FR3124722A1 - Oxidation retardant composition - Google Patents

Abstract

The present invention relates to a retarding composition comprising the components of: 1) a water-soluble chelating agent selected from carboxylic acids comprising at least one heteroatom in addition to the carboxylic group; 2) a pyrazolidine-3,5-dione compound of formula (1): wherein R1 and R2 are each independently H, hydroxy, C1-C30 alkyl, unsubstituted or substituted, C2-C30 alkenyl, unsubstituted or substituted, cycloalkyl, heterocyclic group or alkoxy; and R3 is H, or C1-C10 alkyl unsubstituted or substituted by halogen, C3-C10 cycloalkyl, C3-C10 heterocyclic alkyl, or C3-C10 alkoxy, wherein halogen is preferably an F, Cl or Br. (1) Figure for abstract: none

Description

Oxidation retardant composition

The present invention relates to an oxidation retardant composition, in particular for the oxidation of oxidative dyes.

Context

Dyes are widely used for various applications and fields, such as printing, paper, fabrics, cosmetics, medical science, paint, and others. In many situations, quick dyeing may be desirable. However, in some other situations slow dyeing may be desirable. In particular, slow dyeing can result in a "cancellable" dye effect, allowing some unwanted dyeing to be changed or undone.

For example, many people have long sought to change the color of their hair, and in particular to tint it in order, for example, to mask their gray hair. The dye product can include both at least one oxidative dye and at least one oxidant. For better use, the oxidative dye and the oxidant can be placed in a multi-compartment packaging respectively, and are mixed together immediately before use.

Consumers want to use dyes to tint only the target area. However, in many cases, for example, when dyeing hair, some other areas may be undesirably tinted (stained), such as hands, face, ears and others. Consumers need to pay more attention to avoid unwanted areas, and have been looking for products that help them remedy unwanted dye.

The inventors have now discovered that the use of a specific retarding composition comprising a pyrazolidine-3,5-dione compound makes it possible to slow down the oxidation reaction, in particular of an oxidative dye, so as to reduce or even substantially avoid undesirable stain formation by dyeing on a non-targeted position, which is called anti-stain effect. In particular, when the oxidation reaction involves a polyvalent metal cation, in particular calcium, strontium, zinc, copper, iron, manganese, aluminum, or mixtures thereof, for example, a hair dye product with a high percentage of metal ions, such as Cu ²⁺ or Fe ³⁺ (e.g. Caucasian hair tends to contain higher Cu ²⁺ content) , a chelating agent may be particularly useful in the retarding composition, which may enhance the anti-stain effect.

An object of the present invention is thus an oxidation retardant composition, comprising components of:

1) a water-soluble chelating agent selected from carboxylic acids comprising at least one heteroatom in addition to the carboxylic group;

2) a pyrazolidine-3,5-dione compound of formula (1):

(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, heterocyclic or alkoxy, such as C1-C10 alkyl or C1-C10 alkyl substituted by halogen, preferably C1-C6 alkyl or C1-C6 alkyl substituted by halogen, C3 alkenyl -C10, a C3-C10 cycloalkyl, a C3-C10 unsaturated heterocyclic group, a C3-C10 heterocyclic alkyl or a C3-C10 epoxylalkyl; and R ₃ is H, or C1-C10 alkyl unsubstituted or substituted by halogen, C3-C10 cycloalkyl, C3-C10 heterocyclic alkyl, or C3-C10 alkoxy, such as C1-C6 or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br.

The present invention also provides a dye kit for the oxidative dyeing of keratin fibres, comprising the compositions of:

A) a delay composition according to the present invention; And

B) a dye composition comprising an oxidative dye.

Optionally, the retarding composition is placed together with the dye composition, or in a separate chamber from the dye composition.

According to one embodiment of the invention, the dye composition may in turn comprise:

I) a dye composition I), comprising:

i) at least one oxidative dye; And

II) a developer composition II), comprising:

ii) at least one developer.

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

The present invention thus provides the use of the retarding composition for slowing down oxidation reactions, in particular of dyes or intermediates thereof.

The present invention also provides the use of the retardant composition to reduce the staining tendency of a dye.

The present invention also relates to a method of slowing down reactions of dyes or intermediates thereof, characterized by mixing the retarding composition with the dye. Preferably, the retarding composition is mixed with the dye before application of the dye, or the retarding composition is applied at the position at which the dye has been applied for less than 10 minutes, less than 5 minutes, or less 3 minutes.

Description of the drawings

There shows the stain resistance performance of the blends according to Example 2.

Embodiments of the Invention

Throughout the description, including the claims, the term "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise indicated. In addition, the expression "at least one" used in the present description is equivalent to the expression "one or more".

Throughout the specification, including the claims, an embodiment defined by "comprising" or the like is to be understood to encompass a preferable embodiment defined by "substantially consisting of" and a preferable embodiment defined by "consisting of ".

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

In the application, unless specifically stated otherwise, strengths, parts and percentages are expressed on a weight basis.

Throughout the description, including the claims, the term "retarder" means an agent capable of slowing down oxidation reactions, in particular of dyes or intermediates thereof, such as reactions with a developer, for example, an oxidation reaction between them.

According to the present invention, "reduction of the tendency to spot formation" refers to the reduction of spot formation occurring in undesirable areas, such as the hands, face, scalp, ears, rinse water, towels, soil, etc. Preferably, the effect lasts at least 5 minutes after dyeing the hair, more particularly 10 minutes, or preferably 15 minutes, or 20 minutes.

An object of the present invention is to provide an oxidation retardant composition, comprising components of:

1) a water-soluble chelating agent selected from carboxylic acids comprising at least one heteroatom in addition to the carboxylic group;

2) a pyrazolidine-3,5-dione compound of formula (1):

(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, heterocyclic or alkoxy, such as C1-C10 alkyl or C1-C10 alkyl substituted by halogen, preferably C1-C6 alkyl or C1-C6 alkyl substituted by halogen, C3 alkenyl -C10, a C3-C10 cycloalkyl, a C3-C10 heterocyclic alkyl or a C3-C10 epoxylalkyl; and R ₃ is H, or unsubstituted or halogen-substituted C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocyclic alkyl, or C3-C10 alkoxy. C3-C10, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br.

Preferably, the present invention provides a dye kit, comprising the compositions of:

A) a delay composition according to the present invention; And

B) a dye composition.

Preferably, the present invention provides a dye kit, comprising the compositions of:

A) a delay composition according to the present invention; And

B) a dye composition, comprising:

I) a dye composition I), comprising the components of:

i) at least one oxidative dye; And

II) a developer composition II), comprising the components of:

ii) at least one oxidant.

The dyeing kit of the invention is intended for use in a process for dyeing keratin fibres.

An object of the invention is thus a process for dyeing keratin fibres, which consists in mixing the dye composition I) with the composition II) of the dye composition immediately before use to obtain a dye mixture, optionally by adding a pyrazolidine-3,5-dione compound of formula (1) in the dye mixture, and in applying it to the keratin fibers of the dye kit of the invention.

In an alternative embodiment according to the present invention, a pyrazolidine-3,5-dione compound of formula (1) may be added directly into the dye composition I).

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

Except in the working examples, or if otherwise indicated, all numbers expressing quantities of components and/or reaction conditions are to be understood as being modified in all cases by the term "about", having the meaning conventionally known in the art, for example, within 10% of the number indicated (such that "about 10%" means 9% - 11% and "about 2%" means 1.8% - 2.2%).

Delay composition

An object of the present invention is an oxidation retardant composition. Without being limited to any known theory, it is believed that the pyrazolidine-3,5-dione compound of formula (1) according to the present invention can serve as an active component for slowing down oxidation reactions, in particular for oxidative dyes. Without being limited to any known theory, it is further believed that the use of the chelating agent may enhance the retarding effect.

Component 1), Chelating Agent

The delay composition according to the present invention comprises a chelating agent as component 1).

According to the present invention, the useful chelating agent comprises:

- amino carboxylic 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, tetrasodium EDTA, tetrasodium salt of N,N-bis(carboxymethyl)glutamic acid (glutamic acid diacetic acid, GLDA);

- hydroxyl carboxylic acids, for example, citric acid, tartaric acid, glucuronic acid, succinic acid, ethylenediamine disuccinic acid (EDDS), and in particular the alkali metal salt thereof ;

- hydroxyl aminocarboxylic acids, for example, hydroxyethylethylenediamine triacetic acid (HEDTA), dihydroxyethylglycine (DEG), and in particular the alkali metal salt thereof;

- polyphosphonic acid, and in particular the alkali metal salt thereof; And

- another phosphorus-containing organic acid, e.g. phytic acid, and in particular the alkali metal salt thereof, e.g. sodium phytate, e.g. potassium phytate polycarboxylic acid, polyacrylic acid, polymethacrylic acid, and in particular the alkali metal salt thereof.

In one embodiment, the at least one water-soluble chelating agent can also be an alkali metal hydroxyl polycarboxylate represented by an alkane containing from 1 to 4 carbon atoms, preferably containing 2 or 3 carbon atoms, substituted with 1, 2, or 3 hydroxyl groups (-OH), preferably with one (1) hydroxyl group, and further substituted with 2, 3, 4 or 5 carboxylate groups (-COOM), preferably with 2 or 3 carboxylate (-COOM) groups, wherein multiple M groups are independently H or an alkali metal, provided that at least one of the M groups is 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, the at least one alkali metal hydroxyl polycarboxylate can be chosen from sodium tartrates, sodium citrates, potassium tartrates, potassium citrates, and the hydrates of these, preferably the citrates of sodium, especially trisodium citrate. Here, sodium citrates are used to indicate monosodium citrate, disodium citrate, and trisodium citrate, and other alkali metal hydroxyl polycarboxylates can be understood in a similar way.

Among others, the alkali metal mentioned above is preferably sodium or potassium, in particular sodium. Accordingly, preferable chelating agents may include EDTA, citric acid, GLDA, sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, or a mixture thereof. -this.

According to the present invention, the chelating agent component 1) can be used in an amount by weight similar to that of component 2). In particular, component 1) chelating agent is used in the delay composition at a weight ratio to component 2) of 1:2 to 2:1, preferably 1:1.5 to 1.5:1, or preferably 1:1.2 to 1.2:1, or preferably at a weight ratio of about 1:1, such as 1:1.1 to 1.1:1, or 1:1, 05 at 1.05:1.

Component 2), VS pyrazolidine-3,5-dione compound of formula (1)

The delay composition according to the present invention comprises a pyrazolidine-3,5-dione compound of formula (1):

(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, heterocyclic or alkoxy, such as C1-C10 alkyl or C1-C10 alkyl substituted by halogen, preferably C1-C6 alkyl or C1-C6 alkyl substituted by halogen, C3 alkenyl -C10, a C3-C10 cycloalkyl, a C3-C10 heterocyclic alkyl or a C3-C10 epoxylalkyl; and R ₃ is H, or unsubstituted or halogen-substituted C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocyclic alkyl, or C3-C10 alkoxy. C3-C10, 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 a lower alkyl, such as a C1-C6 alkyl, or a C1-C4 alkyl. For example, R ₁ and R ₂ can be the same alkyl, for example each being a methyl, an ethyl, a propyl or a butyl. According to one embodiment, R ₃ can be H. Accordingly, examples of pyrazolidine-3,5-dione compound of formula (1) can 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.

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

Tinting kit comprising composition A)

According to one embodiment of the present invention, the retarding composition can be used as composition A) for a dye kit. Such a dyeing kit comprising composition A) according to the present invention can be useful for dyeing for various applications, such as printing, paper, fabrics, cosmetics, medical sciences, paint, keratin fibers and others.

According to one embodiment of the invention, the dye kit according to the present invention can be used to form an undyed area/pattern or a lighter shaded area/pattern for an article , such as a fabric or paper product, to be dyed. In particular, the dyeing kit is particularly useful for the oxidative dyeing of keratinous fibers, for example for hair.

Composition A) can preferably be used according to the invention in an amount which can lie in a range of 0.1 to 8% by weight, preferably 0.5 to 5% by weight, or preferably 1 .5 to 3% by weight, based on the total weight of the dye kit.

According to one embodiment of the invention, the dye kit according to the present invention further comprises an AMPS polymer, which is preferably crosslinked or non-crosslinked homopolymers or copolymers comprising at least the acid monomer acrylamido-2- methylpropanesulfonic.

Preferably, the AMPS polymer is selected from a homopolymer of sodium acrylamido-2-methylpropanesulfonate, or an ammonium polyacryloyldimethyl taurate homopolymer, an AMPS/hydroxyethyl acrylate copolymer, or a cross-linked polymer of acryloyldimethyltaurate of ammonium/steareth-25 methacrylate.

Form of addition of composition A)

As stated above, the inventor has surprisingly found that component 2) according to the present invention (namely, pyrazolidine-3,5-dione compound of formula (1)) can be used as an active component of the retarding composition A) to slow down reactions of dyeing or intermediates thereof, for example, oxidative dyeing, while component 1) of the chelating agent can enhance the effect thereof. Namely, composition A) mainly acts on the reaction of the dye.

Accordingly, for the dye kit according to the present invention, composition A) can be added directly into dye composition B), for example, as a mixture with dye composition I) when used in the composition B); or it can be added in an independent chamber, separate from the dye composition.

For the use independently of the dye composition B), the composition A) can comprise any component known in the field of cosmetics benefiting the stability of the pyrazolidine-3,5-dione compound of formula (1).

Composition B), Dye composition

According to one embodiment of the present invention, a dye composition may be included in the dye kit of the present invention. The dye composition placed in the kit according to the present invention may comprise a dye 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 used at a weight ratio of 1:3 to 3:1, preferably 1:2 to 2:1, or preferably 2:3 to 1:1.

Dye composition I)

The dye composition placed in the kit according to the present invention comprises a dye composition I).

The dye composition I) of composition B) according to the present invention may comprise at least one oxidative dye.

Oxidative dye

As indicated above, the dye composition I) according to the invention comprises one or more oxidative dyes for use as component i).

The oxidative dyes which can be used in the present invention are generally chosen from oxidation bases, preferably combined with one or more couplers.

Preferably, the oxidative dye(s) comprise(s) one or more oxidation bases.

The oxidation bases can be chosen in particular from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the addition salts thereof, and mixtures of these.

Among the para-phenylenediamines, an unsubstituted para-phenylenediamine or a para-phenylenediamine substituted with 1 or 2 C1-C4 alkyls is preferred. Among others, examples that may be mentioned 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 para-phenylenediamines 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(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4- N,N–bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β -hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2 -β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thi enyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid, in particular a sulphate of these, for example, N,N-bis(β-hydroxyethyl)-para-phenylenediamine sulphate.

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

Among the para-aminophenols, an unsubstituted para-aminophenol or a para-aminophenol substituted with 1 or 2 C1-C4 alkyls is preferred. Among others, examples that may be mentioned 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-(β-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol, and addition salts of these with an acid.

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

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

Among the pyridine derivatives which may be mentioned are the compounds described, for example, in 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 addition salts thereof.

Other pyridine oxidation bases which are useful in the present invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308. Examples which may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[1,5-a]pyrid-3-ylamine , 2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl )ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6- diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholin-4- yl)pyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1,5-a ]pyrid-3-ylamine, 2-[(3-aminopyra zolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino ]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin- 6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol and addition salts thereof.

Among the pyrimidine derivatives which may be mentioned are 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 addition salts thereof and tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives which may be mentioned are the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, by example 4,5-diaminopyrazole, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3- phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole , 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino -3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and addition salts thereof. 4,5-diamino-1-(β-methoxyethyl)pyrazole can also be used.

4,5-diaminopyrazoles will preferably be used, for example, 4,5-diamino-1-hydroxy C1-C4 alkylpyrazole, and even more preferably 4,5-diamino-1-(β-hydroxyethyl) pyrazole and/or a salt thereof, in particular a sulfate thereof.

The oxidative dye(s) can also comprise one or more couplers, which can be chosen from those conventionally used for dyeing keratin fibres.

Among these couplers, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, couplers based on naphthalene, heterocyclic couplers, and also the addition salts thereof, and mixtures of these. In particular, unsubstituted meta-aminophenol or a meta-aminophenol substituted with 1 or 2 C1-C4 alkyls, unsubstituted meta-diphenol or a meta-diphenol substituted with 1 or 2 C1-C4 alkyls, diamino- phenols, or unsubstituted hydroxyindoles, amino-substituted hydroxypyridine, or hydroxybenzomorpholine may preferably be used.

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-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino -4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 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-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethyl pyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a] benzimidazole, the acid addition salts thereof, and mixtures thereof, such as the hydrochloride or dihydrochloride thereof, for example, 1-beta-hydroxyethyloxy-2,4 dihydrochloride -diamino-benzene (2,4-diaminophenoxyethanol HCl).

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

In a first exemplary embodiment for the oxidation base, examples include unsubstituted para-phenylenediamine or a para-phenylenediamine substituted with 1 or 2 C1-C4 alkyls.

In a second exemplary embodiment for the oxidation base, examples include an unsubstituted para-aminophenol or a para-aminophenol substituted with 1 or 2 C1-C4 alkyls, in particular a para-aminophenol unsubstituted.

In a third exemplary embodiment for the oxidation base, examples including 4,5-diaminopyrazoles will preferably be used, for example, 4,5-diamino-1-hydroxy C1-alkylpyrazole C4, or a salt thereof.

For the oxidation base, unsubstituted para-aminophenol or a para-aminophenol substituted with 1 or 2 C1-C4 alkyls is particularly mentioned.

In particular, for the coupler, the unsubstituted meta-aminophenol or a meta-aminophenol substituted with 1 or 2 C1-C4 alkyls, the unsubstituted meta-diphenol or a meta-diphenol substituted with 1 or 2 C1-C4 alkyls , diaminophenols, or unsubstituted hydroxyindoles, amino-substituted hydroxypyridine, or hydroxybenzomorpholine may preferably be used.

When an unsubstituted hydroxyindole, an amino-substituted hydroxypyridine, or a hydroxybenzomorpholine is used as coupler, it is preferably used in combination with the oxidation base according to the second mode embodiment given by way of example.

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

Further, 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 can be individually mentioned.

Among others, the combination of 4,5-diamino-1-(β-hydroxyethyl)pyrazole sulfate as oxidation base with 2-amino-3-hydroxypyridine as coupler, is particularly mentioned.

The oxidation base(s) can advantageously represent from 0.0001% to 10% by weight, preferably from 0.01% to 5% by weight and even more preferably from 0. 1% to 3% by weight, relative to the total weight of composition I).

The coupler(s), if present, can advantageously represent from 0.0001% to 10% by weight, and preferably from 0.005% to 5% by weight, relative to the total weight of composition I).

antioxidant

The dye composition I) can optionally comprise an antioxidant.

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

The antioxidant can include flavonoids. Flavonoids are an important class of over 5,000 polyphenol phytochemicals with antioxidant properties that act by direct scavenging of free radicals. Flavonoids have anti-inflammatory, antibacterial, antiviral, anti-allergic, anti-mutagenic, anti-thrombotic, anti-tumor and vasodilator effects and these modes of action can also be used to prevent, attenuate or eliminate oxidative damage of dental instruments. Flavonoids also exhibit chelating properties with metal ions and can mitigate oxidative damage to metal ions by chelating ions. The formation and stability of the flavonoid-metal chelate depends on the function of the structure. Flavonoids having a catechol moiety and having a hydrogen bond between the hydroxyl groups at position 5 and position 3 have chelating properties.

Vitamin C and its derivatives can be used, including ascorbic acid, erythorbic acid, or derivatives thereof, for example, sodium ascorbate/erythorbate and tetrahexyl decyl ascorbate/erythorbate d fat-soluble ester and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, glucosamine ascorbate, ascorbyl acetate, and others. In addition, 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 rose bush fruits and citrus fruits, including water-soluble bioflavonoids such as hesperidin methyl chalcone.

Sesamum indicum or a lignan can also be added. Sesame and its lignans (fibrous compounds associated with sesame) act as antioxidants. Sesame seed lignan significantly increases the activity of vitamin E.

Other antioxidants which may 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 ( eg d-α-tocotrienol, d-β-tocotrienol, d-γ-tocotrienol, d-δ-tocotrienol) and vitamin E (α-tocopheryl acetate). These compounds can be isolated from natural sources, prepared by synthetic means, or mixed. 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, cereal or palm oil using high performance liquid chromatography or from barley, distillers grains or oats by alcohol extraction and/or molecular distillation. The term "tocotrienol" as used herein 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.

Additionally, carotenoids, especially of the lutein types, are also useful antioxidants that can be utilized. Lutein-like carotenoids include molecules such as lutein, canthaxanthin, 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: scutellarin, eriodictin, hesperetin, hesperidin, sylvester, isosakuranetin, naringenin, naringin, pinocin, tangrine (poncirin), sakuranetin, sakura glycosides and 7 -O-methyl ergophenol (Sterubin).

The flavonoid may be a dihydroflavonol (a derivative of 3-hydroxy-2,3-dihydro-2-phenylbenzopyran-4-one). Flavanols include: Taxifolin, Aromadedrin, Chrysandroside A, Chrysandroside B, Xeractinol, Astilbin, and Flavonol.

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 a flavonoid ester.

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, kaempferol, isorhamnetin, mulberry pigment, myricetin, naringin (Natsudaïdain), Muskyl flavonol (Pachypodol), Quercetin, Methyl Rhamnosine, Rhamnetin, Azalein, Hyperoside, Isoquercetin, Kaempferol, Myricetin, Sweden Glycosides, Robinin, Rutin, Spiraea, Xanthorhamnine, L Amurensine, Icariine and Tracuridine.

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

The flavonoid may be a flavan-4-ol (a derivative of 2-phenylchroman-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 daidzein equol metabolites.

The antioxidant can be anthocyanin (a cation derivative of 2-phenylbenzopyranoside). Anthocyanins include: Aurantinidin, Cyanidin, Delphinidin, Europinidin, Luteolinidin, Pelargonidin, Malvidin, Peonyidin (Peonidin), Morning Glory Pigment (Petunidin), Rose Pigment (Rosinidin) and xanthone.

The antioxidant may be dihydrochalcone (a derivative of 1,3-diphenyl-1-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 can exert antioxidant effect by reducing active radicals such as active oxygen and reactive nitrogen species.

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

The antioxidant may be a phenylpropanoid (a derivative of cinnamic acid). Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including its pharmacore antioxidant 2,6-dihydroxy acetophenome), 5-hydroxyferric acid, sinapic acid , Coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, 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 chalcone (a derivative of 1,3-diphenyl-2-propen-1-one). Chalcone includes: Zirconia, Okanine, Safflower, Mareine, Sophoradine, Xanthohumol, Flavokvain A, Flavokvain B, Flavokvain C and Synthetic Safalcone.

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

The antioxidant may be a tannin. Tannins include: Tannins, Terflavin B, Glucogallin, Gallic Acid and Quercitannic Acid.

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 (ketotriol), 2,3',4,5'-Tetrahydroxyindole (oxidized resveratrol), 4,4'-dihydroxyindole and its derivatives alpha and beta glucoside, galactoside and mannoside.

The antioxidant may be a coumarin (a derivative of 2H-benzopyran-2-one). Coumarins include: 4-Hydroxycoumarin, Umbelliferone, Aesculetin, Herniarin, Auraptene and Dicoumarin.

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

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

The antioxidant can be: xanthone, butylated hydroxytoluene, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, gallic acid, eugenol, acid uric acid, α-lipoic acid, ellagic acid, cichoric acid, chlorogenic acid, rosmarinic acid, salicylic acid, acetylcysteine, S-allylcysteine, pyridone (Barbigerone), l Chebulagic Acid, Edaravone, Ethoxyquin, Glutathione, Hydroxytyrosol, Idebenone, Melatonin, N-Acetyl Serotonin, Nordihydroguaiaretic Acid, Oleotanthal, Oleuropein, Paradol, Paclitaxel , Probucol, Propyl Gallate, Protocatechuic Acid, Pyrithione, Rutin, Linseed Lignan Diglucoside, Sesamin, Sesame Phenol, Silybin, Silymarin, Theaflavins, Theaflavin Digallate, Thmoquinone , Trolox, tyrosol, polyunsaturated fatty acids and sulfur-based antioxidants such as methionine or lipoic acid.

Reducer

The dye composition I) may include a reducing agent for use as an antioxidant.

In accordance with the present invention, useful reductants may include sodium thiosulfate, sodium metabisulfite, ammonium thiourea sulfite, thioglycolic acid (TGA), thiolactic acid, ammonium thiolactate, diglycidyl ester of mono-carbothioic acid, carbothioic ammonium acetate, thioglycerol, dithio glycolic acid, carbothioic strontium diammonium acetate, thio glycolate, carbothioic isooctyl, cysteine, cysteamine, homocysteine , glutathione peptide, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiodiglycol, 2-mercaptoethanol, dithiothreitol, thioxanthin, thiosalicylic acid, thiopropionic acid, l lipoic acid, N-acetylcysteine and its salts; ammonium thioglycolate, glycerol monothioglycolate, or a mixture thereof.

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

The antioxidant, including the reducing agent, described above is preferably used according to the invention in an amount which may lie in a range of 0.001 to 10% by weight, preferably 0.1 to 7% by weight. , or preferably from 0.5 to 5% by weight, relative to the total weight of the dye composition I).

Surfactant

The dye composition I) according to the invention may comprise one or more surfactant(s), for example, in particular an anionic surfactant and/or a nonionic surfactant.

Anionic surfactant

The dye composition I) according to the invention may also comprise one or more anionic surfactant(s).

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen 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 parts comprising a cationic counterion such as an alkali metal, a metal alkaline earth or an ammonium.

As examples of anionic surfactants which can be used in the dye composition I) according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglycoside polycarboxylic acid and alkyl monoester salts, acyl lactylates, salts of D-galactoside uronic acids, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts, and corresponding non-salified compounds of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 40 carbon atoms and the aryl group designating a phenyl group.

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

The salts of C ₆ -C ₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids can be chosen from C ₆ -C ₂₄ alkyl polyglycoside -citrates, C ₆ -C ₂₄ alkyl polyglycoside -tartrates and C ₆ -C ₂₄ alkyl polyglycoside sulfosuccinates.

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

Examples of amino alcohol salts which may be particularly mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol , 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline earth metal salts, and in particular sodium or magnesium salts, are preferably used.

The preferred anionic surfactants are chosen from alkyl sulphates (C ₆ -C ₃₀ ), alkyl ether sulphates (C ₆ -C ₃₀ ), alkylamido sulphates (C ₆ -C ₃₀ ) ether , alkylaryl polyether sulfates and monoglyceride sulfates, all these compounds optionally comprising from 1 to 20 ethylene oxide units; or preferably from alkyl sulphates (C ₁₂ -C ₂₀ ) and alkyl ether sulphates (C ₁₂ -C ₂₀ ) comprising from 2 to 20 ethylene oxide units, for example, from 1 to 4 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline earth metal salts, or a mixture of these compounds. Even more preferably, it is preferable to use a polyoxyethylene sodium lauryl ether sulphate, such as a sodium lauryl ether sulphate containing 2 or 2.2 mol of ethylene oxide.

Preferably, the anionic surfactants of the invention are sulphates, more specifically are chosen from alkyl sulphates (C ₆ -C ₃₀ ), alkyl ether sulphates (C ₆ -C ₃₀ ), sulphates alkylamido (C ₆ -C ₃₀ ) ether, alkylaryl polyether sulphates and monoglyceride sulphates, their salts such as alkaline salts, such as sodium, and mixtures thereof.

Or preferably, the anionic surfactants of the invention are chosen from alkyl sulphates (C ₆ -C ₃₀ ), alkyl ether sulphates (C ₆ -C ₃₀ ), in particular alkyl ether sulphates (C ₆ -C ₃₀ ) such as lauryl ether sulphate, their salts, such as sodium laureth sulphate.

The amount of said anionic surfactant(s) in the dye 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

The dye composition I) according to the invention may additionally contain one or more nonionic surfactant(s).

The nonionic surfactant(s) which may be used in the compositions are described, for example, in the Handbook of Surfactants by MR Porter, published by Blackie & Son (Glasgow and London), 1991, pages 116-178.

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

- oxyalkylenated (C ₈ -C ₂₄ )alkylphenols;

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

- oxyethylenated fatty alcohols, saturated or unsaturated, linear or branched, C ₈ to C ₄₀ , in particular C ₈ -C ₂₀ and even more preferably C ₁₀ -C ₁₈ comprising from 1 to 100 mol of ethylene oxide , preferably from 2 to 50, more particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide;

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

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

- sucrose fatty acid esters;

- alkyl(poly)glucosides (in C ₈ -C ₃₀ ), alkenyl(poly)glucosides (in C ₈ -C ₃₀ ), which are optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising from 1 to 15 glucose units, esters (C ₈ -C ₃₀ ) alkyl (poly)glucoside;

- oxyethylenated vegetable oils, saturated or unsaturated;

- condensates of ethylene oxide and/or propylene oxide, among others, alone or in the form of mixtures;

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

- aldobionamides;

- amine oxides;

- oxyethylenated and/or oxypropylene silicones;

- and mixtures thereof.

The terms “oxyalkylenated”, “oxyethylenated”, “oxypropylene” and “glycerolated” cover, respectively, mono- or poly-oxyalkylenated, oxyethylenated, oxypropylene and glycerolated compounds, unless specifically mentioned otherwise.

The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

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

Advantageously, the nonionic surfactants according to the invention do not comprise oxypropylene units.

Examples may in particular include lauryl alcohol containing 4 mol of ethylene oxide (INCI name: Laureth-4) and lauryl alcohol containing 12 mol of ethylene oxide (INCI name: Laureth-12). Other examples may include OLETH-10, OLETH-30, DECETH-3, DECETH-5 and others.

As examples of glycerolated nonionic surfactants, use is preferably made of monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.

As examples of compounds of this type, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleyl/cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

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

The nonionic surfactant(s), when present in the dye composition I) according to the invention, are preferably present in a total amount lying within a range of 0.01 to 1 % by weight, relative to the total weight of composition I).

Solvent

The dye composition I) according to the invention can advantageously comprise one or more solvent(s), for example, water and/or an organic solvent.

Water

The dye 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).

The water content in the dye composition I) according to the invention is preferably in a range 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

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

Examples of water-soluble organic solvents which may be mentioned include linear or branched and preferably saturated monoalcohols or diols, 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; polyol ethers, for example ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol or ethers thereof, for example propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, in particular C ₁ -C ₄ alkyl ethers, for example diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

The water-soluble organic solvents, when present, generally represent between 1% and 40% by weight relative to the total weight of the dye composition I) according to the invention, and preferably between 3% and 20 % by weight, or between 4% and 10% by weight.

alkaline agent

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

The alkaline agent(s) can in particular be chosen from aqueous ammonia, alkali metal carbonates or bicarbonates, organic amines having a pKb at 25°C of less than 12 , in particular less than 10 and even more advantageously less than 6; among 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 the highest basicity.

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

Preferably, the amines are chosen from alkanolamines, in particular comprising a primary, secondary or tertiary amine function, and one or more linear or branched C ₁ -C ₈ alkyl groups bearing one or more hydroxyl radicals; from oxyethylenated and/or oxypropylene ethylenediamines, and from amino acids and compounds having the following formula:

in which W is a C ₁ -C ₆ alkylene residue optionally substituted by a hydroxyl group or a C ₁ -C ₆ alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl or C ₁ -C ₆ aminoalkyl radical.

According to one embodiment of the invention, the dye 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 an ethanolamine, or mixtures thereof.

Advantageously, the content of the alkaline agent(s) is within a range of 0.01% to 30% by weight, preferably 0.1% to 20% by weight, or 1 % to 15% by weight relative to the total weight of composition I). It should be noted that this content is expressed by NH ₃ when the alkaline agent is aqueous ammonia.

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

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

Fat phase

The dye composition I) according to the invention may additionally comprise a cosmetically acceptable fatty substance.

According to a particular embodiment, the fatty substance is free of carboxylic acid groups.

The term "fatty substance" means organic compounds which are insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility less than 5%, preferably 1% and even more more preferential by 0.1%). They may preferably have in their structure a sequence of at least two siloxane groups or at least one hydrocarbon-based chain comprising at least 6 carbon atoms. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for example chloroform, ethanol, benzene or decamethylcyclopentasiloxane.

The fatty substances are in particular chosen from lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, oils, in particular mineral, vegetable, animal or synthetic oils without silicone, waxes without silicone, and silicones.

It is recalled that, for the purposes of the invention, fatty alcohols, fatty esters and fatty acids more particularly contain one or more groups based on linear or branched, saturated or unsaturated hydrocarbons, 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 unsaturated, these compounds can have one to three conjugated or unconjugated carbon-carbon double bonds.

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

As non-silicone oils that can be used in the composition of the invention, examples that can be mentioned include:

- oils based on hydrocarbons of animal origin, such as perhydrosqualene;

- oils based on hydrocarbons of vegetable origin, such as triglycerides of liquid fatty acids containing from 6 to 30 carbon atoms, for example triglycerides of heptanoic or octanoic acid, or alternatively, for example, sunflower oil, corn oil, soybean oil, pumpkin seed oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for example those sold by the company Stéarineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel, jojoba oil and shea oil;

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

- fluorinated oils, for example perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.

The fatty alcohols which can be used in the composition of the invention are not oxyalkylenated. 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. Mention may be made of cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleylic.

The useful esters are the esters of C ₁ -C ₂₆ aliphatic mono- or polyacids, saturated or unsaturated, linear or branched, and of C ₁ -C ₂₆ aliphatic mono- or polyalcohols, saturated or unsaturated, linear or branched, the total number of carbon atoms of the esters being more particularly greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C ₁₂ -C ₁₅ 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; myristyl 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, myristyl myristate or stearyl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Still in the context of this variant, esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and C ₁ -C ₂₂ alcohols and esters of mono-, di- or tricarboxylic acids and di-, C ₂ -C ₂₆ tri-, tetra- or pentahydroxy alcohols can also be used.

The following may be particularly mentioned: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; 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.

The composition may also comprise, as fatty ester, sugar esters and diesters of C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. It is recalled that the term “sugar” means compounds based on oxygenated hydrocarbons containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise 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 derivatives thereof, in particular alkylated derivatives, such as methylated derivatives, for example methylglucose.

The sugar esters of fatty acids can be chosen in particular from the group comprising the esters or mixtures of sugar esters described above and of C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may have one to three conjugated or unconjugated carbon-carbon double bonds.

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

These esters can be chosen, for example, from oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, the mixed esters of oleo-palmitate, oleo-stearate and palmito-stearate.

It is more particularly preferable to use monoesters and diesters and in particular mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.

Advantageously, the content of fatty substance(s) is in a range 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).

Additives

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

For example, composition I) may comprise one or more additives which are well known in the art, such as anionic, nonionic or amphoteric polymers or mixtures thereof, agents to prevent hair loss, vitamins and provitamins including panthenol, derivatives of these vitamins (in particular esters) and mixtures thereof; sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifying agents, opacifiers, hydroxy acids, pearlescent agents, perfumes and preservatives.

It goes without saying that those skilled in the art will take care to select this or these optional additional compound(s) in such a way that the advantageous properties intrinsically associated with the invention are not, or are not materially adversely affected by the proposed addition(s).

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

The composition I) according to the invention can be in the form of fluid or thickened liquids, gels or creams, preferably cream.

Developer composition II)

The dye composition placed in the kit according to the present invention may comprise a developer composition II).

According to an embodiment of the present invention, the developer composition II) is placed separately from the dye composition I).

oxidant

Composition II) of composition B) according to the present invention comprises at least one oxidant.

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" is intended to refer to 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-like complex capable of releasing hydrogen peroxide.

Advantageously, the oxidant is hydrogen peroxide.

The concentration of the oxidant may be 0.1 wt% to 50 wt%, or preferably 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, on the basis of the weight of composition II).

Solvent

The developer composition II) of the present invention may comprise one or more solvent(s), for example, water and/or an organic solvent. The useful solvent can be selected from those mentioned for the “solvent” of composition I) above.

Composition I) and II) of dye composition B) may independently use the same or different solvents, respectively.

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

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

The water-soluble organic solvents, when present, generally represent between 0.01% and 10% by weight relative to the total weight of the dye composition I) according to the invention, and preferably between 0, 1% and 5% by weight, or between 0.5% and 1% by weight.

Surfactant

The developer composition II) according to the invention may comprise one or more surfactant(s), for example, in particular an anionic surfactant and/or a nonionic surfactant, preferably a nonionic surfactant. The useful surfactant can be selected from those mentioned for the “surfactant” of composition I) above.

Accordingly, the present invention can advantageously provide a dye kit, comprising:

a dye composition according to the present invention placed in a chamber 1; And

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

Method and use

An object of the invention is the oxidation retardant composition, in particular for the oxidation of oxidative dyes.

Another object of the invention is a process for dyeing human keratin fibres, in particular hair, using the dye kit as described above.

Another object of the invention is a method for reducing the staining tendency of a dye composition, using the dye kit as described above.

Another object of the invention is a method for slowing down reactions of dyes or intermediates, using the dye kit as described above.

The invention also relates to the use of the dyeing kit as described above for dyeing keratin fibres, in particular the hair.

The invention also relates to the use of the dye kit as described above to reduce the staining tendency of the dye kit.

The invention also relates to the use of a dye kit as described above to slow down reactions of dyes or intermediates, using the dye kit as described above.

In particular, the invention relates to a process for slowing down dye reactions or intermediates thereof, characterized in mixing the retarding composition A) comprising a pyrazolidine-3,5-dione compound of formula (1) and the chelating agent 2) with the tincture.

Preferably, the delay composition A) is mixed with the dye before application of the dye, or the delay composition A) is applied at the position at which the dye has been applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes.

The present invention also relates to the use of the retardant composition A) to reduce the staining tendency of a dye.

In another aspect, the present invention relates to the use of a retarder composition A) for dyeing keratin fibres, while reducing the formation of stains in areas other than the keratin fibres, in which the retarder composition A) comprises a pyrazolidine-3,5-dione compound of formula (1) and a water-soluble chelating agent selected from carboxylic acids comprising at least one heteroatom in addition to the carboxylic group.

As stated above in the section "Additional Form of Composition A)", Composition A) can be provided in various forms to be used with Dye Composition I) and Developer Composition II), so as to slow down the reaction of the dye. In particular, if composition A) is placed in a chamber 2 separated from a chamber 1, for the dyeing kit described according to the present invention:

- if the user does not wish to slow down the dyeing, or the formation of stains by the dyeing is not a concern, chamber 2 may not be used;

- if the user wishes to avoid any stain, he can mix chamber 2 with 1 before dyeing;

- if the user wishes to determine the use or not of chamber 2 according to the appearance or not of an actual stain, he can first of all use only chamber 1, and when the dye composition adheres to hand or any other place, Chamber 2 can be immediately applied; And

- if the user wishes to avoid the formation of stains, and wishes a quick dyeing, he can apply the chamber 2 in advance to positions on which stains are most likely to appear but must be avoided, for example the hands.

Alternatively, if composition A) is provided together with dye composition I), for example, being added directly to composition I), the dyeing process is always slowed down, compared to the same dyeing process except of the absence of composition A).

The mixed compositions, including dye composition I) and developer composition II), and optionally composition A), are usually left in place on the fibers for a time generally in the range of 1 minute to 1 hour. and preferably from 5 minutes to 30 minutes.

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

The process can be repeated several times to obtain the desired color.

The dyeing kit mentioned above can also be equipped with a means allowing the distribution of the desired mixture on the hair, such as, for example, the device described in patent FR 2 586 913.

The following examples are given purely by way of illustration of the present invention.

EXAMPLES:

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

Example 1

The dye compositions of the invention I-A to I-C and the comparative dye composition I-D below were prepared from the ingredients indicated in Table 1 below (in which the contents were indicated in % by weight of materials by relative to the total weight of the composition):

Components AI IB IC ID LAURIC ACID 3,000 3,000 3,000 3,000 OLETH-30 4,000 4,000 4,000 4,000 LAURETH-12 7,000 7,000 7,000 7,000 DECETH-3 10,000 10,000 10,000 10,000 PROPYLENE GLYCOL 7,000 7,000 7,000 7,000 HEXADIMETHRIN CHLORIDE 5,000 5,000 5,000 5,000 GLYCOL DISTEARATE 2,000 2,000 2,000 2,000 CETEARYL ALCOHOL 11,500 11,500 11,500 11,500 m-AMINOPHENOL 0.088 0.088 0.088 0.088 N,N-BIS(2-HYDROXYETHYL)-p-PHENYLENEDIAMINE SULFATE 0.099 0.099 0.099 0.099 RESORCINOL 0.638 0.638 0.638 0.638 p-PHENYLENEDIAMINE 0.682 0.682 0.682 0.682 PYRAZOLIN-3,5-DIONE 2,500 2,500 2,500 2,500 EDTA 2,200 0.200 0.200 0.200 ASCORBIC ACID 0.250 0.250 0.250 0.250 SODIUM METABISULPHITE 0.710 0.710 0.710 0.710 ETHANOLAMINE 1,350 1,350 1,350 1,350 AMMONIUM HYDROXIDE 11,100 11,100 11,100 11,100 DISODIUM EDTA - 2,000 - - TETRASODIUM GLUTAMATE DIACETATE - - 0.500 - WATER QS QS QS QS

The developer composition II below was prepared from the ingredients indicated in Table 2 below (in which the contents were indicated in% by weight of materials relative to the total weight of the composition):

Ingredients II-A HYDROGEN PEROXIDE 12 TETRASODIUM ETIDRONATE 0.2 TETRASODIUM PYROPHOSPHATE 0.04 SODIUM SALICYLATE 0.035 GLYCERIN 0.5 TRIDECETH-2 CARBOXAMIDE MEA 0.85 CETEARYL ALCOHOL (and) CETEARETH-25 2.85 WATER QS

Example 2

For application, the following steps were performed to show stain resistance performance:

- 4 g of compositions I-A~D were added respectively with 6 g of composition II-A at a weight ratio of 1:1.5, in the same bowl;

- compositions I-A~D were respectively well mixed with composition II-A using a brush, to provide mixtures A to D;

- mixtures A to D were each applied to 1 g of lock of hair on the hot plate of 27°C and were gently brushed to ensure that the entire lock was impregnated with the mixtures;

- photos were taken every 10 min, to record the experience;

- after 20 min, the locks and the brushes were turned over;

- after 40 min, the locks were washed respectively in beakers with 400 ml of water, then washed with shampoo, and dried with a hair dryer; And

- the stain resistance performance of the blends was rated by an internal panel of experts from 0 to 10, where 10 represented completely clean, and 0 represented extremely dirty.

[Table 3] Stain Resistance Performance Performance Blend A Blend B Blend C Blend D Rinse water Very clean Own Very clean slightly dirty Internal score
(0-10) 9 8 9 6

Photos corresponding to the stain resistance performance shown in Table 3 above have been provided on the .

Claims (10)

Oxidation retardant composition, comprising components of:
1) a water-soluble chelating agent selected from carboxylic acids comprising at least one heteroatom in addition to the carboxylic group;
2) a pyrazolidine-3,5-dione compound of formula (1):
(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, heterocyclic or alkoxy, such as C1-C10 alkyl or C1-C10 alkyl substituted by halogen, preferably C1-C6 alkyl or C1-C6 alkyl substituted by halogen, C3 alkenyl -C10, a C3-C10 cycloalkyl, a C3-C10 heterocyclic alkyl or a C3-C10 epoxylalkyl; and R ₃ is H, or unsubstituted or halogen-substituted C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 unsaturated heterocyclic group, C3-C10 heterocyclic alkyl, or C3-C10 alkoxy. C3-C10, such as C1-C6 alkyl or C1-C4 alkyl, preferably H, wherein the halogen is preferably F, Cl or Br. A retarding composition according to claim 1, wherein the chelating agent is selected from the group consisting of aminocarboxylic acids, hydroxyl carboxylic acids, hydroxyl aminocarboxylic acids, polyphosphonic acid, another phosphorus-containing organic acid, and the alkali metal salt thereof. A delay composition according to any preceding claim, wherein the chelating agent is selected from the group consisting of EDTA, citric acid, GLDA, phytic acid, sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS and sodium phytate. A delay composition according to any preceding claim, wherein R ₁ and R ₂ are each C1-C6 alkyl or C1-C4 alkyl; and/or R ₃ is H. A delay composition according to any preceding claim, 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. Use of the retarding composition according to any one of the preceding claims, for dyeing involving a relatively high concentration of polyvalent metal ions, such as Cu ²⁺ and/or Fe ³⁺ . A method of reducing the staining tendency of a dye or intermediates thereof, characterized in that the mixture of the retarding composition according to any one of claims 1 to 5 with the dye, in which the retarding composition is mixed with the dye before application of the dye, or the retarding composition is applied at the position at which the dye has been applied for less than 10 minutes, less than 5 minutes, or less than 3 minutes . Dye kit for the oxidative dyeing of keratin fibres, comprising the compositions of:
A) a delay composition according to any one of claims 1 to 5; And
B) a dye composition comprising an oxidative dye;
wherein the dye composition B) comprises:
I) a dye composition I), comprising:
i) at least one oxidative dye;
wherein the oxidative dye comprises one or more oxidation bases selected from the group consisting of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, meta-aminophenols, ortho-aminophenols, heterocyclic bases, and addition salts thereof, and mixtures thereof;
and or
wherein the oxidative dye further comprises one or more couplers to be combined with the oxidation base, which is selected from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers , heterocyclic couplers, and addition salts thereof, and mixtures thereof. A dye kit according to claim 8, further comprising an AMPS polymer, which is preferably cross-linked or non-cross-linked homopolymers or copolymers comprising at least the monomer of acrylamido-2-methylpropanesulfonic acid. A dye kit according to claim 9, wherein the AMPS polymer is selected from sodium acrylamido-2-methylpropanesulfonate homopolymer, or ammonium polyacryloyldimethyl taurate homopolymer, AMPS/hydroxyethyl acrylate copolymer, or a cross-linked polymer of ammonium acryloyldimethyltaurate/steareth-25 methacrylate.