CN117597104A - Combinations for dyeing keratin fibers and their uses - Google Patents

Abstract

The present invention relates to a dye combination comprising: a) Dyeing composition a), comprising: i) Colorant composition I), comprising: i) At least one oxidation dye; wherein the oxidative dye comprises one or more oxidative chromophores selected from the group consisting of para-phenylenediamines, bis (phenyl) alkylene diamines, para-aminophenols, meta-aminophenols, ortho-aminophenols, and addition salts thereof, and mixtures thereof; and/or wherein the oxidative dye comprises one or more coupling agents selected from the group consisting of meta-phenylenediamines, meta-aminophenols, and addition salts thereof, and mixtures thereof; and B) pyrazolidine-3, 5-dione compounds of formula (1).

Description

Combinations for dyeing keratin fibers and their uses

Technical field

The present invention relates to combinations for dyeing keratin fibers, in particular human keratin fibers such as hair.

Background of the invention

Many people have long tried to change the color of their hair, and especially to dye it, in order to cover up their gray hair, for example.

"Permanent" dyeing methods, also known as oxidative dyeing, use colorant compositions containing oxidation dye precursors, often called oxidative color bases, such as o- or p-phenylenediamines, o-aminophenols, or p-phenylenediamines. Aminophenols and heterocyclic compounds, have been developed to dye human keratin fibers in a durable manner. These oxidative chromophores are colorless or light-colored compounds that, when combined with oxidation products, can produce colored compounds through an oxidative condensation process.

Dyeing products may contain both at least one oxidation dye and at least one oxidizing agent. For better use, oxidation dyes and oxidants can be placed separately in multi-compartment packages and mixed together just before use.

Consumers want dyes to dye only targeted areas. However, in many cases, such as when hair is dyed, other areas can be undesirably stained (stained), such as the hands, face, ears, etc. Consumers have to be more careful to avoid unwanted areas and are always looking for products to help them remedy unwanted staining.

Summary of the invention

The inventors have now discovered that the use of specific retardants together with oxidation dyes can lead to a method for keratin that overcomes the disadvantages mentioned above and in particular reduces or even substantially avoids undesired staining of non-target sites by the dye. Compositions for oxidative dyeing of fibers.

Therefore, a subject of the present invention is a dye combination for oxidative dyeing of keratin fibers, comprising:

A) Dyeing composition a), containing:

I) Colorant composition I), comprising:

i) at least one oxidation dye;

The oxidation dyes include one or more selected from p-phenylenediamines, bis(phenyl)alkylenediamines, p-aminophenols, o-aminophenols and their addition salts, and mixtures thereof The oxidation color base;

and / or

wherein the oxidation dye comprises one or more coupling agents selected from m-phenylenediamines, m-aminophenols and their addition salts, and mixtures thereof; and

B) Pyrazolidine-3,5-dione compound of formula (1):

Wherein R ₁ and R ₂ are each independently H, hydroxyl, unsubstituted or substituted C1-C30 alkyl, unsubstituted or substituted C2-C30 alkenyl, cycloalkyl, unsaturated heterocyclic group, hetero Cyclic groups or epoxyalkyl groups such as C1-C10 alkyl or halogen-substituted C1-C10 alkyl, preferably C1-C6 alkyl or halogen-substituted C1-C6 alkyl, C3-C10 alkenyl, C3-C10 Cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocycloalkyl, or C3-C10 alkoxy; and R ₃ is H, or unsubstituted or halogen-substituted C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br.

Optionally, the pyrazolidine c3,5-dione compound of formula (1) is placed together with the dyeing composition a) or in a separate chamber from the dyeing composition a).

According to one embodiment of the invention, the dyeing composition a) may further comprise:

II) Developer composition II), which contains:

ii) at least one developer.

Optionally, a pyrazolidine-3,5-dione compound of formula (1) is placed in composition I).

The present invention thus provides the use of pyrazolidine-3,5-dione compounds of formula (1) as retarders for slowing down the reaction of dyes or intermediates thereof.

The present invention also provides the use of the pyrazolidine-3,5-dione compound of formula (1) for reducing dye staining.

The present invention also provides the use of a composition for reducing dye staining, wherein the composition comprises a pyrazolidine-3,5-dione compound of formula (1).

The invention also relates to a method for dyeing keratin fibers, in particular human keratin fibers such as hair, using the dyeing composition a) according to the invention.

The invention also relates to a method of reducing staining of dyed keratin fibers such as hair using a dyeing composition according to the invention a).

The present invention also relates to a method for slowing down the reaction of dyes or intermediates thereof, characterized in that a pyrazolidine-3,5-dione compound of formula (1) is mixed with a dye. Preferably, the pyrazolidine-3,5-dione compound of formula (1) is mixed with the dye before applying the dye, or the pyrazolidine-3,5-dione compound of formula (1) is applied to Where the dye has been applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes.

Figure overview

Figure 1 shows the blocking properties of the mixture according to Example 4.

Embodiments of the invention

Throughout the specification (including the claims), unless otherwise mentioned, the term "comprising one" shall be understood to be synonymous with "comprising at least one". Furthermore, the term "at least one" used in this specification is equivalent to the term "one or more".

Embodiments defined by "comprising" and the like throughout the specification (including the claims) should be understood to cover preferred embodiments defined by "consisting essentially of" and preferred embodiments defined by "consisting of."

Throughout the specification, including the claims, "keratin fibers" according to the invention are hair, eyelashes, eyebrows or body hair. Preferably, the keratin fibers according to the invention are hair.

In this application, contents, parts and percentages are expressed on a weight basis unless expressly mentioned otherwise.

Throughout the specification (including the claims), the term "retarder" refers to an agent capable of slowing down the reaction of a dye or its intermediates, such as with a developer, for example between them oxidation reaction.

According to the present invention, "reducing staining" means reducing staining in undesirable areas (eg hands, face, scalp, ears, rinse water, towels, floors, etc.). Preferably, the effect lasts for at least 5 minutes, more particularly 10 minutes, or preferably 15 minutes, or 20 minutes after dyeing the hair.

A subject of the present invention is to provide a dye combination for oxidative dyeing of keratin fibers, comprising:

A) Dyeing composition a), containing:

I) Colorant composition I), comprising the following components:

i) at least one oxidation dye; and

II) Developer composition II), comprising the following components:

ii) at least one oxidizing agent;

Know

B) Pyrazolidine-3,5-dione compound of formula (1):

Wherein R ₁ and R ₂ are each independently H, hydroxyl, unsubstituted or substituted C1-C30 alkyl, unsubstituted or substituted C2-C30 alkenyl, cycloalkyl, unsaturated heterocyclic group, hetero Cyclic group or epoxyalkyl group, such as C1-C10 alkyl or halogen-substituted C1-C10 alkyl, preferably C1-C6 alkyl or halogen-substituted C1-C6 alkyl, C3-C10 alkenyl, C3-C10 Cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, and _R3 is H or unsubstituted or halogen-substituted C1-C10 alkyl, C3 -C10 cycloalkyl, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br.

The dye combinations of the invention are intended for use in methods of dyeing keratin fibers.

The subject of the invention is thus a method for dyeing keratin fibers, which consists in mixing the colorant composition I) of the dyeing composition a) with the composition II) immediately before use to obtain a dye mixture, optionally into the dye mixture The pyrazolidine-3,5-dione compound of formula (1) is added and the dye combination of the invention is applied to the keratin fibers.

In a variant embodiment according to the invention, the pyrazolidine-3,5-dione compound of formula (1) can be added directly to the colorant composition I).

Other features and advantages of the invention will appear more clearly on reading the following description and examples.

Except in the operating examples, or where otherwise stated, all numbers expressing amounts of components and/or reaction conditions are to be understood as being modified in all cases by the term "about", which has the meaning conventionally known in the art. Meaning, for example, within 10% of the number shown (e.g. "about 10%" means 9%-11%, "about 2%" means 1.8%-2.2%).

Dyeing composition a)

Coloring composition a) in the combination according to the invention may comprise a coloring agent composition I) and a developer composition II).

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

Colorant composition I)

Coloring composition a) in the combination according to the invention comprises colorant composition I).

Colorant composition I) of composition a) according to the invention may comprise at least one oxidation dye.

Oxidation dyes

As shown above, the colorant composition I) according to the invention comprises one or more oxidation dyes as component i).

Oxidation dyes useful in the present invention are generally selected from oxidative chromophores, preferably in combination with one or more coupling agents.

The one or more oxidation dyes preferably contain one or more oxidation chromophores.

The oxidative chromophore may be selected from p-phenylenediamines, bis(phenyl)alkylenediamines, p-aminophenols, o-aminophenols, heterocyclic chromophores (heterocyclic bases), and their addition salts, and The mixture; preferably selected from p-phenylenediamines, bis(phenyl)alkylenediamines, p-aminophenols, o-aminophenols and mixtures thereof; more preferably from p-aminophenols, o-aminophenols and its mixture.

Among the p-phenylenediamines, unsubstituted p-phenylenediamine or p-phenylenediamine substituted by 1 or 2 C ₁ -C ₄ alkyl groups is preferred. Of these, examples that may be mentioned include p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-methyl-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-diamine Methyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine. Other p-phenylenediamines may also be used, such as 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(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(β-hydroxyethyl) Amino-2-methylaniline, 4-N, N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine , 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl -p-Phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4′- Aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-β-hydroxyethoxy-p-phenylenediamine, 2-β-acetylaminoethoxy-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene, and 3 -Hydroxy-1-(4′-aminophenyl)pyrrolidine and its addition salts with acids.

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

Among the p-aminophenols, unsubstituted p-aminophenol or p-aminophenol substituted by 1 or 2 C ₁ -C ₄ alkyl groups is preferred. Among these, examples that may be mentioned include p-aminophenol, 4-amino-3-cresol and 4-amino-2-cresol. Other p-phenylenediamines that can also be used include 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxycresol, 4-amino-2-hydroxycresol, 4 -Amino-2-methoxycresol, 4-amino-2-aminocresol, 4-amino-2-(β-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol and their Addition salt with acid.

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

Among heterocyclic chromophores, examples that may be mentioned include pyridine derivatives and pyrimidine derivatives. According to one embodiment of the invention, it is further preferred not to use pyrazole derivatives as oxidation dyes.

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

Pyrimidine derivatives that may be mentioned are in particular the compounds described in patent 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- Triaminopyrimidines and their addition salts and their tautomeric forms (when tautomeric equilibrium exists).

The one or more oxidation dyes may also comprise one or more coupling agents, which may be selected from those conventionally used for dyeing keratin fibers.

Among these coupling agents, mention may be made in particular of m-phenylenediamines, m-aminophenols, resorcinols, naphthalene-based coupling agents, heterocyclic coupling agents and their addition salts, and mixtures thereof. In particular, it is preferable to use unsubstituted m-aminophenol or m-aminophenol substituted by 1 or 2 C ₁ -C ₄ alkyl groups, unsubstituted resorcinol or m-aminophenol substituted by 1 or 2 C ₁ -C ₄ alkyl groups. substituted resorcinol, diaminophenols, or unsubstituted hydroxyindole, amino-substituted hydroxypyridine, or hydroxybenzomorpholine.

Examples that may be mentioned include 1-hydroxy-3-aminobenzene, 1-methyl-2-hydroxy-4-aminobenzene, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 5-amino-6-chloro-o-cresol, 2-methyl-5-hydroxyethylaminophenol, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyl oxy)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, α-naphthol, 2-Methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxy Ethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, its addition salts with acids and their mixtures, such as their chlorhydrate or dichlorhydrate , such as 1-β-hydroxyethoxy-2,4-diamino-benzene dihydrochloride (2,4-diaminophenoxyethanol HCL).

In general, the addition salts of oxidative chromophores and coupling agents that can be used in the context of the present invention are especially selected from the group consisting of addition salts with acids, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, Tartrate, lactate, tosylate, benzenesulfonate, phosphate and acetate.

In a first exemplary embodiment of the oxidative chromophore, examples include unsubstituted p-phenylenediamine or p-phenylenediamine substituted by 1 or 2 C ₁ -C ₄ alkyl groups.

In a second exemplary embodiment of the oxidative chromophore, examples include unsubstituted p-aminophenol or p-aminophenol substituted by 1 or 2 C ₁ -C ₄ alkyl groups, in particular unsubstituted p-aminophenol.

For oxidative chromophores, particular mention is made of unsubstituted p-aminophenols or p-aminophenols substituted by 1 or 2 C ₁ -C ₄ alkyl groups.

In particular, for the coupling agent, unsubstituted m-aminophenol or m-aminophenol substituted by 1 or 2 C 1 -C ₄ alkyl groups, unsubstituted resorcinol or m-aminophenol substituted by 1 or 2 C ₁ -C 4 alkyl groups can be preferably used. C ₁ -C ₄ alkyl substituted resorcinol, diaminophenols or unsubstituted hydroxyindole, amino substituted hydroxypyridine, or hydroxybenzomorpholine.

When unsubstituted hydroxyindole, amino-substituted hydroxypyridine or hydroxybenzomorpholine is used as a coupling agent, it is preferably used in combination with the oxidative chromophore according to the second exemplary embodiment.

When the oxidized chromophore according to the third exemplary embodiment of the oxidized chromophore is used, it is preferably used in combination with an amino-substituted hydroxypyridine as a coupling agent.

Furthermore, 2-amino-3-hydroxypyridine as a coupling agent in combination with the oxidized chromophore according to the second exemplary embodiment, or 5-amino-6-chloro-o-methyl as a coupling agent can be mentioned individually Combination of phenol and oxidative chromophore according to the second exemplary embodiment.

Without being bound by any known theory, it is believed that aminophenol is preferably used when used in combination with component B). More particularly, preference is given to the use of meta-aminophenol, which when used in combination with component B) according to the invention produces particularly desirable non-staining results.

The one or more oxidative chromophores 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) %.

If present, the coupling agent(s) may advantageously comprise from 0.0001% to 20% by weight, relative to the total weight of composition I), and preferably from 0.001% to 10% by weight, or from 0.01% to 5% by weight weight%.

Antioxidants

Colorant composition I) may optionally contain antioxidants.

Antioxidants used may include natural exogenous phytochemical antioxidants such as phenols and carotenoids.

Antioxidants can include flavonoids. Flavonoids constitute a large class of more than 5,000 polyphenolic phytochemicals with antioxidant properties that act by direct free radical scavenging. Flavonoids have anti-inflammatory, antibacterial, antiviral, antiallergic, antimutagenic, antithrombotic, antitumor, and vasodilatory effects, and these modes of action may also be used to prevent, reduce, or eliminate oxidative damage from dental instruments. Flavonoids also exhibit chelating properties with metal ions and can alleviate oxidative damage from metal ions by chelating the ions. The formation and stability of flavonoid-metal chelates depend on the functionality of the structure. Flavonoids with a catechol moiety and hydrogen bonds between the hydroxyl groups at the 5- and 3-positions have chelating properties.

Vitamin C and derivatives may be used, including ascorbic acid, erythorbic acid or derivatives thereof, such as sodium ascorbate/sodium erythorbate and the fat-soluble esters tetrahexyldecanol ascorbate/tetrahexyldecanol isoascorbyl and ascorbyl palmitate, ascorbic acid Magnesium phosphate, ascorbyl glucoside, glucosamine ascorbyl ester/salt, ascorbyl acetate, etc. In addition, it is possible to use plants containing high amounts of vitamin C, such as extracts of Camu camu camu (Myrciaria dubia), acerola, emblica officinalis, and bioflavonoids from rose hips and citrus, including Water-soluble bioflavonoids such as hesperidin methylchalcone.

Sesamum indicum or lignan can also be added. Sesame and its lignans (fibrous compounds related to sesame) act as antioxidants. Sesame seed lignans significantly enhance vitamin E activity.

Other antioxidants that may be incorporated into the compositions of the present invention include tocopherols (eg, d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol, d-delta-tocopherol), tocotrienes Phenols (such as d-alpha-tocotrienol, d-beta-tocotrienol, d-gamma-tocotrienol, d-delta-tocotrienol) and vitamin E (alpha-tocopherol acetate ). These compounds can be isolated from natural sources, prepared by synthetic means or mixed. Tocotrienol-rich vitamin E products can be obtained by fractionating the vitamin E product to remove a portion of the biophenols and recover a more concentrated tocotrienol product. Useful tocotrienols are natural products isolated, for example, from wheat germ oil, cereals or palm oil using high performance liquid chromatography or from barley, distiller's meal or oats by alcohol extraction and/or molecular distillation. The term "tocotrienols" as used herein includes tocotrienol-rich fractions obtained from these natural products as well as pure compounds. Increased glutathione peroxidase activity protects skin from oxidative damage.

In addition, carotenoids, especially the lutein type, are also useful antioxidants that can be used. Lutein-type carotenoids include molecules such as lutein, canthaxantin, cryptoxanthin, zeaxanthin and astaxanthin. Lutein compounds protect compounds such as vitamin A, vitamin E and other carotenoids.

The flavonoid may be a flavanone (a derivative of 2,3-dihydro-2-phenylbenzopyran-4-one). Flavanones include: hesperetin, erioridin, hesperetin, hesperidin, sylvestre, isozakuratin, naringenin, naringin, pinocin, tangrin (citrin), sakuranetin, sakura Glycoside (sakura glycoside) and 7-O-methylergophenol (Sterubin).

The flavonoid may be dihydroflavonol (a derivative of 3-hydroxy-2,3-dihydro-2-phenylchroman-4-one). Flavanols (Flavanols) include: dagocyanidin, Aromadedrin, Chrysandroside A, Chrysandroside B, Xeractinol, astilbin and flavonols.

The flavonoid may be a flavonoid (derivative of 2-phenylbenzopyran-4-one). Flavonoids include: apigenin, luteolin, tangeretin, chrysin, baicalein, baicalein, wogonin, synthetic flavonoids: diosmin and flavonoid esters .

The flavonoid may be a flavonol (a derivative of 3-hydroxy-2-phenylbenzopyran-4-one). Flavonols include: 3-hydroxyflavone, rhodoflavin, quercetin, galangin, cotton dermatan, kaempferol, kaempferol, isorhamnetin, mulberry red pigment, myricetin , Naringin (Natsudaidain), Muskyl flavonol (Pachypodol), quercetin, methyl rhamnosin (methyl rhamnosin), rhamnetin, rhododendron ( azalein), hyperoside, isoquercetin, kaempferol, myricetin, suedeGlycosides, Robinin, rutin, Spiraea, Xanthorhamnin, Phellodendron Glycosides (Amurensin), icariin and Tracuridine.

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, epiafcatechin, fisetin Fisetinidol, Guibourtinidol, Mesquitol and Robinetinidol.

The flavonoid may be flavan-4-ol (a derivative of 2-phenylchromogen-4-ol). Flavan-4-ols include: Apiforol and Luteoforol.

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

The antioxidant may be anthocyanins (derivatives of the 2-phenylbenzopyranoside cation). Anthocyanins include: Aurantinidin, cyanidin, delphinidin, Europinidin, Luteolinidin, Pelargonidin, and Malvidin , Peonyidin (Peonidin), morning glory pigment (Petunidin), rose pigment (rose red primrose, Rosinidin) and xanthones.

The antioxidant may be dihydrochalcone (a derivative of 1,3-diphenyl-1-propanone). Dihydrochalcones include: phloretin, dihydrochalcone phloridin (phloridin), cisplatin, aspalathin, naringin dihydrochalcone, neohesperidin dihydrochalcone and Nothofagin. Without limiting the mode of action of the present invention, dihydrochalcone can exert an antioxidant effect by reducing reactive free radicals, such as reactive oxygen species and reactive nitrogen species.

Antioxidants can be anthocyanins. Anthocyanins and their derivatives are antioxidants. Anthocyanins comprise a class of flavonoid compounds that are responsible for the red, purple and blue colors of many fruits, vegetables, grains and flowers, and are naturally occurring water-soluble compounds. In addition, anthocyanins are collagenase inhibitors. Inhibition of collagenase helps prevent and reduce wrinkles caused by reduction of skin collagen, improve skin elasticity, etc. Anthocyanins can be obtained from any part of various plant sources such as fruits, flowers, stems, leaves, roots, bark or seeds. Those skilled in the art will recognize that certain parts of plants may contain higher natural levels of anthocyanins and therefore use these parts to obtain the desired anthocyanins. In some cases, the antioxidant may include one or more betaines. Betatin, similar to anthocyanins, is available from natural sources and is an antioxidant.

Antioxidants can be phenylpropanoids (derivatives of cinnamic acid). Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including its antioxidant pharmacore 2,6-dihydroxyacetophenone, acetophenome), 5-hydroxyferulic acid (5-hydroxyferic acid), sinapic acid, coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, piperonol (Chavicol), baicalein, P-coumaric acid and sinapinic acid. Without limiting the mode of action of the present invention, phenylpropanoids can neutralize free radicals.

The antioxidant may be a chalcone (a derivative of 1,3-diphenyl-2-propen-1-one). Chalcones include: zirconium oxide, Okanin, safflower, Marein, Sophoradin, Xanthohumol, Flavokvain A, Flavokavain B, Flavokavin C and synthetic Safalcone.

Antioxidants can be curcuminoids. Curcuminoids include: curcumin, demethoxycurcumin, bisdemethoxycurcumin, tetrahydrocurcumin, and tetrahydrocurcumin. Curcumin and tetrahydrocurcumin can be derived from the rhizome of turmeric. Tetrahydrocurcumin (a metabolite of curcumin) has been found to be a more potent antioxidant than curcumin and is more stable.

Antioxidants can be tannins. Tannins include: tannins, Terflavin B, gallic acid glucose (Glucogallin), gallic acid (Dgallic acid) and white quercitannic acid (Quercitannic acid).

The antioxidant may be a stilbenoid. Subcategories include: resveratrol, rosewood, 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 Hydroxyindole (oxidized resveratrol), 4,4'-dihydroxyindole and its alpha and beta glucoside, galactoside and mannoside derivatives.

The antioxidant may be coumarin (a derivative of 2H-benzopyran-2-one). Coumarins include: 4-hydroxycoumarin, umbelliferone, acetate, hynialin, auraptene and dicoumarin.

Antioxidants can be carotenoids. Carotenoids include: β-carotene, α-carotene, γ-carotene, β-cryptoxanthin, lycopene, lutein and idebenone.

Antioxidants can be vitamins or derivatives thereof. Vitamins include: retinol, ascorbic acid or erythorbic acid, L-ascorbic acid, tocopherols, tocotrienols and the vitamin cofactor: Coenzyme Q10.

Antioxidants can 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, chicoric acid, chlorogenic acid, rosmarinic acid, salicylic acid, acetylcysteine, S-allylcysteine, pyridone (Barbigerone), myrobalan tannic acid (Chebulagic acid), Edaravone, Ethoxyquin, Glutathione, Hydroxytyrosol, Idebenone, Melatonin, N-Acetyl Serotonin, Nordihydroguaiaretic Acid, Oleotanthal, Olive Picroside, Paradol, taxol, probucol, propyl gallate, protocatechuic acid, pyrithione, rutin, flax lignan diglucoside, sesamin, Sesamol, silybin, silymarin, theaflavins, theaflavin digallate, Thmoquinone, water-soluble vitamins (Trolox), tyrosol, polyunsaturated fatty acids and sulfur-based Antioxidants such as methionine or lipoic acid.

reducing agent

The colorant composition I) may contain reducing agents serving as antioxidants.

According to the present invention, useful reducing agents may include sodium thiosulfate, sodium metabisulfite, ammonium thioureasulfite, thioglycolic acid (TGA), thiolactic acid, ammonium thiolactate, diglycidyl monothiocarbamate (mono- carbothioic aciddiglycidyl ester), carbothioic ammonium acetate, thioglycerol, dimercaptoacetic acid, diammonium carbothioic strontium acetate, thio glycolate, thio Carbothioic isooctyl, cysteine, cysteamine, homocysteine, glutathione, 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, glyceryl monothioglycolate esters or mixtures thereof.

Examples of preferred reducing agents that may be mentioned include thioglycolic acid, dimioglycolic acid, thiolactic acid, thiomalic acid, salts thereof, or mixtures thereof.

The abovementioned antioxidants, including reducing agents, are preferably used according to the invention in an amount which may be 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 colorant composition I) .

Surfactant

The colorant composition I) according to the invention may comprise one or more surfactants, such as in particular anionic surfactants and/or nonionic surfactants.

anionic surfactant

The colorant composition I) according to the invention may further comprise one or more anionic surfactants.

The term "anionic surfactant" refers to a surfactant that contains only anionic groups as ionic or ionizable groups. These anionic groups are preferably selected from the following groups:

-COOH, -COO ^- , -SO ₃ H , -SO ₃ ^- , -OSO ₃ H , -OSO ₃ ^- , -PO ₂ H ₂ , -PO ₂ H ^- , -PO ₂ ^2- , -P(OH) _2. =P(O)OH, -P(OH)O ^- , =P(O)O ^- , =POH, =PO ^- , the anionic part contains cationic counterions, such as alkali metals, alkaline earth metals or ammonium.

As examples of anionic surfactants usable in the colorant composition I) according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkyl amidoether sulfates, alkyl aryl polyether sulfates Salt, glyceryl monoester sulfate, alkyl sulfonate, alkyl amide sulfonate, alkyl aryl sulfonate, alpha-olefin sulfonate, paraffin sulfonate, alkyl sulfosuccinate, Alkyl ether sulfosuccinate, alkyl amide sulfosuccinate, alkyl sulfoacetate, acyl sarcosinate, acyl glutamate, alkyl sulfosuccinamate, acyl hydroxyethyl Sulfonate and N-acyl taurate, polyglycoside polycarboxylic acid and alkyl monoester salt, acyl lactylate, D-galactoside uronate, alkyl ether carboxylic acid salts, alkyl aryl ether carboxylates, alkyl amido ether carboxylates, and the corresponding non-salt-forming forms of all of these compounds; all of these compounds have alkyl and acyl groups containing from 6 to 40 carbon atoms and the aryl group is Refers to phenyl.

These compounds can be oxyethylenated and then preferably contain from 1 to 50 ethylene oxide units.

The salt of polyglycoside-C ₆ -C ₂₄ alkyl monoester of polycarboxylic acid may be selected from the group consisting of C ₆ -C ₂₄ alkyl polyglycoside - citrate, C ₆ -C ₂₄ alkyl polyglycoside - tartrate and C ₆ -C ₂₄ Alkyl Polyglycoside-Sulfosuccinate.

When the one or more anionic surfactants are in salt form, they may be selected from alkali metal salts, such as sodium or potassium salts, and preferably sodium salts, ammonium salts, amine salts, and especially aminoalcoholates, or alkaline earth metal salts Salt, such as magnesium salt.

Examples of aminoalcohol salts that may be mentioned in particular include salts of monoethanolamine, diethanolamine and triethanolamine, salts of mono-, di- or triisopropanolamine, 2-amino-2-methyl -1-Propanoxide salt, 2-amino-2-methyl-1,3-propanedioxide salt and tris(hydroxymethyl)aminomethane salt.

Preference is given to using alkali metal or alkaline earth metal salts, and in particular sodium or magnesium salts.

Preferred anionic surfactants are selected from (C ₆ -C ₃₀ ) alkyl sulfates, (C ₆ -C ₃₀ ) alkyl ether sulfates, (C ₆ -C ₃₀ ) alkyl amido ether sulfates, alkyl Aryl polyether sulfates and glyceryl monoester sulfates, all of which compounds optionally contain from 1 to 20 ethylene oxide units; or are preferably selected from the group consisting of from 2 to 20 ethylene oxide units, for example from 1 to 4 rings (C ₁₂ -C ₂₀ ) alkyl sulfates and (C ₁₂ -C ₂₀ ) alkyl ether sulfates of oxyethane units, especially in the form of alkali metal, ammonium, aminoalcohol and alkaline earth metal salts, or mixtures of these compounds . Even better, it is preferred to use polyoxyethylated sodium lauryl ether sulfate, such as sodium lauryl ether sulfate containing 2 or 2.2 moles of ethylene oxide.

The anionic surfactant of the present invention is preferably a sulfate ester, more particularly selected from (C ₆ -C ₃₀ ) alkyl sulfate, (C ₆ -C ₃₀ ) alkyl ether sulfate, (C ₆ -C ₃₀ ) alkyl Amidoether sulfates, alkylaryl polyether sulfates and glyceryl monoester sulfates, their salts, such as alkali metal salts, such as sodium salts, and mixtures thereof.

Or the anionic surfactant of the present invention is preferably selected from (C ₆ -C ₃₀ ) alkyl sulfate, (C ₆ -C ₃₀ ) alkyl ether sulfate, especially (C ₆ -C ₃₀ ) alkyl ether sulfate. , such as lauryl ether sulfate, and their salts, such as sodium laureth sulfate.

The amount of one or more said anionic surfactants in the colorant composition I) according to the invention is 0.01 to 20% by weight, preferably 0.1 to 10% by weight or preferably 0.1 to 8% by weight.

nonionic surfactant

The colorant composition I) according to the invention may further contain one or more nonionic surfactants.

One or more nonionic surfactants which may be used in the compositions are described, for example, in M.R. Porter's Handbook of Surfactants, Blackie & Son, Glasgow and London, 1991, pages 116-178.

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

- Oxyalkylenated (C ₈ -C ₂₄ )alkylphenol;

- Saturated or unsaturated, linear or branched oxyalkylenated C ₈ -C ₃₀ fatty acid amides;

- Saturated or unsaturated, linear or branched, oxyethylenated C ₈ to C ₄₀ , especially C ₈ to _{C 20} and better C ₁₀ to C ₁₈ fatty alcohols, containing from 1 to 100 mol of ethylene oxide , preferably 2 to 50 mol, more particularly 2 to 40 mol, or even 3 to 20 mol ethylene oxide;

- Esters of saturated or unsaturated, linear or branched C ₈ -C ₃₀ acids and polyethylene glycols;

- esters of saturated or unsaturated, linear or branched C ₈ -C ₃₀ acids and sorbitol, which are preferably oxyethylenated;

-Fatty acid esters of sucrose;

-(C ₈ -C ₃₀ )alkyl (poly)glucosides, (C ₈ -C ₃₀ )alkenyl (poly)glucosides, which are optionally oxyalkyleneated (0 to 10 oxyalkylene units) and comprise 1 to 15 glucose units, (C ₈ -C ₃₀ ) alkyl (poly)glucoside ester;

- Saturated or unsaturated oxyethylenated vegetable oils;

- in particular the condensates of ethylene oxide and/or propylene oxide, alone or in mixtures;

-N-(C ₈ -C ₃₀ )alkylglucamine and N-(C ₈ -C ₃₀ )acylmethylglucamine derivatives;

-Aldobionamides;

-Amine oxides;

- oxyethylenated and/or oxypropylated silicones;

- and mixtures thereof.

Unless specifically mentioned, the terms "oxyalkyleneated", "oxyethylenated", "oxypropylated" and "glycerolated" cover mono- or polyoxyalkyleneated, oxyethylated, oxypropylated and glycerol respectively. chemical compounds.

The alkylene oxide units are more particularly ethylene oxide or propylene oxide units or combinations thereof, preferably ethylene oxide units.

The number of moles of ethylene oxide and/or propylene oxide is preferably from 1 to 250, more particularly from 2 to 100, and even better still from 2 to 50; the number of moles of glycerol is especially from 1 to 50, and still better Land is 1 to 10.

Advantageously, the nonionic surfactants according to the invention do not contain any propylene oxide units.

Examples may include in particular 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, etc.

As examples of glycerolated nonionic surfactants, monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols containing 1 to 50 moles of glycerol, and preferably 1 to 10 moles of glycerol are preferably used.

As examples of compounds of this type, mention may be made of lauryl alcohol containing 4 moles of glycerol (INCI name: polyglyceryl-4-lauryl ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: Polyglycerol-4 oil ether), oleyl alcohol containing 2 moles of glycerol (INCI name: polyglycerol-2 oil ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, containing Oleyl/cetyl alcohol with 6 moles of glycerol and stearyl alcohol with 6 moles of glycerol.

Among the glycerolated alcohols, it is more particularly preferred to use C ₈ /C ₁₀ alcohols containing 1 mol of glycerol, C ₁₀ /C ₁₂ alcohols containing 1 mol of glycerol and C ₁₂ alcohols containing 1.5 mol of glycerol.

The one or more nonionic surfactants, when present in the colorant composition I) according to the invention, are preferably present in a total amount of from 0.01 to 1% by weight relative to the total weight of the composition.

Solvent

The colorant composition I) according to the invention may advantageously comprise one or more solvents, such as water and/or organic solvents.

water

The colorant composition I) according to the invention advantageously contains water in an amount less than or equal to 40% by weight relative to the total weight of the composition I).

The water content in the dye composition I) according to the invention is preferably 10% to 40% by weight, more preferably 15% to 35% by weight, or 20% to 30% by weight relative to the total weight of the composition I). weight%.

Organic solvents

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

Examples of water-soluble organic solvents that may be mentioned include linear or branched and preferably saturated mono- or diols containing 2 to 10 carbon atoms, such as ethanol, isopropanol, hexanediol (2-methyl- 2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenethyl alcohol; contain more than two hydroxyl functions polyols, such as glycerol; polyol ethers, such as ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol or ethers thereof, such as propylene glycol monomethyl ether; and diethylene glycol alkyl ethers, especially is a C ₁ -C ₄ alkyl ether, such as diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

When present, the water-soluble organic solvent generally accounts for 1 to 20% by weight relative to the total weight of the colorant composition I) according to the invention, and preferably 3 to 15% by weight, or 4 to 10% by weight weight%.

alkaline agent

The colorant composition I) according to the invention may further comprise one or more alkaline agents.

The one or more alkaline agents may in particular be selected from ammonia, alkali metal carbonates or bicarbonates, organic amines with a pKb at 25° C. of less than 12, in particular less than 10 and even more advantageously less than 6; selected from the group above Salts of amines with acids such as carbonic acid or hydrochloric acid are mentioned: it should be noted that this is the pKb corresponding to the function with the highest basicity.

Preferably, the composition I) according to the invention may be free or essentially free of ammonia.

Preferably, the amine is selected from alkanolamines, in particular alkanols containing primary, secondary or tertiary amine functions and one or more linear or branched C ₁ -C ₈ alkyl groups bearing one or more hydroxyl groups Amine; selected from oxyethylenated and/or oxypropylated ethylenediamine, and selected from amino acids and compounds having the following formula:

Where W is a C ₁ -C ₆ alkylene residue optionally substituted by hydroxyl or C ₁ -C ₆ alkyl; Rx, Ry, Rz and Rt can be the same or different and represent a hydrogen atom or a C ₁ -C ₆ alkyl group, C ₁ -C ₆ hydroxyalkyl group or C ₁ -C ₆ aminoalkyl group.

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

Advantageously, the content of one or more alkaline agents is from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, or from 1% to 10% by weight or 5%, relative to the total weight of composition I) weight%. It should be noted that when the alkaline agent is ammonia water, this content is expressed as _NH3 .

The pH of the composition I) of the invention is preferably between 6 and 11.

The pH can be adjusted by adding acidifying agents, such as hydrochloric acid, (ortho)phosphoric acid, sulfuric acid, boric acid and carboxylic acids, such as acetic acid, lactic acid or citric acid, or sulfonic acid. Alkali agents, such as those mentioned above, may also be used.

fatty phase

The colorant composition I) according to the invention may also comprise cosmetically acceptable fatty substances.

According to a particular embodiment, the fatty substance does not contain carboxylic acid groups.

The term "fatty substance" refers to an organic compound that is insoluble in water (solubility less than 5%, preferably 1%, and more preferably 0.1%) at normal temperature (25°C) and atmospheric pressure (760mmHg). They may preferably have in their structure a sequence of at least two siloxane groups or at least one hydrocarbon-based chain containing at least 6 carbon atoms. Furthermore, fatty substances are generally soluble in organic solvents such as chloroform, ethanol, benzene or decamethylcyclopentasiloxane under the same conditions of temperature and pressure.

The fatty substance is selected in particular from the group consisting of lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, oils, in particular mineral, vegetable, animal or synthetic non-silicone oils, non-silicone waxes and silicones.

It is reiterated that for the purposes of the present invention, fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups containing from 6 to 30 carbon atoms, which Optionally substituted in particular by one or more (especially 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may contain from 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

Regarding lower alkanes, these alkanes contain from 6 to 16 carbon atoms and are straight or branched chain, optionally cyclic. For example, the alkanes may be hexane and dodecane, and isoparaffins such as isohexadecane and isodecane.

As non-silicone oils useful in the compositions of the present invention, examples that may be mentioned include:

-Hydrocarbon-based oils of animal origin, such as perhydrosqualene;

- Hydrocarbon-based oils of vegetable origin, such as liquid fatty acid triglycerides containing 6 to 30 carbon atoms, such as enanthate or caprylic acid triglycerides, or, for example, sunflower oil, corn oil, soybean oil, zucchini oil, grapeseed oil , sesame oil, hazelnut oil, almond oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric triglycerides, such as those sold by Stéarineries Dubois or under the name Dynamit Nobel Those sold under the names 810, 812 and 818, jojoba and shea butter;

- straight-chain or branched-chain hydrocarbons having more than 16 carbon atoms and of inorganic or synthetic origin, such as liquid paraffin, petrolatum, liquid petrolatum, polydecene and hydrogenated polyisobutylene, such as

-Fluorinated oils such as BNFL Fluorochemicals PC1 and/> Perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane sold under the name PC3; perfluoro-1,2-dimethylcyclobutane; perfluoroalkane, such as 3M Company’s PF /> Know PF/> sold as dodecafluoropentane and tetradecafluorohexane, or by Atochem as Bromoperfluorooctyl sold under the names; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 3M Company under the name PF/> 4-Trifluoromethylperfluoromorpholine sold under the name.

The fatty alcohols useful in the compositions of the present invention are not oxidatively alkyleneated. They are saturated or unsaturated, linear or branched, and contain from 6 to 30 carbon atoms, and more particularly from 8 to 30 carbon atoms. Mention may be made of cetyl alcohol, stearyl alcohol and mixtures thereof (cetestearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecane Alcohol, oleyl alcohol or linoleyl alcohol.

Useful esters are saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyacids with saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyalcohols Esters of alcohols, the total carbon number of the ester being more particularly greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl alcohol lactate; C ₁₂ -C ₁₅ lactic acid alkane ester; isostearyl alcohol lactate; lauryl alcohol lactate; linoleyl alcohol lactate; oleyl alcohol lactate; (iso)stearyl caprylate; isocetyl caprylate; octyl caprylate; spermaceti Alcohol octanoate; decyl oleate; isocetyl alcohol isostearate; isocetyl alcohol laurate; isocetyl alcohol stearate; isodecyl octanoate; isodecyl oleate; isononyl Isononyl acid; Isostearyl palmitate; Methyl acetyl ricinoleate; Myristyl stearate; Octyl isononanoate; 2-ethylhexyl isononanoate; Octyl palmitate; Nonyl Octyl acid; Octyl stearate; Octyldodecyl erucate; Oleyl erucate; Ethyl and isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate Esters, alkyl myristate, such as isopropyl myristate, butyl myristate, cetyl myristate, 2-octyldodecyl myristate, myristyl alcohol Myristate or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate .

Still within the scope of this variant, it is also possible to use esters of C ₄ -C ₂₂ dicarboxylic acids or tricarboxylic acids with C ₁ -C ₂₂ alcohols as well as mono-, di- or tricarboxylic acids and C ₂ -C ₂₆ Esters of di-, tri-, tetra- or pentahydroxy alcohols.

In particular, the following may be mentioned: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl alcohol Diacid ester; dioctyl maleate; glyceryl undecylenate; octyldodecanol stearyloxystearate; pentaerythritol monoricinoleate; pentaerythritol tetraisononanoate; tetrakisinate Pentaerythritol nonanoate; Pentaerythritol tetraisostearate; Pentaerythritol tetracaprylate; Propylene glycol dicaprylate; Propylene glycol dicaprate; Tridecyl erucate; Triisopropyl citrate; Triisostearyl alcohol. Citrate; Glyceryl trilactate; Glyceryl tricaprylate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dicaprylate; neopentyl glycol diheptanoate; diethylene glycol Alcohol diisonononate; ethylene glycol distearate; diethylene glycol distearate and polyethylene glycol distearate.

The composition may also comprise as fatty esters sugar esters and diesters of C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. To reiterate, the term "sugar" refers to oxygen-containing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and containing at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars which may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose and their derivatives, especially alkyl Derivatives, such as methyl derivatives, such as methylglucose.

Sugar esters of fatty acids may in particular be selected from the group consisting of esters or ester mixtures of the aforementioned sugars and linear or branched, saturated or unsaturated C ₆ -C ₃₀ , and preferably C ₁₂ -C ₂₂ fatty acids. If they are unsaturated, these compounds may contain from 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

Esters according to this variant can also be selected from the group consisting of monoesters, diesters, triesters, tetraesters and polyesters and mixtures thereof.

These esters may be selected from, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate and arachidonic acid esters or mixtures thereof, in particular such as oil palmitate, oil stearate and palm stearate mixed esters.

More particularly preferred are the use of monoesters and diesters, and especially mono- or di-oleate, stearate, behenate, oil palmitate, linoleate, of sucrose, glucose or methylglucose, Linolenate and oil stearate.

Advantageously, the content of one or more fatty substances is 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).

Adjuvant

The colorant composition I) according to the invention may also comprise one or more cosmetic adjuvants.

For example, composition I) may comprise one or more additives known in the art, such as anionic, nonionic or amphoteric polymers or mixtures thereof, anti-hair loss agents, vitamins and provitamins, including panthenol, derivatives of these vitamins substances (especially esters) and their mixtures; sunscreens, inorganic or organic pigments, chelating agents, plasticizers, solubilizers, acidulants, opacifiers, hydroxy acids, pearlescent agents, fragrances and preservatives.

Needless to say, one skilled in the art will be careful to select the optional additional compound(s) so that the contemplated addition(s) does not, or does not substantially, adversely affect the advantages inherently associated with the present invention. nature.

The above-mentioned adjuvants may each generally be present in an amount of from 0 to 20% by weight, or from 0 to 10% by weight, relative to the total weight of composition I).

The composition I) according to the invention may be in the form of a fluid or thickened liquid, gel or cream, preferably in the form of a cream.

Developer composition II)

Coloring composition a) in the combination according to the invention may comprise developer composition II).

According to one embodiment of the invention, the developer composition II) is placed separately from the colorant composition I).

oxidizing agent

Composition II) of composition a) according to the invention contains at least one oxidizing agent.

The developer composition II) of the invention may comprise one or more oxidizing agents which are usually used as one of the active components of the composition II). The term "oxidizing agent" means an oxidizing agent other than atmospheric oxygen. More particularly, the oxidizing agent is selected from the group consisting of hydrogen peroxide, carbamide peroxide, alkali metal bromates, peroxide salts, such as persulfates or perborates, peracids and their precursors, and alkali metal or alkaline earth metal salts; or polymeric complexes capable of releasing hydrogen peroxide.

Advantageously, the oxidizing agent is hydrogen peroxide.

The concentration of the oxidizing agent may be from 0.1% to 50% by weight, or preferably from 0.5% to 20% by weight, or from 1% to 15% by weight, based on the weight of composition II).

Solvent

The developer composition II) of the invention may comprise one or more solvents, such as water and/or organic solvents. Useful solvents may be selected from those discussed above for the "solvents" of composition I).

Compositions I) and II) of dyeing composition a) can independently each use the same or different solvents.

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

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

When present, the water-soluble organic solvent generally accounts for 0.01% to 10% by weight relative to the total weight of the colorant composition I) according to the invention, and preferably from 0.1% to 5% by weight or from 0.5% to 1% by weight. weight%.

Surfactant

The developer composition II) according to the invention may comprise one or more surfactants, in particular for example anionic surfactants and/or nonionic surfactants, preferably nonionic surfactants. Useful surfactants may be selected from those discussed above for the "surfactants" of composition I).

chelating agent

The colorant composition I) and/or the developer composition II) of the dyeing composition a) according to the invention may comprise at least one chelating agent.

Useful chelating agents according to the invention include aminocarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, and in particular their alkali metal salts, such as N,N- Bis(carboxymethyl)glutamic acid, tetrasodium EDTA, tetrasodium salt of N,N-bis(carboxymethyl)glutamic acid (glutamic acid diacetic acid, GLDA); hydroxycarboxylic acids, such as citric acid, tartaric acid , glucuronic acid, succinic acid, ethylenediamine disuccinic acid (EDDS), and especially their alkali metal salts; hydroxyaminocarboxylic acids, such as hydroxyethylethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DEG), especially their alkali metal salts; polyphosphonic acids, and especially their alkali metal salts; other phosphorus-containing organic acids, such as phytic acid, and especially their alkali metal salts, such as sodium phytate , potassium phytate; polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, and especially alkali metal salts thereof.

In one embodiment, at least one water-soluble chelating agent is an alkali metal hydroxypolycarboxylate represented by: substituted with 1, 2 or 3 hydroxyl groups (-OH), preferably with one (1) hydroxyl group, and further substituted by 2, 3, 4 or 5 carboxylic acid (salt) groups (-COOM), preferably by 2 or 3 carboxylic acid (salt) groups (-COOM) containing 1 to 4 carbon atoms, Alkanes containing 2 or 3 carbon atoms are preferred, in which multiple groups M independently represent H or an alkali metal, provided that at least one group M represents an alkali metal, such as Na, K or Li, preferably all groups M represent a base. Metal, such as Na, K or Li, preferably Na. More specifically, the at least one alkali metal hydroxypolycarboxylate may be selected from the group consisting of sodium tartrate, sodium citrate, potassium tartrate, potassium citrate and their hydrates, preferably sodium citrate, especially trisodium citrate. Sodium citrate is used herein to mean monosodium citrate, disodium citrate and trisodium citrate, and other alkali metal hydroxypolycarboxylates may be understood in a similar manner.

The alkali metal mentioned above is particularly preferably sodium or potassium, especially sodium. Accordingly, preferred chelating agents may comprise sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate or mixtures thereof.

Component B), pyrazolidine-3,5-dione compounds of formula (1)

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

Wherein R ₁ and R ₂ are each independently H, hydroxyl, unsubstituted or substituted C1-C30 alkyl, unsubstituted or substituted C2-C30 alkenyl, cycloalkyl, unsaturated heterocyclic group, hetero Cyclic group or epoxyalkyl group, such as C1-C10 alkyl or halogen-substituted C1-C10 alkyl, preferably C1-C6 alkyl or halogen-substituted C1-C6 alkyl, C3-C10 alkenyl, C3-C10 Cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, and _R3 is H or unsubstituted or halogen-substituted C1-C10 alkyl, C3 -C10 cycloalkyl, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br.

According to a preferred embodiment of the present invention, R ₁ and R ₂ are each lower alkyl, such as C1-C6 alkyl, or C1-C4 alkyl. For example, _R1 and _R2 may be the same alkyl group, such as each being methyl, ethyl, propyl or butyl. According to one embodiment, _R3 can be H. Therefore, examples of the pyrazolidine-3,5-dione compound of formula (1) may include 1,2-dimethyl-pyrazolidine-3,5=dione, 1,2-diethyl-pyrazolone Azolidine-3,5-dione, 1,2-dipropyl-pyrazolidine=3,5-dione and 1,2-dibutyl-pyrazolidine-3,5-dione.

The pyrazolidine-3,5-dione compound of formula (1) according to the present invention is usually present in an amount of 0.001% to 25% by weight, or 0.0001% to 10% by weight, preferably 0.005% to 25% by weight relative to the total weight of the combination. It is present in an amount of 5% by weight, in particular from 0.01% to 3% by weight.

Addition form of pyrazolidine-3,5-dione compound of formula (1)

As mentioned above, the inventors have surprisingly found that the pyrazolidine-3,5-dione compounds of formula (1) can be used as slow dyes or intermediates thereof, for example oxidation dyes useful in composition I) i) reaction blocker.

That is, the pyrazolidine-3,5-dione compound of formula (1) mainly acts on the reaction of the dye. Therefore, for dye combinations, the pyrazolidine-3,5-dione compound of formula (1) can be added directly to the dyeing composition a), for example as a mixture with the colorant composition I); or it can be combined with the dyeing Substance a) is added separately to a separate chamber, for example in the form of a pyrazolidine-3,5-dione composition comprising a pyrazolidine-3,5-dione compound of formula (1).

In order to be used as a pyrazolidine-3,5-dione composition independently of the coloring composition a), the pyrazolidine-3,5-dione composition may contain pyrazolidine-3,5-dione compositions known in the cosmetic field to be beneficial to formula (1). Any component of the stability of oxazolidine-3,5-dione compounds.

Therefore, the present invention can advantageously provide a dyeing combination comprising:

Dyeing composition a) according to the invention placed in chamber 1; and

A pyrazolidine-3,5-dione composition comprising a pyrazolidine-3,5-dione compound of formula (1) according to the present invention is placed in chamber 2, which is separate from chamber 1.

As mentioned above, AMPS polymers may be used to slow down the reaction of dyes or intermediates thereof, such as oxidation dyes i) which may be used in composition i). Without being bound by any known theory, it is believed that the pyrazolidine-3,5-dione compound of formula (1) used in combination with the AMPS polymer described above can bring about a synergistic effect in the form of a retardant.

Methods and uses

A subject of the present invention is a method for dyeing human keratin fibers, in particular hair, using a combination of dyes as described above.

Another subject of the invention is a method for reducing staining of a dye composition using a dye combination as described above.

Another subject of the invention is a method of slowing down the reaction of dyes or intermediates using dye combinations as described above.

The invention also relates to the use of a dye combination as described above for dyeing keratin fibers, in particular hair.

The invention also relates to the use of a dye combination as described above for reducing staining of the dye combination.

The present invention also relates to the use of a dye combination as described above for slowing down the reaction of a dye or intermediate (using a dye combination as described above).

In particular, the present invention relates to a method for slowing down the reaction of dyes or intermediates thereof, characterized by mixing a pyrazolidine 3,5-dione compound of formula (1) including phenylmethylpyrazolone with a dye.

Preferably, the pyrazolidine 3,5-dione compound of formula (1) is mixed with the dye before applying the dye, or the pyrazolidine 3,5-dione compound of formula (1) is applied to the applied dye for less than 10 minutes, less than 5 minutes, or less than 3 minutes.

The present invention also relates to the use of pyrazolidine 3,5-dione compounds of formula (1) including phenylmethylpyrazolone for reducing staining of dyes.

In another aspect, the invention relates to the use of a composition for dyeing keratin fibers while reducing staining in areas of non-keratin fibers, wherein the composition comprises a phenylmethylpyrazolone of the formula (1 ) of pyrazolidine 3,5-dione compounds.

According to a preferred embodiment, the dyeing method of the invention consists in mixing colorant composition I) with composition II) just before use and applying the mixture obtained as described above to the keratin fibers.

More particularly, "mixing" or a variant thereof is intended to mean the act of placing the colorant composition I) of the invention together with the developer composition II) as described above in a container or in the palm of the hand, stirring it or Do not stir.

According to a preferred variant of the preferred embodiment, the colorant composition I) of the invention is placed in a container or in the palm of a hand together with the developer composition II) as described above without stirring them.

Regardless of the method used and the amount of composition used, one or more of the above-mentioned compositions, optionally premixed, are applied to wet or dry keratin fibers.

As described above in the section "Incorporation forms of the pyrazolidine 3,5-dione compound of formula (1)", the pyrazolidine 3,5-dione compound of formula (1) can be provided in various forms For use with colorant composition I) and developer composition II), thereby slowing down the reaction of the dye. In particular, if the pyrazolidine 3,5-dione compound of formula (1) is placed in chamber 2 separate from chamber 1, for the dye combination according to the invention:

- If the user does not want to slow down dyeing, or does not care about staining caused by dye, chamber 2 may not be used;

- If the user wishes to avoid any staining, he/she can mix chambers 2 and 1 before staining;

- If the user wants to decide whether to use Chamber 2 based on whether staining actually occurs, he/she can first use Chamber 1 only, and as soon as the staining composition adheres to the hands or anywhere else, Chamber 2 can be applied; and

- If the user wants to avoid staining and expects quick staining, he/she can pre-apply Chamber 2 to the location where staining is most likely to occur but should be avoided, such as the hands.

Alternatively, if the pyrazolidine 3,5-dione compound of formula (1) is provided together with the colorant composition I), for example directly added to the composition I), with the exception that there is no pyrazole of formula (1) present The dyeing process is often slowed down compared to the same dyeing process except for alkanes 3,5-dione compounds.

The mixed composition (comprising colorant composition I) and developer composition II), and optionally the pyrazolidine 3,5-dione compound of formula (1)) is usually left in place on the fiber Usually 1 minute to 1 hour and preferably 5 minutes to 30 minutes.

The temperature during the process is generally 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 further washed with shampoo and then rinsed with water and dried or left to dry.

This process can be repeated several times to obtain the desired coloration.

The dye combinations described above may also be provided with a device allowing delivery of the desired mixture to the hair, such as is described for example in patent FR 2586 913.

The following examples are given merely as illustrations of the invention.

Example:

Ingredient amounts/concentrations in the following compositions/formulations are expressed in weight % relative to the total weight of each composition/formulation.

Example 1

Colorant compositions I-A and I-B were prepared from the ingredients shown in Table 1 below (wherein levels are expressed as weight % of material relative to the total weight of the composition):

Table 1

The following developer composition II-A was prepared from the ingredients shown in Table 2 below (wherein content is expressed as weight % of material relative to the total weight of the composition):

Table 2

Element II-A Cetearyl Alcohol (and) Cetearyl Ether-25 2.85 Trideceth-2 formamide MEA 0.85 glycerin 0.5 Pentasodium Pentetate 0.15 hydrogen peroxide 12 water QS

Example 2

For application, compositions I-A to B were mixed with composition II-A, respectively, in a weight ratio of 1:1.5 to provide mixtures A and B.

The viscosity of the mixture was then measured according to CID-012-02H. The results are given in Table 3 below:

table 3

nature Mixture A Mixture B Viscosity(M4) 20.5 28.5

Example 3

Similar to Example 1, the following colorant compositions I-C to E were prepared from the ingredients shown in Table 4 below (the content is expressed in weight % of the material relative to the total weight of the composition):

Table 4

Example 4

Compositions I-C to E are respectively mixed with composition II-A in a weight ratio of 1:1.5 to provide mixtures C to E.

At 30 minutes, the mixtures were photographed individually. As shown in Figure 1, it is clear from visual inspection that mixture D produces a much lighter color than the other two due to the different dyes used in combination with component B). In particular, for mixture E, the skilled person can recognize that the oxidation reaction is hardly retarded at all.

Table 5 Performance of cleaning levels

performance Mixture C Mixture D Mixture E blocking effect Genhao excellent Difference

Claims (14)

1. A dye combination for oxidatively dyeing keratin fibers, comprising: A) Dyeing composition a), containing: I) Colorant composition I), comprising: i) at least one oxidation dye; The oxidation dyes include one or more selected from p-phenylenediamines, bis(phenyl)alkylenediamines, p-aminophenols, o-aminophenols and their addition salts, and mixtures thereof The oxidation color base; and / or wherein the oxidation dye comprises one or more coupling agents selected from m-phenylenediamines, m-aminophenols and their addition salts, and mixtures thereof; and B) Pyrazolidine-3,5-dione compound of formula (1): Wherein R ₁ and R ₂ are each independently H, hydroxyl, unsubstituted or substituted C1-C30 alkyl, unsubstituted or substituted C2-C30 alkenyl, cycloalkyl, unsaturated heterocyclic group, hetero Cyclic group or epoxyalkyl group, such as C1-C10 alkyl or halogen-substituted C1-C10 alkyl, preferably C1-C6 alkyl or halogen-substituted C1-C6 alkyl, C3-C10 alkenyl, C3-C10 Cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, and _R3 is H or unsubstituted or halogen-substituted C1-C10 alkyl, C3 -C10 cycloalkyl, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br. 2. Dye combination according to claim 1, wherein the pyrazolidine-3,5-dione compound of formula (1) is placed in a separate chamber from the dyeing composition a). 3. The dye combination according to any one of the preceding claims, wherein _R1 and _R2 are each C1-C6 alkyl or C1-C4 alkyl; and/or _R3 is H. 4. The dye combination according to any one of the preceding claims, wherein the pyrazolidine-3,5-dione compound of formula (1) is selected from 1,2-dimethyl-pyrazolidine-3,5 -Diketone, 1,2-diethyl-pyrazolidine-3,5-dione, 1,2-dipropyl-pyrazolidine-3,5-dione and 1,2-dibutyl- Pyrazolidine-3,5-dione. 5. The dye combination according to any one of the preceding claims, wherein the pyrazolidine-3,5-dione compound of formula (1) is present in an amount of: 0.0001 to 10% by weight, or preferably 0.005 to 5% by weight or in particular 0.01 to 3% by weight, or preferably 0.1 to 2% by weight, relative to the total weight of the combination. 6. The dye combination according to any one of the preceding claims, wherein the oxidation dye does not comprise any pyrazole derivatives. 7. The dye combination according to any one of the preceding claims, wherein the oxidation dye is selected from aminophenols, preferably meta-aminophenols. 8. The dye combination according to any one of the preceding claims, wherein the oxidizing alkali agent is present in the following amount: 0.0001 to 20% by weight, preferably 0.01 to 10% by weight, and still better 0.1% by weight % to 5% by weight, relative to the total weight of composition I); and/or the coupling agent is present in an amount from 0.0001% to 20% by weight, and preferably from 0.001% to 10% by weight, or from 0.01% to 10% by weight. 5% by weight, relative to the total weight of composition I). 9. The dye combination according to any one of the preceding claims, wherein the colorant composition I) comprises a reducing agent used as an antioxidant, the reducing agent being selected from the group consisting of thioglycolic acid, dimercaptoacetic acid, thiolactic acid , Thiomalic acid, its salts and mixtures thereof; and / or Wherein the colorant composition I) contains selected from the group consisting of natural exogenous phytochemical antioxidants, flavonoids, vitamins such as vitamin C and/or E and their derivatives, tocopherols, tocotrienols, carotenoids, anthocyanins , dihydrochalcones, phenylpropanoids, chalcones, curcuminoids, tannins, stilbenoids, coumarins, carotenoids or additional antioxidants of mixtures thereof. 10. The dye combination according to claim 9, wherein the antioxidant is used in an amount of 0.001 to 10% by weight relative to the total weight of the colorant composition I), preferably 0.1 to 7% by weight, more preferably 0.5 to 7% by weight. 4% by weight. 11. The dye combination according to claim 1, wherein the pyrazolidine-3,5-dione compound of formula (1) is placed in the colorant composition I). 12. The dye combination according to any one of the preceding claims, wherein said dyeing composition a) comprises: II) Developer composition II), comprising: ii) At least one oxidizing agent, wherein said oxidizing agent is selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromates, peroxide salts; and polymeric complexes capable of releasing hydrogen peroxide. 13. A method for reducing staining in areas other than keratin fibers or slowing down the reaction of dyes or intermediates thereof, characterized by mixing the pyrazolidine-3,5-dione compound of formula (1) with the dye: Wherein R ₁ and R ₂ are each independently H, hydroxyl, unsubstituted or substituted C1-C30 alkyl, unsubstituted or substituted C2-C30 alkenyl, cycloalkyl, unsaturated heterocyclic group, hetero Cyclic group or epoxyalkyl group, such as C1-C10 alkyl or halogen-substituted C1-C10 alkyl, preferably C1-C6 alkyl or halogen-substituted C1-C6 alkyl, C3-C10 alkenyl, C3-C10 Cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, and _R3 is H or unsubstituted or halogen-substituted C1-C10 alkyl, C3 -C10 cycloalkyl, C3-C10 heterocycloalkyl, or C3-C10 alkoxy, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br. 14. The method of claim 13, wherein the pyrazolidine-3,5-dione compound of formula (1) is mixed with the dye before applying the dye, or the pyrazole compound of formula (1) The alkane-3,5-dione compound is applied to a location where the dye has been applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes.