CA2754959A1 - A 5-amino-1,2,3,4-tetrahydroquinoline derivative and 4,5-diamino-pyrazole derivative for oxidative dyeing of keratin fibers - Google Patents

Abstract

An oxidative dyeing composition comprising a combination of 5-amino-1,2,3,4-tetrahydroquinoline derivative according to formula (I) in combination with 4,5-diamino-pyrazole derivative of formula (II).
(see formula I)(see formula II).

Description

A 5-AMINO-1,2,3,4-TETRAHYDROQUINOLINE DERIVATIVE AND 4,5-DIAMINO-PYRAZOLE DERIVATIVE FOR OXIDATIVE DYEING OF KERATIN FIBERS

FIELD OF THE INVENTION

The present invention relates to a composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline derivative as defined in formula (I) hereafter, a physiologically compatible water-soluble salt thereof, or mixtures thereof, (B) a 4,5-diamino-pyrazole derivative as defined in formula (II) hereafter, a physiologically compatible water-soluble salt thereof, or mixtures thereof, and (C) an oxidizing agent.
BACKGROUND OF THE INVENTION

The oxidative dyeing process using one or more oxidative hair coloring precursors in combination with one or more oxidizing agent is the most extensively used method to color hair.
Commonly, a peroxy oxidizing agent is used in combination with one or more primary intermediates and/or couplers, generally small molecules capable of diffusing into hair. A wide variety of primary intermediates and couplers have been employed in such oxidative hair coloring systems and compositions. Selection of specific combination of couplers and primary intermediates has also shown to provide some additional color benefits.
Besides providing the desired colour, these dye precursors used for oxidative hair coloring have to also meet some additional requirements. Indeed, the combination of couplers and primary intermediates used in this coloration process should deliver the desired intensity together with good light fastness, permanent wave fastness, acid fastness, and rubbing fastness and remain stable over a period of at least 4 to 6 weeks.
Compositions of the prior art comprising 5-amino-1,2,3,4-tetrahydroquinoline derivatives do not satisfy the above mentioned requirements in all aspects. Oxidative dyeing compositions comprising 5-amino-1,2,5,4-tetrahydroquinoline as coupler component is known, see DE
2441895. However, this disclosure does not exemplify a combination of 5-amino-1,2,3,4-tetrahydroquinoline derivative and 4,5-diamino-pyrazole derivative.

The oxidative dyeing composition of the invention overcomes known color intensity-drawbacks together with color-rich shades, good resistance against shampooing and rubbing- It has surprisingly been found that the composition of the invention provides color-rich shades, which are resistant against shampooing and rubbing.

SUMMARY OF THE INVENTION

According to a first aspect the present invention relates to a composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, comprising (A) a 5-amino-l,2,3,4-tetrahydroquinoline compound of general formula (I), a physiologically compatible water-soluble salt thereof, or mixtures thereof; (B) a 4,5-diamino-pyrazole compound of general formula (II), a physiologically compatible water-soluble salt thereof, or mixtures thereof;
and (C) an oxidizing agent;

CN R N N\ NR7R8 (I) (II) wherein R1, R2, R3, R4, R5., R6, R7, Rg, R9 are further defined hereinafter.
According to a second aspect the present invention relates to a method of dyeing hair comprising the steps of:
(i) providing a tint component comprising (A) a 5 -amino- 1,2,3,4-tetrahydroquinoline derivative compound of the general formula (I), a physiologically compatible water-soluble salt thereof, or mixtures thereof; and (B) a 4,5-diamino-pyrazole derivative of the general formula (II), a physiologically compatible water-soluble salt thereof, or mixtures thereof;
(ii) providing a developer component comprising (C) an oxidizing agent;
(iii) mixing the tint component and the developer component to obtain a composition for the oxidative dyeing of keratin fibers; and (iv) applying said composition for the oxidative dyeing of keratin fibers onto the hair.
According to a third aspect, the present invention relates to a kit comprising: (i) a tint component comprising (A) a 5 -amino- 1,2,3,4-tetrahydroqu inoline compound of general formula (I), a physiologically compatible water-soluble salt thereof, or mixtures thereof; (B) a 4,5-diamino-pyrazole compound of general formula (II), a physiologically compatible water-soluble salt thereof, or mixtures thereof; and (ii) a developer component comprising (C) an oxidizing agent.
DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "composition for the oxidative dyeing of keratin fibers" means a ready-to-use composition in a suitable carrier medium for dyeing keratin fibers, in particular human hair, comprising oxidative dye precursors (primary intermediates and couplers) and an oxidizing agent. These compositions can typically be the result of a mixture of two compositions namely a tint component comprising the dye precursors and usually an alkalizing agent such as ammonia and a developer component comprising the oxidizing agent.
As used herein, the term "keratin" refers to a scleroprotein found in epidermal tissues and modified into hard structures such as horns, hair, and nails. As used herein, the term "hair" refers to keratinous fibers on a living, e.g. a person, or non-living body, e.g. in a wig, hairpiece, or other aggregation of non-living keratinous fibers. Mammalian, preferably human, hair is preferred.
Notably, hair, wool, fur, and other keratinous fibers are suitable substrates for coloring by the compounds and compositions described herein.
As used herein, the term "dye precursors" refers to compounds that may be used in the composition to act as primary intermediates, couplers, or both, in order to provide color to ketatinous fibers.
It is to be understood that when this development refers to a particular structure, all of the reasonable additional tautomeric structures are included. In the art, tautomeric structures are frequently represented by one single structure and the invention follows this general practice.
The 5-amino-1,2,3,4-tetrahydroquinoline compound of general formula (I), a physiologically compatible water-soluble salt, or mixtures thereof are defined as following:

CN Rr (1) R1, R2 and R3 are substituents selected independently of each other from the group consisting of:
(a) C-linked substituents selected from the group consisting of-(i) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems, (ii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl systems, and (iii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, heteroaryl systems, and wherein said systems of (i), (ii) and (iii) comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of 0, F, N, P and Si;

(b) S -linked substituents selected from the group consisting of SA', S02A', SO3A', SSA', SOA', SO2NA'A2, SNA'A2, and SONA'A2;
(c) O-linked substituents selected from the group consisting of OA', ONA'A2;
(d) N-linked substituents selected from the group consisting of NA'A2, (NA'A2A3)+
NA'SA2, NO2, NA'A2;

(e) substituents selected from the group consisting of COOA', CONA', CONA'COA2, C(=NA')NA2A3, CN, and X;

(f) fluoroalkyl substituents selected from the group consisting of mono-, poly-, and per-fluoro alkyl systems comprising from 1 to 12 carbon atoms and from 0 to 4 heteroatoms; and (g) H;

wherein A', A2, and A' are selected independently of each other from the group consisting of. H; mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems; mono- or poly-substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl or heteroaryl systems; and substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems; or A' and A2 together with nitrogen atoms to which they are bound form a ring; wherein said systems comprise from I to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of 0, S, N, P, and Si; and wherein X is a halogen selected from the group consisting of F, Cl, Br, and I.

Suitable physiologically compatible water soluble salts of formula (I) are also included such as chlorides, bromides, sulfates, such as hemisulfates, tartrates, lactates, malates and acetates.

In a preferred embodiment, R,, R2 and R3 are selected independently of each other from the group consisting of a hydrogen atom; a halogen atom; an amino substituent, a hydroxyl substituent; a cyano substituent; a Cl-C4 alkyl substituent; a trifluoromethyl substituent; an alkylamino substituent; a hydroxyalkylamino substituent; an acetylamido substituent; a carboxyl substituent or its esters; an alkoxy substituent; an alkoxyalkyl substituent;
a carbamoyl substituent; an alkylcarbamoyl substituent; a hydroxyalkylcarbamoyl substituent; an amido substituent; an alkylamido substituent; an alkylcarbonyl substituent; an alkoxycarbonyl substituent; an aryloxy substituent; an acyloxy substituent; an alkylthio substituent; an arylthio substituent; a heteroarylthio substituent; a heteroaryloxy substituent; a thiocyano substituent; a 3-, 4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen, oxygen or sulfur atom; an aryl substituent which is optionally substituted; a sulfonyl substituent; a sulfinyl substituent; a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent; an acyloxy substituent; a carbamoyloxy substituent; a sulphonamide substituent; an imide substituent; a ureido substituent;
a sulfamoylamino substituent; an alkoxycarbonylamino substituent; an aryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and a benzenesulfonamido substituent.

5 The 5-amino-1,2,3,4-1:etrahydroquinoline derivative (I) may be a compound with formula N
H
(LI) The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with formula (1.2) The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with formula (1.3):

N
H OH
(1.3) The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with formula (1.4):

N
H
(1.4) In order to reach the desired hair color, the 5-amino-1,2,3,4-tetrahydroquinoline derivative of formula (I) needs to be combined with a primary intermediate, in particular but not limited to an 4,5-diamino-pyrazole derivative of general formula (II) hereafter, a physiologically compatible water-soluble salt thereof, or mixtures thereof:

N' N NR7R8 (II) wherein R4 has the same definition given above for R1, R2, R3 of the 5-amino-1,2,3,4-tetrahydroquinoline compound of general formula (I);
wherein R5, R6, R7, R8 and R9 are substituents selected independently of each other from the group consisting of.

(h) C-linked substituents selected from the group consisting of-(i) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems, (ii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl systems, and (iii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, heteroaryl systems, and wherein said systems of (i), (ii) and (iii) comprise from about 1 to 10 carbon atoms and from about 0 to 5 heteroatoms selected from the group consisting of 0, F, N, P
and Si;
(i) substituents selected from the group consisting of COOA', CONA', CONA'COA2, C(=NA')NA'A2, CN; and (j) H;
Preferably R4, R5, R6. R7, R8 and R9 are substituents selected independently of each other from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 hydroxalkyl, C2-C4 alkoxy and mixtures thereof.

In a preferred embodiment the 4,5-diamino pyrazole derivative (II) is a compound with formula (11.1):

N_N\ NH2 OH
(I1.l) Oxidizing Agent The compositions of the invention comprise an oxidizing agent. Typical suitable oxidizing agents for the oxidative dyeing of keratin fibers may be selected from hydrogen peroxide, sodium periodate, urea peroxide, melamine peroxide, perborates, percarbonates, perphosphates, persilicates, persulfates, oxidizing enzymes such as uricases, oxidases, and peroxidases, and mixtures thereof. Hydrogen peroxide, perborates, or percarbonates may be preferred. Another potential oxidizing agent for use herein is a source of peroxymonocarbonate ions. Preferably, such a source is formed in situ from a source of hydrogen peroxide and a hydrogen carbonate ion source. Such an oxidizing agent has been found to be particularly effective at a pH of up to and including 9.5, preferably from about 7.5 to about 9.5 more preferably about pH 9. Moreover, this system is also particularly effective in combination with a source of ammonia or ammonium ions.
Accordingly, any source of these peroxymonocarbonate ions may be utilized.
Suitable sources for use herein include sodium, potassium, guanidine, arginine, lithium, calcium, magnesium, barium or ammonium salts of carbonate, carbamate and hydrocarbonate ions and mixtures thereof. In particular, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, ammonium carbonate, ammonium hydrogen carbonate and mixtures thereof may be preferred.
Percarbonate salts may also be utilized to provide both the source of carbonate ions and as an oxidizing agent.
Preferred sources of carbonate ions, carbamate and hydrocarbonate ions are sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium carbamate, and mixtures thereof.
The hair dyeing composition may usually comprise from about 1% to about 15% by total weight of the composition, typically from about 1.5% to about 10% by weight, and more typically from about 2% to about 8% by weight of the oxidizing agent relative to the total weight of the composition.

The oxidizing agent may be provided in a developer component which is mixed to a tint component to obtain the composition of the invention. The developer component may be based on any desired formulation chassis, including any commercial product, for example an oil-in-water emulsion. Typical developer components comprise about 6% or about 9% of H202 by total weight of the composition. A commercial example is the Welloxon Emulsion with respectively about 6% and about 9% H2O2, marketed by Wella and comprising as INCI
ingredients: Water, Hydrogen Peroxide, Cetearyl Alcohol, Ceteareth-25, Salicylic Acid, Phosphoric Acid, Disodium Phosphate, Etidronic Acid.

The hair dyeing composition of the invention may be formed as thick liquid, cream, gel, emulsion, foam, aerosol mousse or as a solid form to which water is added to generate the oxidant and form a thickened vehicle suitable for hair coloring. They may comprise in addition to the ingredients indicated above further ingredients in order to further enhance the properties of the composition, including but not limited to: solvents; oxidative dyes, direct dyes; oxidizing agents; radical scavengers; thickeners and or rheology modifiers; chelants; pH
modifiers and buffering agents; carbonate ion sources; peroxymonocarbonate ion sources;
anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof;
anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or mixtures thereof; fragrances; enzymes;
dispersing agents; peroxide stabilizing agents; antioxidants; natural ingredients, e.g.
proteins and protein compounds, and plant extracts; conditioning agents including silicones and cationic polymers, ceramides, preserving agents; and opacifiers and pearling agents (such as titanium dioxide and mica). Some adjuvants referred to above, but not specifically described below, which are suitable are listed in the International Cosmetics Ingredient Dictionary and Handbook, (8th ed.; The Cosmetics, Toiletry, and Fragrance Association). Particularly, vol. 2, sections 3 (Chemical Classes) and 4 (Functions) are useful in identifying specific adjuvants to achieve a particular purpose or multipurpose. A few of these ingredients are discussed hereinbelow, whose disclosure is of course non-exhaustive.
Alkalizing agent The composition for the oxidative dyeing of keratin fibers may further comprise, generally in the tint component, an alkalizing agent as known in the art. Any alkalizing agent known in the art may be used such as ammonia, alkanolamines for example monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-l-propanol, and 2-amino-2-hydroxymethyl-1,3-propanediol, guanidium salts, alkali metal and ammonium hydroxides such as sodium hydroxide, alkali metal and ammonium carbonates, and mixtures thereof. Typical alkalizing agents are ammonia and/or monoethanolamine.

Typically, the compositions for the oxidative dyeing of keratin fibers comprise from about 0.1% to about 10%, preferably from about 0.5% to about 6%, more preferably from about 1% to about 4% by weight of the alkalizing agent relative to the total weight of the composition.

Primary intermediates In addition to the pyrazole compounds of the invention, the hair dyeing compositions of the invention may comprise further primary intermediates. Suitable primary intermediates for use in the compositions described herein include, but are not limited to: toluene-2,5-diamine, p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine), 2-methoxymethyl-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, 2,2'-(2-(4-arninophenylamino)ethylazanediyl)diethanol, 2-(2,5-diamino-4-methoxyphenyl)propane- 1,3 -diol, 2-(7-amino-2H-benzo[b][I,4]oxazin-4(3H)-yl)ethanol, 2-chloro-p-phenylenediamine, p-aminophenol, p-methylaminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 5-ethyl -o-aminophenol, 2-methoxy-p-phenylenediamine, 2,2'-methylenebis-4-aminophenol, 2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-pyrimidinol, 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 4,5-diamino-l-methylpyrazole, 4,5-diamino-l-ethylpyrazole, 4,5-diamino-l-isopropylpyrazole, 4,5-diamino-l-butylpyrazole, 4,5-diamino-l-pentylpyrazole, 4,5-diamino-l-benzylpyrazole, 2,3-diamino-6,7-dihydropyrazolo[1,2-a]pyrazol-1(5H)-one dimethosulfonate, and mixtures thereof.
Typically, the compositions for the oxidative dyeing of keratin fibers comprise from about 0.1% to about 10%, preferably from about 0.3% to about 6%, more preferably from about 0.5% to about 4% by weight of the primary intermediates relative to the total weight of the composition.
Couplers In addition to the quinoline compounds of the invention, the hair dyeing compositions of the invention may comprise couplers to obtain various shades. Suitable couplers for use in the compositions described herein include, but are not limited to: resorcinol, 4-chlororesorcinol, 2-chlororesorcinol, 2-methylresorcinol, 4,6-dichlorobenzene-1,3-diol, 2,4-dimethylbenzene-1,3-diol, m-aminophenol, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dim ethyl phenol, 3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol, 5-amino-4-chloro-o-cresol, 6-hydroxybenzomorpholine, 2-amino-5-ethylphenol, 2-amino-5-phenylphenol, 2-amino-5-methylphenol, 2-am ino-6-methylphenol, 2-am ino-5-ethoxyphenol, 5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol, 2-amino-4-hydroxyethylaminoanisole, 1,3-bis-(2,4-d iaminophenoxy)-propane, 2,2'-(2-methyl-1,3-phenylene)bis(azanediyl)diethanol, benzene- l,3-diamine, 2,2'=(4,6-diamino-1,3-phenylene)bis(oxy)diethanol, 3-(pyrrolidin-l-yl)aniline, 1-(3-(dimethylamino)phenyl)urea, 1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-l-naphthol, 1,5-naphthalenediol, 2,7-naphthalenediol or 1-acetoxy-2-methylnaphthalene, 4-chloro-2-methylnaphthalen-1-ol, 4-methoxy-2-methylnaphthalen-l-ol, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, pyridine-2,6-diol, 5,6-5 dihydroxyindole, 6-hydroxyindole, 5,6-dihydroxyindoline, 3-methyl-l-phenyl-lH-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene, 2-(benzo[d][1,3]dioxol-5-ylamino)ethanol (also known as hydroxyethyl-3,4-methylene(lioxyaniline), and mixtures thereof. When the composition is obtained by mixing a tint component and a developer component, additional primary intermediates and couplers may be preferably incorporated in the tint component.

10 Typically, the compositions for the oxidative dyeing of keratin fibers comprise from about 0.1% to about 10%, preferably from about 0.3% to about 6%, more preferably from about 0.5% to about 4% by weight of the couplers relative to the total weight of the composition.
Direct Dyes The compositions of the present invention may also comprise compatible direct dyes, in an amount sufficient to provide additional coloring, particularly with regard to intensity.
Typically, such an amount will range from about 0.05% to about 4%, by weight of the direct dyes relative to the total weight of the composition. When the composition is obtained by mixing a tint component and a developer component, the direct dyes are usually incorporated in the tint component.
The following direct dyes are commonly used: Acid dyes such as Acid Yellow 1, Acid Orange 3, Acid Black 1, Acid Black 52, Acid Orange 7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Violet 43, HC Blue 16, Acid Blue 62, Acid Blue 25, Acid Red 4, Basic Dyes such as Basic Brown 17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown 16, Basic Yellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2, Basic Blue 99, Basic Yellow 29, Basic Red 51, Basic Orange 31, Basic Yellow 87, 4-(3-(4-amino-9,10-dioxo-9,10-dihydroanthracen-l-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate, (E)-1-(2-(4-(4,5-dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-3-ium chloride, (E)-4-(2-(4-(dimethylamino)phenyl)diazenyl)-1-methyl-1 H-imidazol-3-ium-3-yl)butane-l -sulfonate, (E)-4-(4-(2-methyl -2-phenyl hydrazono)methyl)pyridinium-l-yl)butane-l-suIfonate, N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,I0-tetrahydroanthracen-1-ylamino)-N-propylpropan-l-aminium bromide, Disperse Dyes such as Disperse Red 17, Disperse Violet 1, Disperse Red 15, Disperse Violet 1, Disperse Black 9, Disperse Blue 3, Disperse Blue 23, Disperse Blue 377, Nitro Dyes such as 1-(2-(4-nitrophenylamino)ethyl)urea, 2-(4-methyl-2-nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine, 2-nitrobenzene-1,4-diamine, Picramic acid, HC Red No. 13, 2,2'-(2-nitro-1,4-phenylene)bis(azanediyl)diethanol, HC
Yellow No. 5, HC
Red No. 7, HC Blue No.2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No. 1, HC
Red No.
1, 2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HC Red No. 3, 4-amino-3-nitrophenol, 4-(2-hydroxyethylamino)-3-nitrophenol, 2-amino-3-nitrophenol, 2-(3-(methylamino)-4-nitrophenoxy)ethanol, 3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No.
11, HC Violet No. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10, HC
Red No. 11, 2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No. 12, HC Yellow No. 6, HC
Yellow No.

12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HC Blue No. 9, 2-chloro-(ethylamino)-4-nitrophenol, 6-nitropyridine-2,5-diamine, HC Violet No. 2, 2-amino-6-chloro-4-nitrophenol, 4-(3-hydroxypropylamino)-3-nitrophenol, HC Yellow No. 13, 6-nitro-1,2,3,4-tetrahydroquinoxaline, HC Red No. 14, HC Yellow No. 15, HC Yellow No. 14, N2-methyl-6-nitropyridine-2,5-diamine, N 1-allyl-2-nitrobenzene-l,4-diamine, HC Red No. 8, HC Green No.1, HC Blue No. 14, and Natural dyes such as Annato, Anthocyanin, Beetroot, Carotene, Capsanthin, Lycopene, Chlorophyll, Henna, Indigo, Cochineal.
Thickeners The hair dyeing compositions of the present invention may comprise a thickener in an amount sufficient to provide the composition with a viscosity so that it can be readily applied to the hair without unduly dripping off the hair and causing mess. Typically, such an amount will be at least 0.05%, preferably at least 0.5%, more preferably at least 1%, by weight of thickener relative to the total weight of the composition. When the composition is obtained by mixing several components, the thickener may be present in any of the components.
Preferred for use herein are salt tolerant thickeners, including but not limited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose, ethyl cellulose (available as AQUACOTE(TM)), hydroxyethyl cellulose (NATROSOL(TM)), carboxymethyl cellulose, hydroxypropylmethyl cellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose, hydroxypropyl cellulose (available as KLUCEL(TM)), hydroxyethyl ethyl cellulose, cetyl hydroxyethyl cellulose (available as NATROSOL(TM)) Plus 330), N-vinylpyrollidone (available as POVIDONE(TM)), Acrylates/Ceteth-20 Itaconate Copolymer (available as STRUCTURE(TM) 3001), hydroxypropyl starch phosphate (available as STRUCTURE(TM) ZEA), polyethoxylated urethanes or polycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer (available as ACULYN(TM) 44), PEG-150/Stearyl/SMDI copolymer available as ACULYN(TM) 46), Acrylates/Beheneth-25 Methacrylate Copolymer (available as ACULYN(TM) 28), Acrylates/Vinyl Neodecanoate Crosspolymer (available as ACULYN(TM) 38), Acrylates/Steareth-20 Methacrylate Crosspolymer (available as ACULYN(TM) 88), Distearate (available as ACULYN(TM) 60), trihydroxystearin (available as THIXCIN(TM)), acrylates copolymer (e.g. available as ACULYN(TM) 33) or hydrophobically modified acrylate copolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer (available as ACULYN(TM) 22), non-ionic amphophilic polymers comprising at least one fatty chain and at least one hydrophilic unit selected from polyether urethanes comprising at least one fatty chain.
Also preferred for use herein are thickeners based on lamellar gel network systems, comprising at least one surfactant or amphophile having an HLB of 6 or less and a melting point of at least 30 C, preferably selected from fatty alcohols comprising from 14 to 30 carbon atoms, or oxyethylenated fatty alcohols comprising from 16 to 30 carbon atoms and 2 units or less of ethylene oxide, and further comprising at least one ionic or nonionic surfactant, preferably selected from:

anionic surfactants selected from C8-C30 alkyl sulfates, preferably C12-C18 alkyl sulfates, anionic surfactants according to the formula RfX,,,YM, wherein R is independently selected from alkyl, alkenyl or alkylaryl groups having from 8 to 30 carbon atoms, X is independently selected from polar groups comprising at least one carbon atom and at least one oxygen or nitrogen atom, Y is an anionic group selected from carboxylates, sulfates, sulfonates or phosphates, n and m are independently 1 or 2, and M is hydrogen or a salt forming cation and mixture thereof, most preferably selected from C8-C30 alkyl ether phosphates having from 1 to 20, preferable 2 to 10 ethylene oxide units (e.g. available as CRODAFOS(TM) CES);
non-ionic surfactant comprising one or more polyethyleneoxide chains, preferably each polyethyleneoxide chain has on average at least 50 ethylene oxide units and most preferably 100 to 200 ethylene oxide units (e.g. available as VOLPO(TM) S200), cationic surfactants selected from quaternary ammonium salts or amido-amines having at least one fatty chain, preferably comprising at least 16 carbon atoms and most preferably at least 20 carbon atoms, - and mixture thereof.
Examples of such lamellar gel network systems are disclosed in EPI,832,273 and EP2,103,299.

The composition preferably comprises a mixture of cetearyl alcohol and dicetyl phosphate and ceteth-10 phosphate (e.g. available as CRODAFOS(TM) CES).

Chelants The compositions of the present invention may comprise chelants in an amount sufficient to reduce the amount of metals available to interact with formulation components, particularly oxidizing agents, more particularly peroxides and percarbonates. Typically, such an amount range from at least 0.15%, preferably at least 0.25%, by weight of the chelants relative to the total weight of the composition. Suitable chelants for use herein include but are not limited to:
diethylenetriamine-N,N',N"-polyacids, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), diamine-N,N'-dipolyacids, monoamine monoamide-N,N'-dipolyacids, a N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, preferably EDDS (ethylenediaminedisuccinic acid), carboxylic acids (preferably aminocarboxylic acids), phosphonic acids (preferably aminophosphonic acids) and polyphosphoric acids (in particular straight polyphosphoric acids), their salts and derivatives.
When the composition is obtained by mixing a tint component and a developer component, the chelants may be incorporated in the tint component or in the developer component or in both. A
chelant is usually present in developer components for stability reason.
pH Modifiers The compositions of the present invention may comprise in addition to the alkalizing agent discussed above a pH modifier and/or buffering agent in an amount that is sufficiently effective to adjust the pH of the composition to fall within a range from about 3 to about 13, preferably from about 8 to about 12, more preferably from about 9 to about 11.
Radical Scavengers According to the present invention, the compositions may comprise a radical scavenger.
As used herein the term radical scavenger refers to a species that can react with a radical, to convert the radical species by a series of fast reactions to an unreactive or less reactive species.
The radical scavenger is also preferably selected such that it is not an identical species as the alkalising agent and is present in an amount sufficient to reduce the damage to the hair during the colouring /bleaching process. The compositions of the present invention comprise a radical scavenger from about 0.1 % to about 10%, preferably from about l % to about 7%
by weight of the radical scavenger relative to the total weight of the composition.
Suitable radical scavengers for use herein may be selected from the classes of alkanolamines, amino sugars, amino acids, esters of amino acids and mixtures thereof. Suitable compounds include 3-substituted-pyrazol-5 -ones, 3 -carboxy- I H-pyrazol-5 -one, 3-methyl-l-phenyl-pyrazol-5-one, 3-methyl-l-p-tolyl-pyrazol-5-one, 3-methyl-l-(4-sulfophenyl)-pyrazol-5-one, 3-methyl-l-(4-suI foam idophenyl)-pyrazol-5-one, 3-methyl-l-(3-sulfophenyl)-pyrazol-5-one, 3-methyl -l -(3-suI foamidophenyl)-pyrazol-5-one, 3-methyl-l -(2-chloro-5-sulfophenyl)-pyrazol-5-one, 3-methyl-1 -(2,5-dichloro-4-sulfophenyl)-pyrazol-5-one, 3-methyl-l-(4-chlorophenyl)-pyrazol-5-one, 3-methyl- 1-(4-carboxyphenyl)-pyrazol-5-one, 3 -carboxy- I -phenyl-pyrazol-5 -one, 3 -carboxy- I -(4-sul fophenyl)-pyrazol-5 -one, 1,3 -diphenyl-pyrazol-5 -one, methyl pyrazol-5-one-3-carboxylate, 3-amino-l-propanol, 4-amino-l-butanol,5-amino-l-pentanol, I-amino-2-propanol, I-amino-2-butanol, 1-amino-2-pentanol, I-amino-3-pentanol, I-amino-4-pentanol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine, N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine, histidine, sarcosine, serine, glutamic acid, tryptophan, or mixtures thereof, or the salts, such as the potassium, sodium, or ammonium salts thereof, or mixtures thereof. In some embodiments, the inventive compositions may comprise glycine, sarcosine, lysine, serine, 2-methoxyethylamine, glucosamine, glutamic acid, morpholine, piperidine, ethylamine, 3-amino-l-propanol, or mixtures thereof.
Method of hair dyeing In order to use the dyeing composition, the tint component and developer component are usually mixed immediately prior to use and a sufficient amount of the mixture is applied to the hair, according to the hair abundance, generally from about 60 to about 250 grams. Upon such preparation the composition is applied to the hair to be dyed and remains in contact with the hair for an amount of time effective to dye the hair. Typically, the hair dye composition is allowed to act on the hair from about 2 to about 60, preferably about 15 to about 45, more preferably about minutes, at a temperature ranging from 15 C to about 50 C. Thereafter, the hair is rinsed with water to remove the composition and dried. If necessary, the hair is washed with a shampoo and rinsed, e.g., with water or a weakly acidic solution, such as a citric acid or tartaric acid solution, and dried. Optionally, a separate conditioning product may also be provided.
25 The method of dyeing hair with the composition may therefore comprise the steps of-(i) providing a tint component comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline derivative compound of the general formula (I) as defined above, a physiologically compatible water-soluble salt thereof or mixtures thereof and; (B) a 4,5-diamino-pyrazole derivative as defined in formula (II) of the general formula (II) as defined above, a physiologically compatible 30 water-soluble salt thereof or mixtures thereof;

(ii) providing a developer component comprising (C) an oxidizing agent;

(iii) mixing the tint component and the developer component to obtain a composition for the oxidative dyeing of keratin fibers;

(iv) applying said composition for the oxidative dyeing of keratin fibers onto the hair.
The method may further comprise waiting a period of time, typically between 2 minutes and 60 minutes, and then rinsing the composition from the hair.
The compositions can be applied on hair via applicator bottle or brush. It can be used on 5 full head or partly on single strands (highlight application) as common highlight applicator foils, caps and special applicators can be used, but also freehand techniques such as balayage, with brush and/or combs can be possible. The composition can also be applied as a mousse via a manual spray, a pressurized container or an aerosol mousse.
The composition may be dispensed as a solid form to which water is added to generate 10 the oxidant and form a thickened vehicle suitable for hair coloring.
The dye combination of the invention may also be used in three components system. See for example disclosed US2010/0223739A2 assigned to L'Oreal. Such a process and kit for lightening or dyeing keratin fibers may comprise the following composition applied to the hair fibers: an aqueous cosmetic composition (A) comprising at least one fatty substance and at least 15 one surfactant; a cosmetic composition (B) comprising at least one alkaline agent and the oxidative dyes of the invention and if present direct dyes and other oxidative dyes, a cosmetic composition (C) comprising at least one oxidizing agent, wherein the amount of the at least one fatty substance in composition (A) is greater than 20% by weight relative to the total weight of composition (A).

Methods of making - Kit The composition, and its tint component and developer component, may be manufactured by conventional processes known in the art for manufacturing oxidative dyeing products, and ad-mixing the ingredients of each component composition in suitable vessels, followed by packaging in appropriate individual containers. The components may be for example packaged in plastic or aluminium bottles.
In particular, the present invention may be provided as a kit comprising different components to be mixed by the consumer or salon stylist to obtain a hair dyeing composition according to the invention. Such a kit may comprise:
(i) a tint component comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline derivative of general formula (1), a physiologically compatible water-soluble salt thereof, or mixtures thereof, (B) a 4,5-diamino-pyrazole derivative of general formula (II), a physiologically compatible water-soluble salt, or mixtures thereof, and ii) a developer component comprising (C) an oxidizing agent.

The kit may be presented in a single package comprising separate containers for the tint component, the developer component, and optionally a conditioner, a color refresher or other hair treatment product, instructions for use, gloves. The instructions for use include the steps of the method described above and optionally provide visual cues or pictures for the desired steps of the method. Kits are usually sold in retail products with enough material in each component for preparing a hair dyeing composition for one use.
The composition may be dispensed as a foam using for example manually-actuable, non-aerosol dispenser such as a pump or squeeze foamers, aerosol mousse. See for example EP
613,728 BI, WO 97/013585 Al, EP 1,716,933A1, US 3,709,437, US 3,937,364, US
4,022,351, US 4,147,306, US 4,184,615, US 4,615,467 and FR 2,604,622. One particular example of a squeeze foamer useful herein is able to dispense from an upright or inverted position such as the one discussed in US 6,604,693 assigned to Taplast, and more specifically, at column 2, line 65, through column 4, line 67 of that patent.
EXAMPLES
The following are non-limiting examples of the compositions of the present invention.
The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention, which would be recognized by one of ordinary skill in the art.
The 5-amino-1,2,3,4-tetrahydroquinoline derivatives of the formula (I) can be synthesized following the experimental protocol described by D. Roberts, J.A. Joule in Journal of Organic Chemistry, 62 (1997) pages 568-577.

The synthesis of 5-amino-1,2,3,4-tetrahydroquinoline derivatives of the formula (I) as shown in the following scheme.

~ R1 R1 NiC12/NaBH4 C

(1) Examples I to 4: Hair dyes (1:1 combinations) 1.25 mmol 5-amino-1,2,3,4-tetrahydroquinoline of the formula (I) as described in examples I to 4.
1.25 mmol primary intermediate substance (II.1) 10.0 g lauryl ether sulfate (28 percent aqueous solution) 9.0 g ammonia (22 percent aqueous solution) 7.8 g ethanol 0.3 g ascorbic acid 0.3 g ethylenediaminotetraacetic acid disodium salt hydrate ad 100.0 g water, demineralized 10 g of the above dye solution were mixed directly prior to application with 10 g of a 6 percent hydrogen peroxide solution. The mixture was then applied to bleached hair.
After a contact time of 30 minutes at 40 C, the hair was rinsed with water, washed with a standard commercial shampoo and dried. The resulting colorations are summarized in table 1.
Table 1:

Example No Coupler substance of the formula (I) Shade obtained 1 N C ICI darkest burgundy red H
(1.1) 5-amino-1,2,3,4-tetrahydroquinoline 2 CN~ NH2 red H
(1.2) 5,7-dlamino-1,2,3,4-tetrahydroquinoline 3 H C pink OH
(1.3) 5-am ino-8-hydroxy- 1,2,3,4-tetrahydroquinoline C &1:
4 H violet (1.4) 5-am ino-6-methyl-1,2,3,4-tetrahydroqu inol ine Unless stated otherwise, all of the percentages given in the present application are percentages by weight.
Except as otherwise noted, all amounts including part, percentages, and proportions are understood to be modified by the word "about", and amounts are not intended to indicate significant digits. Except as otherwise noted, the articles "a", "an", and "the" mean "one or more".
All percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight percent" may be denoted as "wt. %" herein.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Every document cited herein, including any cross referenced or related patent or application is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (12)

1. A composition for the oxidative dyeing of keratin fibers comprising:
- (A) a 5-amino-1,2,3,4-tetrahydroquinoline compound of general formula (I), a physiologically compatible water-soluble salt thereof, or mixtures thereof;

wherein R1, R2 and R3 are substituents selected independently of each other from the group consisting of:
(a) C-linked substituents selected from the group consisting of:
(i) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems, (ii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl systems, and (iii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, heteroaryl systems, and wherein said systems of (i), (ii) and (iii) comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, F, N, P and Si;
(b) S-linked substituents selected from the group consisting of SA1, SO2A1, SO3A1, SSA1, SOA1, SO2NA1A2, SNA1A2, and SONA1A2;
(c) O-linked substituents selected from the group consisting of OA1, ONA1A2;
(d) N-linked substituents selected from the group consisting of NA1A2, (NA1A2A3)+
NA1SA2, NO2, NA1A2;
(e) substituents selected from the group consisting of COOA1, CONA1, CONA1COA2, C(=NA1)NA2A3, CN, and X;

(f) fluoroalkyl substituents selected from the group consisting of mono-, poly-, and per-fluoro alkyl systems comprising from 1 to 12 carbon atoms and from 0 to 4 heteroatoms;
and (g) H; and wherein A1, A2, and A3 are selected independently from the group consisting of: H;
mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems; mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl or heteraryl systems; and substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems, or A1 and A2 together with nitrogen atoms to which they are bound form a ring;
wherein said systems comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, S, N, P, and Si;
and wherein X is a halogen selected from the group consisting of F, Cl, Br, and I; and - (B) a 4,5-diamino-pyrazole compound of general formula (II) hereafter, a physiologically compatible water-soluble salt thereof, or mixtures thereof;

wherein R4 has the same definition given above for R1, R2, R3 of the 5-amino-1,2,3,4-tetrahydroquinoline compound of general formula (I);

wherein R5, R6, R7, R8 and R9 are substituents selected independently of each other from the group consisting of:

(h) C-linked substituents selected from the group consisting of:
(i) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, alkyl or heteroalkyl systems, (ii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, aryl systems, and (iii) mono- or poly- substituted or unsubstituted, straight or branched, saturated or mono-or poly- unsaturated, heteroaryl systems, and wherein said systems of (i), (ii) and (iii) comprise from about 1 to 10 carbon atoms and from about 0 to 5 heteroatoms selected from the group consisting of O, F, N, P
and Si;
(i) substituents selected from the group consisting of COOA1, CONA1, CONA1COA2, C(=NA1)NA1A2, CN; and (j) H;
- (C) an oxidizing agent.

2. A composition according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are substituents selected independently of each other from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 hydroxalkyl, C2-C4 alkoxy and mixtures thereof.

3. A composition according to claim 1 or 2, wherein said R1, R2 and R3 are selected independently of each other from the group consisting of a hydrogen atom; a halogen atom; an amino substituent; a hydroxyl substituent; a cyano substituent; a C1-C4 alkyl substituent; a trifluoromethyl substituent; an alkylamino substituent; a hydroxyalkylamino substituent; an acetylamido substituent; a carboxyl substituent or its esters;
an alkoxy substituent; an alkoxyalkyl substituent; a carbamoyl substituent; an alkylcarbamoyl substituent; a hydroxyalkylcarbamoyl substituent; an amido substituent; an alkylamido substituent; an alkylcarbonyl substituent; an alkoxycarbonyl substituent; an aryloxy substituent; an acyloxy substituent; an alkylthio substituent; an arylthio substituent; a heteroarylthio substituent; a heteroaryloxy substituent; a thiocyano substituent; a 3-, 4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen, oxygen or sulfur atom; an aryl substituent which is optionally substituted; a sulfonyl substituent; a sulfinyl substituent; a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent; an acyloxy substituent; a carbamoyloxy substituent; a sulphonamide substituent;
an imide substituent; a ureido substituent; a sulfamoylamino substituent; an alkoxycarbonylamino substituent; an aryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and a benzenesulfonamido substituent.

4. A composition according to any of the preceding claims, further comprising fatty alcohols comprising from 14 to 30 carbon atoms, or oxyethylenated fatty alcohols comprising from 16 to 30 carbon atoms and 2 units or less of ethylene oxide.

5. A composition according to any of the preceding claims, further comprising at least one ionic or nonionic surfactant selected from:
- anionic surfactants selected from C8-C30 alkyl sulfates, preferably C12-C18 alkyl sulfates, - anionic surfactants according to the formula R n X m YM, wherein R is independently selected from alkyl, alkenyl or alkylaryl groups having from 8 to 30 carbon atoms, X is independently selected from polar groups comprising at least one carbon atom and at least one oxygen or nitrogen atom, Y is an anionic group selected from carboxylates, sulfates, sulfonates or phosphates, n and m are independently 1 or 2, and M

is hydrogen or a salt forming cation and mixture thereof, most preferably selected from C8-C30 alkyl ether phosphates having from 1 to 20, preferably 2 to 10, ethylene oxide units;
non-ionic surfactant comprising one or more polyethyleneoxide chains, preferably each polyethyleneoxide chain having on average at least 50 ethylene oxide units, and most preferably 100 to 200 ethylene oxide units;
cationic surfactants selected from quaternary ammonium salts or amido-amines having at least one fatty chain, preferably comprising at least 16 carbon atoms and most preferably at least 20 carbon atoms; and - mixtures thereof.

6. A composition according to any of the preceding claims comprising a mixture of cetearyl alcohol and dicetyl phosphate and ceteth-10 phosphate.

7. A composition according to any of the preceding claims further comprising a chelant selected from the group consisting of. diethylenetriamine-N,N',N"-polyacids, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), diamine-N,N'-dipolyacids, monoamine monoamide-N,N'-dipolyacids, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, EDDS

(ethylenediaminedisuccinic acid), carboxylic acids (preferably aminocarboxylic acids), phosphonic acids (preferably aminophosphonic acids) and polyphosphoric acids (in particular straight polyphosphoric acids), their salts and derivatives.

8. A composition according to any of the preceding claims wherein said oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium periodate, urea peroxide, melamine peroxide, perborates, percarbonates, perphosphates, persilicates, persulfates, oxidizing enzymes such as uricases, oxidases, and peroxidases, a source of peroxymonocarbonate ions and mixtures thereof.

9. A composition according to claim 8 wherein the source of peroxymonocarbonate ions selected from the group consisting of. sodium, potassium, guanidine, arginine, lithium, calcium, magnesium, barium or ammonium salts of carbonate, carbamate and hydrocarbonate ions and mixtures thereof.

10. A composition according to any of the preceding claims, wherein said composition is dispensed as a foam.

11. A method of dyeing hair comprising the steps of:
(i) providing a tint component comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline derivative compound of the general formula (I) as defined in claim 1, a physiologically compatible water-soluble salt or mixtures thereof and; (B) a 4,5-diamino-pyrazole derivative of the general formula (II) as defined in claim 1, a physiologically compatible water-soluble salt thereof or mixtures thereof;
(ii) providing a developer component comprising (C) an oxidizing agent;
(iii) mixing the tint component and the developer component to obtain a composition for the oxidative dyeing of keratin fibers;
(iv) applying said composition for the oxidative dyeing of keratin fibers onto the hair.

12. An oxidative hair dyeing kit comprising: (i) a tint component comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline derivative of general formula (I) as defined in claim 1, a physiologically compatible water-soluble salt thereof, or mixtures thereof, (B) a 4,5-diamino-pyrazole derivative of general formula (II) as defined in claim 1, a physiologically compatible water-soluble salt thereof, or mixtures thereof;
and ii) a developer component comprising (C) an oxidizing agent.