % by weight, relative to the total weight of each composition / formula. Example 1

[0250] The following colour compositions LA and LB were prepared from the ingredients indicated in Table 1 below (in which the contents are indicated as % by weight of matter relative to the total weight of the composition):

[0251] [Tables 1] Ingredients: LA LB LAURIC ACID 3 3 LAURETH-12 7 7 CETEARYL ALCOHOL 11.5 11.5 DISTEARATE GLYCOL 2 2 DECETH-3 10 10 ETHANOLAMINE 1.35 1.35 PROPYLENE GLYCOL 7 7 EDTA 0.2 0.2 ASCORBIC ACID 0.25 0.25 SODIUM METABISULFITE 0.71 0.71 AMMONIUM HYDROXIDE 12 12 1-METHYL-2-HYDROXY-4-AMINOBENZENE 1.44 1.44 PYRAZOLIN-3,5-DIONE 2.5 WATER QS QS

[0252] The following ILA developer composition was prepared from the ingredients indicated in Table 2 below (in which the contents are indicated as % by weight of materials relative to the total weight of the composition):

[0253] [Tables2] Ingredients: Cetearyl Alcohol (and) Ceteareth-25 2.85, Trideceth-2 Carboxamide MEA 0.85, Glycerin 0.5, Pentasodium Pentatate 0.15, Hydrogen Peroxide 12, Water q.s. Example 2

[0254] For the application, compositions LA and B were mixed respectively with composition II-A with a weight ratio of 1:1.5, to give mixtures A and B.

[0255] The viscosity of the mixtures was then measured according to standard CID-012-02 H. The results are shown in Table 3 below:

[0256] [Tables3] Properties Mixture A Mixture B Viscosity (M4) 20.5 28.5 Example 3

[0257] The following LC to E colour compositions were prepared in a similar manner to Example 1, from the ingredients indicated in Table 4 below (in which the contents are indicated as % by weight of materials relative to the total weight of the composition):

[0258] [Tables4] Ingredients LC LD LAURIC ACID 3 3 3 LAURETH-12 7 7 7 CETEARYL ALCOHOL 11.5 11.5 11.5 GLYCOL DISTEARATE 2 2 2 DECETH-3 10 10 10 ETHANOLAMINE 1.35 1.35 1.35 PROPYLENE GLYCOL 7 7 7 EDTA 0.2 0.2 0.2 ASCORBIC ACID 0.25 0.25 0.25 SODIUM METABISULFITE 0.71 0.71 0.71 AMMONIUM HYDROXIDE 12 12 12 p-PHENYLENEDIAMINE 0.338 - - L-METHYL-2-HYDROXY-4-AMINOBENZENE - 0.384 - L-Hydroxyethyl 4,5-Diaminopyrazole Sulfate - - 0.751 PYRAZOLIN-3,5-DIONE 0.488 0.488 0.488 WATER QS QS QS Example 4

[0259] Compositions LC to E were mixed respectively with composition ILA in a weight ratio of 1:1.5, to give mixtures C to E.

[0260] After 30 minutes, the mixtures were photographed. As shown in [Fig. 1], it was explicitly observed visually that, due to the different tint used in combination with component B, mixture D produced a much lighter color than the other two. In particular, for mixture E, qualified personnel could see that the oxidation reaction was practically unaffected.

[0261] [Table 5] Cleanliness Level Performance Performance Mixture C Mixture D Mixture E Retardant Effect Good Excellent Poor

Claims

Demands

1. A combination of dyes for the oxidative dyeing of keratinous fibers, comprising: A) a dye composition a), comprising: I) a coloring composition I), comprising: i) at least one oxidizing tint; in which the oxidizing tint comprises one or more oxidation bases selected from the group consisting of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, and addition salts thereof, and mixtures thereof; and / or wherein the oxidizing tint comprises one or more couplers selected from the group consisting of meta-phenylenediamines, meta-aminophenols, and their addition salts, and mixtures thereof; and B) a pyrazolidine-3,5-dione compound of formula (1): .9 (1) J ü in which Ri and R2 are each independently H, a hydroxyl, an unsubstituted or substituted Ci-C30 alkyl, an unsubstituted or substituted C2-C30 alkenyl, a cycloalkyl, an unsaturated heterocyclic group, a heterocyclic group or an epoxyalkyl such as a Ci-Cio alkyl or a halogen-substituted Ci-Cio alkyl, preferably a Ci-C6 alkyl or a halogen-substituted Ci-C6 alkyl, a C3-Ci0 alkenyl, a C3-Ci0 cycloalkyl, an unsaturated C3-Ci0 heterocyclic group, a C3-Ci0 heterocyclic alkyl or a C3-Ci0 alkoxy; and R3 is H, or a Ci-Cio alkyl, a C3-Cio cycloalkyl, a C3-CiO heterocyclic alkyl, or a C3-CiO alkoxy, unsubstituted or substituted with a halogen, such as a Ci-C6 alkyl or a Ci-C4 alkyl, preferably H, the halogen preferably being F, Cl, or Br, in which the compound pyrazolidine-3,5-dione of formula (1) is placed in a separate chamber from the dye composition a).

2. Shade combination according to claim 1, wherein Ri and R2 are each a Ci-C6 alkyl or a Ci-C4 alkyl; and / or R3 is H.

3. A color combination according to any one of the preceding claims, wherein the pyrazolidine-3,5-dione compound of formula (1) is selected from the group consisting of 1,2-dimethyl-pyrazolidine-3,5-dione, 1,2-diethyl-pyrazolidine-3,5-dione, 1,2-dipropyl-pyrazolidine-3,5-dione and 1,2-dibutyl-pyrazolidine-3,5-dione.

4. A tint combination according to any one of the preceding claims, wherein the oxidizing tint does not comprise any pyrazole derivative.

5. A tint combination according to any one of the preceding claims, wherein the oxidizing tint is selected from the group consisting of aminophenols, preferably meta-aminophenols.

6. A color combination according to any one of the preceding claims, wherein the color composition I) comprises a reducing agent for use as an antioxidant, which is selected from the group consisting of thioglycolic acid, dithioglycolic acid, thiolactic acid, thiomalic acid, salts thereof and a mixture thereof; and / or wherein the color composition I) comprises another antioxidant selected from a natural exogenous phytochemical antioxidant, a flavonoid, a vitamin such as vitamin C and / or E and a derivative thereof, tocopherols, a tocotrienol, a phenol, a carotenoid, an anthocyanin, a dihydrochalcone, a phenylpropanoid, a chalcone, a curcuminoid, a tannin, a stilbenoid, a coumarin, a carotenoid, or a mixture thereof.

7. Use of a color combination according to any one of claims 1 to 6, to reduce the coloration of said color combination or slow down the reactions of the color or intermediates.

8. Use according to claim 7, wherein the pyrazolidine-3,5-dione compound of formula (1) is mixed with the tint before the tint is applied, or the pyrazolidine-3,5-dione compound of formula (1) is applied to the area where the tint was applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes.

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