WO2013107524A1

WO2013107524A1 - Hair colouring composition

Info

Publication number: WO2013107524A1
Application number: PCT/EP2012/050894
Authority: WO
Inventors: Stephen Norman Batchelor; Lalitesh Chandra
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2012-01-20
Filing date: 2012-01-20
Publication date: 2013-07-25

Abstract

A hair colouring composition comprising: i) at least 0.05 wt% of the total composition of beeswax and ii) at least 0.01 wt%, of the total composition of a 4, 5-diaminopyrazole.

Description

Hair Colouring Composition

The present invention relates to compositions for dyeing of keratin fibres, in particular human keratin fibres such as the hair. Prior art

It is known to dye keratin fibers, and in particular human hair, with dye

compositions containing oxidation dye precursors, in particular para- phenylenediamines, and/or para-aminophenols, which are generally referred to as oxidation bases, developers or primary intermediates. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes by a process of oxidative condensation. Pyrazole compounds have been developed as oxidation bases for red shades. The shades obtained with these oxidation bases can be varied by combining them with couplers or colour modifiers. Couplers are generally colourless molecules that form colours in the presence of activated oxidation bases. When the dye component and the oxidizing component are mixed, oxidizing agent present in the oxidizing component begins to oxidize developers present in the dye component and the oxidized developers begin to react with couplers to form chromophores. Typical couplers being selected in particular from aromatic meta-diamines, meta- aminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of compounds used as regards the oxidation bases and the couplers allows a wide range of colours to be obtained.

It is also known that in order to vary the shades obtained further and to give them tones, it is possible to use, in combination with the oxidation dye precursors and the couplers, direct dyes, that is to say coloured substances which provide coloration in the absence of an oxidizing agent. The so-called "permanent" coloration of hair by oxidation dyes must satisfy a certain number of requirements. Thus, it must allow shades of the desired intensity to be obtained and it must be able to withstand external agents (light, bad weather, washing, permanent waving, perspiration, rubbing) and it should not stain fabrics or skin.

The present invention relates to compositions that even when including direct dyes have good endurance properties. Furthermore the compositions of the invention mitigate the staining of fabric.

Summary of the invention

Accordingly the present invention relates to A hair colouring composition comprising:

i) at least 0.1 wt% beeswax and

ii) at least 0.01 wt%, of a 4, 5-diaminopyrazole.

Description of the invention Viscosities, except where otherwise specified, are dynamic viscosities. These may be measured using a cone and plate rheometer at 25°C and at a shear rate of 0.01 s^"1.

Where particles are referred to in the description, the broad definition of particles is meant, indicating that a material is present in a divided form. If the material is a liquid, the particles will be in the form of droplets.

Particle sizes are suitably measured by laser light scattering using an instrument such as a Malvern™ Mastersizer. Particle diameters are expressed as median particle diameters (D₅₀).

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. When more than one composition are used during a treatment, as in mixing of the components of a typical oxidative dye product, the total weight to be considered is the total weight of all the compositions applied on the hair simultaneously (i.e. the weight found "on head") unless otherwise specified.

Beeswax

The composition of the present invention comprise at least 0.05 wt% of beeswax. The beeswax is suitably present from 0.1 to 4% by weight of the composition, preferably from 0.15 % to 3%, more preferably from 0.2% to 1 %. The beeswax may be pre-formed into an emulsion or dispersion before addition to the rest of the composition

The wax is available as a commercial by-product of the harvesting and refining of honey. The beeswax is used in the invention preferably in a particulate form as particles with a median (D₅₀) diameter of 50 micrometres or less, preferably 20 micrometres or less, more preferably 10 micrometres or less and even more preferably 1 micrometre or less.

Oxidation Base/Developer Compositions of the invention comprise at least 0.01 wt%, preferably 0.1 to

3.5wt%, most preferably 2.5 to 3.5wt% of a 4, 5-diaminopyrazole. Preferably the 4,5-diaminopyrazole is 4,5-diamino-1 -(2'hydroxyethyl)-1 H pyrazole. ln addition to the 4,5-diaminopyrazole other developers may be present in the composition. Suitable developers for use in the dyeing compositions described herein include, but are not limited to, p-phenylenediamine derivatives, e.g. benzene- 1 ,4-diamine (commonly known as p-phenylenediamine); 2-chloro-benzene- 1 ,4-diamine; N- phenyl-benzene- 1 ,4-diamine; N-(2- ethoxyethyl)benzene- 1 ,4-diamine; 2-[(4- amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol (commonly known as N,N-bis(2- hydroxyethyl)-p-phenylenediamine); (2, 5-diamino-phenyl)- methanol; l-(2'- Hydroxyethyl)-2,5-diaminobenzene; 2-(2,5-diamino-phenyl)-ethanol; N-(4- aminophenyl)benzene- 1 ,4-diamine; 2,6-dimethyl -benzene- 1 ,4-diamine; 2- isopropyl-benzene- 1 ,4-diamine; l-[(4-aminophenyl)amino]-propan-2-ol; 2-propyl- benzene- 1 ,4-diamine; 1 ,3- bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2- ol; N ,N ,2-trimethylbenzene- 1 ,4- diamine; 2-methoxy-benzene- 1 ,4-diamine; I- (2,5-diaminophenyl)ethane-l,2-diol; 2, 3-dimethyl- benzene- 1 ,4-diamine; N-(4- amino-3-hydroxy-phenyl)-acetamide; 2,6-diethylbenzene- 1 ,4- diamine; 2, 5- dimethylbenzene- 1 ,4-diamine; 2-thien-2-ylbenzene- 1 ,4-diamine; 2-thien-3- ylbenzene- 1 ,4-diamine; 2-pyridin-3-ylbenzene-l,4-diamine; l,l'-biphenyl-2,5- diamine; 2- (methoxymethyl)benzene- 1 ,4-diamine; 2-(aminomethyl)benzene- 1 ,4- diamine; 2-(2,5- diaminophenoxy)ethanol; N-[2-(2,5-diaminophenoxy)ethyl]- acetamide; Ν,Ν-dimethylbenzene- 1 ,4-diamine; Ν,Ν-diethylbenzene- 1 ,4-diamine; Ν,Ν-dipropylbenzene- 1 ,4-diamine; 2-[(4- aminophenyl)(ethyl)amino]ethanol; 2- [(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]- ethanol; N-(2- methoxyethyl)-benzene- 1 ,4-diamine; 3-[(4-aminophenyl)amino]propan-l-ol; 3- [(4- aminophenyl)-amino]propane-l,2-diol; N-{4-[(4-aminophenyl)amino]butyl}benzene- l,4- diamine; 2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene- 1 ,4-diamine; 1 ,3- bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol; 2,2'-[l,2-Ethanediyl-bis-(oxy- 2,l-ethanediyloxy)]-bis-benzene-l,4-diamine; p- aminophenol derivatives such as: 4-amino- phenol (commonly known as p- aminophenol); 4-methylamino-phenol; 4-amino-3 -methyl- phenol; 4-amino-2- hydroxymethyl-phenol; 4-amino-2-methyl-phenol; 4-amino-l-hydroxy-2-(2'- hydroxyethylaminomethyl)benzene; 4-amino-2-methoxymethyl-phenol; 5-amino-2- hydroxy- benzoic acid; l-(5-amino-2-hydroxy-phenyl)-ethane-l,2-diol; 4-amino-2-(2- hydroxy-ethyl)- phenol; 4-amino-3-(hydroxymethyl)phenol; 4-amino-3-fluoro- phenol; 4-amino-2- (aminomethyl)-phenol; 4-amino-2-fluoro-phenol; l-hydroxy-2,4- diaminobenzene; o- phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid and salts thereof; o- aminophenol derivatives such as: 2-amino-phenol (commonly known as o-aminophenol); 2,4- diaminophenol; 2-amino-5-methyl- phenol; 2-amino-5-ethyl-phenol; 2-amino-6-methyl-phenol; N-(4-amino-3-hydroxy- phenyl)-acetamide; and 2-amino-4-methyl-phenol; and heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6- tetraaminopyrimidine); l-methyl-IH-pyrazole-4,5-diamine; 2-(4,5-diamino-IH- pyrazol-l- yl)ethanol; N²,N²-dimethyl-pyridine-2,5-diamine; 2-[(3-amino-6- methoxypyridin-2- yl)amino]ethanol; 6-methoxy-N²-methyl-pyridine-2,3-diamine; 2,5,6-triaminopyrimidin-4(IH)- one; pyridine-2,5-diamine; l-isopropyl-IH-pyrazole- 4,5-diamine; l-(4-methylbenzyl)-IH- pyrazole-4,5-diamine; 1 -(benzyl)- IH-pyrazole- 4,5-diamine; l-(4-chlorobenzyl)-IH-pyrazole- 4,5-diamine; pyrazolo[l,5-a]- pyrimidine-3,7-diamine; 5,6,7-trimethylpyrazolo[l,5-a]pyrimidin- 3-ylamine hydrochloride; 7-methylpyrazolo[l,5-a]pyrimidin-3-ylamine hydrochloride; 2,5,6,7- teramethyl-pyrazolo[ 1 ,5-a]pyrimidin-3-ylamine hydrochloride; 5,7-di-tert- butylpyrazolo[ 1 ,5- a]pyrimidin-3 -ylamine hydrochloride; 5,7 -di-trifluoromethyl- pyrazolo [1 ,5- ajpyrimidin- 3 - ylamine hydrochloride; 2-methylpyrazolo[l,5- a]pyrimidin-3,7-diamine hydrochloride; 4- hydroxy-2,5,6-triaminopyrimidine; I- hydroxyethyl-4,5-diaminopyrazole; 2,5- diaminophenylethyl alcohol; and salts thereof.

Additional developers may be selected from 7V-(3-furylmethyl)ben/ene-l,4- diamine; N- thiophen-3-ylmethyl-benzene-l,4-diamine; A/-(2-furylraethyl)ben/ene- l,4-diaitune; N-thiophen- 2-ylmethyl-benzene-l,4-diamine: 3-(2,5-diamino-phenyl)- N-ethyl-acrylamide; 2-[3-(3-amino- phenylamino)-propenyl]-benzene-l,4-diamine; 2-[3-(4-amino-phenylamino)-propenyl]-benzene- 1 ,4-diamine; 2-(6-methyl-pyridin- 2-yl)-benzene-l,4-diamine; 2-pyridin-2-yl-benzene-l,4- diamine; 2-[3-(4-amino- phenylamino)-propenyl]-benzene-l,4-diamine; 2-[3-(3-amino- phenylamino)- propenyl]-benzene-l,4-diamine: 3-(2,5-diamino-phenyl)-N-ethyl-acrylamide: 2- thiazol-2-yl-benzene-l,4-diamine; 4-hydroxy-benzoic acid (2,5-diamino- benzylidene)- hydrazide; 3'-fluoro-biphenyl-2,5-diamine; 2-propenyl-benzene-l,4- diamine; 2'-chloro-biphenyl- 2,5-diamine; N-thiophen-3-ylmethyl-benzene-l,4- diamine; ?/-(3-furylmethyl)benzene- 1 A- diamine; 4'-methoxy-biphenyl-2,5- diamine; N-(4-amino-benzyl)-benzene-l,4-diamine; 2- methyl-5-[(l-H-pyrrol-2- ylmethyl)-amino]-phenol; 5-[(furan-2-ylmethyl)-amino]-2-methyl- phenol: 5- isopropylamino-2-methyl-phenol; biphenyl-2,4,4'-triamine hydrochloride: 5-(4- amino- phenyl)aminomethyl-benzene-l,3-diamine hydrochloride: 5- phenylaminomethyl-benzene-l,3- diamine hydrochloride; 2-[4-amino-2-(3,5- diamino-benzylamino)-phenoxy]-ethanol hydrochloride; 5-(3-amino- phenyl)aminomethyl-benzene-l,3-diamine hydrochloride; N-(2- amino-benzyl)- benzene-l,3-diamine hydrochloride; N-furan-2-ylmethyl-benzene- 1 ,3 -diamine hydrochloride; 2-[(3-amino-phenylamino)-methyl]-phenol hydrochloride; 4-amino- 2- propylaminomethyl-phenol; N-benzo [1 ,3] dioxol- 5 -ylmethyl-benzene- 1 , 3 - diamine hydrochloride; N-[4-amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5- amino-2-hydroxy- phenyl)-acrylamide; 4-amino-2-(isopropylamino-methyl)-phenol; 4-thiophen-3-yl-benzene-l,3- diamine; 5-phenylaminomethyl-benzene-l,3-diamine hydrochloride; 5-(3-amino- phenyl)aminomethyl-benzene-l,3-diamine

hydrochloride; 4-thiophen-3-yl-benzene-l,3-diamine; 2',4'-diamino-biphenyl-4-ol; 5- cyclobutylamino-2-methyl-phenol; 5-cyclobutylamino-2-methyl- phenol: 4-amino-2- (pyridin-3-ylaminomethyl)-phenol; 5-(3-amino-phenyl)aminomethyl- benzene-l,3- diamine hydrochloride; 5-allylaminomethyl-benzene-l,3-diamine hydrochloride; N- (4-amino-benzyl)-benzene-l,3-diamine hydrochloride; N-benzyl-benzene- 1 ,3 - diamine hydrochloride; 3-[(3-amino-phenylamino)-methyl]-phenol hydrochloride; N-(4-methoxy- benzyl) -benzene- 1 ,3 -diamine hydrochloride; N-thiophen-2- ylmethyl-benzene-l,3-diamine hydrochloride; 4-Amino-2-[(2-hydroxy-5-nitro- phenylamino)-methyl]-phenol; 2',4'- diamino- biphenyl-4-ol hydrochloride;

biphenyl-2,4,4'-triamine; 5-(4-amino-phenyl)aminomethyl- benzene- 1 , 3 -diamine hydrochloride; 2- [4- amino-2- (3, 5 -diamino-benzylamino) -phenoxy ] - ethanol hydrochloride; 5-allylaminomethyl-benzene-l,3-diamine hydrochloride; 5-(3-amino- phenyl)aminomethyl-benzene- 1 ,3-diamine hydrochloride; N-(4-amino-benzyl)- benzene- 1 ,3- diamine hydrochloride; N-benzyl-benzene- 1 ,3-diamine

hydrochloride: 3-[(3-amino- phenylamino) -methyl] -phenol hydrochloride; N-(2- amino-benzy 1 ) -benzene- 1 , 3 -diamine hydrochloride; N-(4-methoxy-benzyl)- benzene-l,3-diamine hydrochloride; N-furan-2-ylmethyl- benzene- 1 ,3-diamine hydrochloride; 2-[(3-amino-phenylamino)-methyl]-phenol hydrochloride; N- thiophen-2-ylmethyl-benzene- 1 ,3-diamine hydrochloride; N-benzo[l,3]dioxol-5- ylmethyl- benzene- 1 ,3-diamine hydrochloride; N-[4-amino-2-(2-hydroxy-ethyl)-2H- pyrazol-3-yl]-3-(5- amino-2-hydroxy-phenyl)-acrylamide hydrochloride; 4-amino-2- propylaminomethyl-phenol; 4- amino-2-(isopropylamino-methyl)-phenol

hydrochloride; 4-amino-2-[(2-hydroxy-5-nitro- phenylamino) -methyl] -phenol hydrochloride; 2-methyl-5-[(l-H-pyrrol-2-ylmethyl)-amino]- phenol; 5-[(furan-2- ylmethyl)-amino]-2-methyl-phenol; 5-isopropylamino-2-methyl-phenol; 5- cyclobutylamino-2-methyl-phenol; 4-amino-2-(pyridin-3-ylaminomethyl)-phenol; 5- cyclobutylamino-2-methyl-phenol; 4,5-diamino-l-methyl-IH-pyrazole-3-carbonitrile; 3- methoxy-1 -propyl- IH-pyrazole-4,5-diamine; 3-methoxy-l-(2-methoxyethyl)-l?- pyrazole-4,5- diamine; l-(2-aminoethyl)-3-methoxy-IH-pyrazole-4,5-diamine; 8- methoxy-1,2,4,5- tetrahydropyrazolo[5,l-d][l,3,5]oxadiazepin-9-amine; l-(2- hydroxyethyl)-3-methoxy-IH- pyrazol-4,5-diamine; l-cyclohexyl-3-methoxy-IH- pyrazole-4,5-diamine; 6-methoxy-l -methyl- 2,3-dihydro-IH-imidazo[l,2-b]pyrazol-7-amine; 2-methoxy-4,5,6,7

tetrahydropyrazolo[l,5- a]pyrimidin-3 -amine; 3-methoxy- l-octyl-IH-pyrazole-4,5- diamine; 3-methoxy- 1 -pentyl- IH- pyrazole-4,5-diamine; 6-methoxy-2,3-dihydro- IH-imidazo[l,2-b]pyrazol-7-amine; 3-methoxy- N,N -dimethyl- l-propyl-IH-pyrazole- 4,5-diamine; l-hexyl-3-methoxy-IH-pyrazole-4,5- diamine; l-butyl-3-methoxy-IH- pyrazole-4,5-diamine; l-isopropyl-3-methoxy-IH-pyrazole- 4,5-diamine; l-ethyl-3- methoxy-IH-pyrazole-4,5-diamine; 3-methoxy- l-(4-methoxybenzyl)- IH-pyrazole- 4,5-diamine; 3-methoxy-l-(pyridin-2-yl)-IH-pyrazole-4,5-diamine; l-(4- ethylphenyl)- 3-methoxy-IH-pyrazole-4,5-diamine; 3-methoxy-l-p-tolyl-IH-pyrazole-4,5- diamine; 3-cyano-l-(2-hydroxyethyl)-IH-pyrazole-4,5-diamine; l-butyl-3-cyano-IH-pyrazole- 4,5-diamine; 3-cyano-l-phenyl-IH-pyrazol-4,5-diamine; 3-cyano- l-hexyl-IH-pyrazol- 4,5- diamine; l-butyl-3-cyano- IH-pyrazol-4,5-diamine; 3-cyano- 1-(4- methoxybenzyl)- IH-pyrazol- 4,5-diamine; 3-cyano- l-isopropyl-IH-pyrazol-4,5- diamine; l-cyclohexyl-3-fluoro-N⁵-isopropyl- IH-pyrazole-4,5-diamine; l-methyl-3- (trifluoromethoxy)-IH-pyrazole-4,5-diamine; 3-fluoro-l- octyl-IH-pyrazole-4,5- diamine; 3-chloro-l-hexyl-IH-pyrazole-4,5-diamine; 3-fluoro-l-(2- hydroxyethyl)- IH- pyrazol-4,5-diamine; 3-chloro- l-(2-hydroxyethyl)- IH-pyrazol-4,5-diamine; 3- chloro-l-(4-hydroxybutyl)-IH-pyrazol-4,5-diamine; 3-chloro-l-(pyridin-2-yl)-IH- pyrazole- 4,5-diamine; 3-chloro- 1 -phenyl- IH-pyrazole-4,5-diamine; 3-chloro- 1- ethyl-IH-pyrazole-4,5- diamine; l-(3-methoxypropyl)-3-(methylsulfinyl)-IH-pyrazole- 4,5-diamine; l-(3- hydroxypropyl)-3-(methylsulfinyl)-IH-pyrazole-4,5-diamine; l-(4- methoxybenzyl)-3-(methylsulfonyl)-IH-pyrazole-4, 5-diamine; l-methyl-3- (methylsulfonyl)-IH-pyrazole-4,5- diamine; and salts thereof.

In some embodiments, developers include but are not limited to: p-preferred phenylenediamine derivatives such as: 2-methyl-benzene-l,4-diamine; benzene- 1 ,4-diamine; l-(2,5-diamino- phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol; 2- (methoxymethyl)benzene- 1 ,4-diamine; ?- (2-methoxyethyl)benzene- 1 ,4-diamine; 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol; l-(2,5- diaminophenyl)ethane-l,2-diol; l-(2'-hydroxyethyl)-2,5-diaminobenzene; l,3-bis(?- (2- hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol; 2,2'-[l,2-ethanediyl-bis- (oxy-2,l- ethanediyloxy)]-bis-benzene-l,4-diamine; N,N-bis(2-hydroxyethyl)-p- phenylenediamine; and mixtures thereof; p-aminophenol derivatives such as: 4- amino-phenol; 4-methylamino-phenol; 4-amino-3-methyl-phenol; 4-amino-2- methoxymethyl-phenol; l-(5-amino-2-hydroxy-phenyl)- ethane-l,2-diol; 4-amino-2- aminomethylphenol; 4-amino-l-hydroxy-2-(2'- hydroxyethylaminomethyl)benzene; 5-aminosalicylic acid and salts thereof; and mixtures thereof; o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid and salts thereof; o- aminophenol derivatives such as: 2-amino-phenol; 2-amino-5-methyl-phenol; 2-amino-6- methyl-phenol; N-(4-amino-3-hydroxy-phenyl)-acetamide; 2-amino-4-methyl- phenol; 2-amino- 5-ethyl-phenol; and mixtures thereof; and heterocyclic

derivatives such as: pyrimidine-2,4,5,6- tetramine; l-methyl-IH-pyrazole-4,5- diamine; 2-(4,5-diamino-IH-pyrazol-l-yl)ethanol; l-(4- methylbenzyl)-IH-pyrazole- 4,5-diamine; l-(benzyl)-IH-pyrazole-4,5-diamine; N²,N²-dimethyl- pyridine-2,5- diamine; 4-Hydroxy-2,5,6-triaminopyrimidine; salts thereof; and mixtures thereof.

Particularly preferred developers for combination with 4, 5-diaminopyrazole are base selected from toluene 2-5 diamine sulphate and para-amino-phenol.

Preferably the weight ratio of beeswax to the 4,5 diaminopyrazole is from 10: 1 to 1 :2, more preferably from 5: 1 to 1 : 1 .

Couplers Suitable couplers for use in the dyeing compositions include, but are not limited to: phenols, resorcinols, naphthols, m-aminophenols, m-phenylenediamines, and heterocyclic compounds, and derivatives thereof such as: 2-amino-5-ethyl-phenol; naphthalene- 1 ,7-diol; benzene- 1 ,3-diol; 4-chlorobenzene-l,3-diol; naphthalen-1 - ol; 2-methyl-naphthalen-l-ol; naphthalene- 1 ,5-diol; naphthalene-2,7-diol;

benzene- 1 ,4-diol; 2-methyl-benzene-l,3-diol; 7- amino-4-hydroxy-naphthalene-2- sulfonic acid; 2-isopropyl-5-methylphenol; 1 ,2,3,4-tetrahydro- naphthalene- 1 ,5- diol; 2-chloro-benzene-l,3-diol; 4-hydroxy-naphthalene-l-sulfonic acid; benzene- 1,2,3-triol; naphthalene-2,3-diol; 5-dichloro-2-methylbenzene-l,3-diol; 4,6- dichlorobenzene- 1 ,3-diol; 2,3-dihydroxy-[l,4]naphthoquinone; and l-Acetoxy-2- methylnaphthalene; m-phenylenediamines such as: 2,4-diaminophenol; benzene- 1 ,3 -diamine; 2- (2,4-diamino-phenoxy)-ethanol; 2-[(3-amino-phenyl)-(2-hydroxy- ethyl)-amino]-ethanol; 2- mehyl-benzene-l,3-diamine; 2-[[2-(2,4-diamino-phenoxy)- ethyl]-(2-hydroxy-ethyl)-amino]- ethanol; 4-{3-[(2,4- diaminophenyl)oxy]propoxy}benzene-l,3-diamine; 2-(2,4-diamino-phenyl)- ethanol; 2-(3-amino-4-methoxy-phenylamino)-ethanol; 4-(2-amino-ethoxy)-benzene-l,3- diamine; (2,4-diamino-phenoxy)-acetic acid; 2-[2,4-diamino-5-(2-hydroxy-ethoxy)- phenoxy]- ethanol; 4-ethoxy-6-m ethyl -benzene- 1 ,3-diamine; 2-(2,4-diamino-5- methyl-phenoxy)-ethanol; 4,6-dimethoxy-benzene-l,3-diamine; 2-[3-(2-hydroxy- ethylamino)-2-methyl-phenylamino]- ethanol; 3-(2,4-diamino-phenoxy)-propan-l-ol; N-[3-(dimethylamino)phenyl]urea; 4-methoxy- 6-methylbenzene-l,3-diamine; 4-fluoro-6-methylbenzene-l,3-diamine; 2-({3- [(2hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol; 3-(2,4- diaminophenoxy)-propane- 1 ,2-diol; 2-[2-amino-4-(methylamino)-phenoxy]ethanol; 2-[(5-amino-2-ethoxy-phenyl)-(2- hydroxy-ethyl)-amino]-ethanol; 2-[(3- aminophenyl)amino]ethanol; 2,4-Diamino-5-(2'- hydroxyethyloxy)toluene; N,N- Dimethyl-3-ureidoaniline; N-(2-aminoethyl)benzene- 1 ,3- diamine; 4- {[(2,4- diamino-phenyl)oxy]methoxy} -benzene- 1 ,3-diamine; l-methyl-2,6-bis(2- hydroxyethylamino)benzene; and 2,4-dimethoxybenzene-l,3-diamine; m- aminophenols such as: 3-amino-phenol; 2-(3-hydroxy-4-methyl-phenylamino)- acetamide; 2-(3-hydroxy-phenylamino)- acetamide; 5-amino-2-methyl-phenol; 3- amino-2,6-dimethylphenol; 5-(2-hydroxy-ethylamino)- 2-methyl-phenol; 5-amino- 2,4-dichloro-phenol; 3-amino-2-methyl-phenol; 3-amino-2,6- dimethyl -phenol; 3- amino-2-chloro-6-methyl-phenol; 5-amino-2-(2-hydroxy-ethoxy)-phenol; 2- chloro- 5-(2,2,2-trifluoro-ethylamino)-phenol; 5-amino-4-chloro-2-methyl-phenol; 3- cyclopentylamino-phenol; 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol; 5-amino-4- methoxy-2-methylphenol; 3-(dimethylamino)phenol; 3-

(diethylamino)phenol; 5-amino-4-fluoro- 2-methylphenol; 5-amino-4-ethoxy-2- methylphenol; 3-amino-2,4-dichloro-phenol; 3-[(2- methoxyethyl)amino]phenol; 3- [(2-hydroxyethyl)amino]phenol; 5-amino-2-ethyl-phenol; 5- amino-2- methoxyphenol; 5-[(3-hydroxy-propyl)amino]-2-methylphenol; 3-[(3-hydroxy-2- methylphenyl)-amino]propane-l,2-diol; 3-[(2-hydroxyethyl)amino]-2-methylphenol; 1 -methyl- 2-hydroxy-4-(2'-hydroxyethyl)amino-benzene; 1 ,3-bis-(2,4- diaminophenoxy)propane; and heterocyclic derivatives such as: 3,4-dihydro-2H- l,4-benzoxazin-6-ol; 6-methoxyquinolin-8- amine; 4-methylpyridine-2,6-diol; 2,3- dihydro-l,4-benzodioxin-5-ol; l,3-benzodioxol-5-ol; 2- (l,3-benzodioxol-5- ylamino)ethanol; 3,4-dimethylpyridine-2,6-diol; 5-chloropyridine-2,3-diol; 2,6- dimethoxypyridine-3,5-diamine; l,3-benzodioxol-5-amine; 2-{ [3,5-diamino-6-(2- hydroxy- ethoxy)-pyridin-2-yl]oxy}-ethanol; IH-indol-4-ol; 5-amino-2,6- dimethoxypyridin-3-ol; IH- indole-5,6-diol; IH-indol-7-ol; IH-indol-5-ol; IH-indol-6-ol; 6-bromo-l,3-benzodioxol-5-ol; 2- aminopyridin-3-ol; pyridine-2,6-diamine; 3-[(3,5- diaminopyridin-2-yl)oxy]propane-l,2-diol; 5- [(3,5-diaminopyridin-2-yl)oxy]pentane- l,3-diol; indoline-5,6-diol; 3,5-dimethoxypyridine-2,6- diamine; 6-methoxypyridine- 2,3-diamine; 3,4-dihydro-2H-l,4-benzoxazin-6-amine; 4-hydroxy- N-methylindole; IH-5-methylpyrazol-5-one; l-phenyl-3-methylpyrazol-5-one; 2,6- dimethylpyrazolo[l,5-b]-l,2,4-triazole; 2,6-dimethyl[3,2-c]-l,2,4-triazole; 6- methylpyrazolo- [l,5-a]benzimidazole; 2,6-dihydroxypyridine; 2,6-dihydroxy-3,4- dimethylpyridine; 5- methylpyrazolo[5,l-e]-l,2,3-triazole; 5-methyl-6- chloropyrazolo[5,l-e]-l,2,3-triazole; 5- phenylpyrazolo[5,l-e]-l,2,3-triazole and its addition salts; IH-2,6-dimethylpyrazolo[l,5-b]- 1 ,2,4-triazole tosylate; 7,8-dicyano- 4-methylimidazolo-[3,2-a]imidazole; 2,7- dimethylpyrazolo[l,5-a]pyrimidin-5-one; 2,5-dimethylpyrazolo[l,5-a]pyrimidin-7-one; and 2- methyl-5-methoxymethyl- pyrazolo[l,5-a]pyrimidin-7-one; 6-hydroxybenzomorpholine; and 3- amino-2- methylamino-6-methoxypyridine; salts thereof; and mixtures thereof.

In some embodiments, couplers include but are not limited to: phenol, resorcinol, and naphthol derivatives such as: 2-amino-5-ethyl-phenol; naphthalene- 1 ,7-diol; benzene-l,3-diol; 4-chlorobenzene-l,3-diol; naphthalen-1 -ol; 2-methyl-naphthalen- l-ol; naphthalene- 1 , 5 -diol; naphthalene-2,7-diol; benzene- 1 ,4-diol; 2-methyl - benzene- 1 ,3-diol; and 2-isopropyl-5- methylphenol; 1 ,2,4-trihydroxybenzene; I- acetoxy-2-methylnaphthalene; and mixtures thereof; m-phenylenediamine derivatives such as: benzene- 1 ,3 -diamine; 2-(2,4-diamino-phenoxy)- ethanol; 4- {3-[(2,4-diaminophenyl)oxy]propoxy}benzene-l,3-diamine; 2-(3-amino-4-methoxy- phenylamino)-ethanol; 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol; and 3-(2,4- diamino-phenoxy)-propan-l-ol; 2,4-diamino-5-(2'-hydroxyethyloxy)toluene; N,N-dimethyl-3- ureidoaniline; 2,4-diamino-5-fluorotoluene; l-methyl-2,6-bis(2- hydroxyethylamino)benzene; and mixtures thereof; m-aminophenol derivatives such as: 3-aminophenol; 5-amino-2-methyl- phenol; 3-amino-2,6-dimethylphenol; 5-(2-hydroxy-ethylamino)-2-methyl-phenol; and 3-amino- 2-methyl-phenol; I- hydroxy-3-amino-2,4-dichlorobenzene; l,3-bis-(2,4- diaminophenoxy)propane; I- hydroxy-2-methyl-5-amino-6-chlorobenzene; 5-Amino-4-chloro-2- methylphenol; and mixtures thereof; and heterocyclic derivatives such as: 3,4-dihydro-2H-l,4- benzoxazin-6-ol; l,3-benzodioxol-5-ol; l,3-benzodioxol-5-amine; IH-indol-4-ol; IH- indole-5,6- diol; IH-indol-7-ol; IH-indol-5-ol; IH-indol-6-ol; pyridine-2,6-diamine; 2- aminopyridin-3-ol; 4-hydroxy-N-methylindole; IH-5-methylpyrazol-5-one; l-phenyl- 3-methylpyrazol-5-one; 2,6- dimethylpyrazolo[l,5-b]-l,2,4-triazole; 2,6-dimethyl[3,2- c]-l,2,4-triazole; 6-methylpyrazolo- [l,5-a]benzimidazole; 2,6-dihydroxypyridine; 2,6-dihydroxy-3,4-dimethylpyridine; 6- hydroxybenzomorpholine; 2,6-dihydroxy- 3,4-dimethylpyridine; 3,5-diamino-2,6- dimethoxypyridine; 3-amino-2- methylamino-6-methoxypyridine; salts thereof; and mixtures thereof.

Preferred coupler include : 2-methylresorcinol, 2,4-diaminophenoxyethananol, resorcinol, 1 -napthol, 2-methyl-5-hydroxyethylaminophenol, 4-amino-2- hydroxytoluene, meta-aminophenol and 2-amino-4-hydroxyethylaminoanisole sulphate. Particularly preferred is meta amino-phenol, especially when used in combination with a second coupler.

Levels of oxidation base/developers and Couplers

Any of the developers and couplers described above may be combined to form a mixture of developers and couplers. The dyeing compositions of the present invention will generally comprise from about 0.001 percent to about 10 percent by weight of the dyeing composition of developer and coupler dyes. For example, dyeing compositions providing low intensity dyeing such as natural blond to light brown hair shades generally comprise from about 0.001 percent to about 5 percent, in some embodiments, from about 0.1 percent to about 2 percent, in certain embodiments, from about 0.2 percent to about 1 percent by weight of dyeing composition of developers and couplers. Darker shades such as browns and black typically comprise from 0.001 percent to about 10 percent by weight, in some embodiments, from about 0.05 percent to about 7 percent by weight, in certain embodiments, from about 1 percent to about 5 percent by weight of the dyeing composition of developers and couplers. Developer compounds are generally used in approximately equimolar quantities with respect to coupler compounds., preferably at molar ratio of developer to coupler from 0.95 to 1 .05.

The developer compound may, however, be present in a greater or lesser quantity with respect to the coupler compound.

Preferably the mole fraction ratio of coupler to 4, 5-diaminopyrazole a hair colouring is from 0.70 to 1.30. This is of particular benefit when the coupler is an amino phenol, especially meta-amino phenol.

Direct Dyes

The dyeing compositions may also comprise compatible direct dyes, in an amount sufficient to provide coloring, particularly with regard to intensity. Typically, such an amount will range from about 0.05 percent to about 4 percent, by weight of the dyeing composition. Suitable direct dyes include but are not limited to: Acid Yellow 1 ; Acid Orange 3; Disperse Red 17; Basic Brown 17; Acid Black 52; Acid Black 1 ; Disperse Violet 4; 4-nitro-o-phenylenediamine; 2- nitro-p-phenylenediamine;

Picramic Acid; HC Red No. 13; 1, 4-bis-(2'-hydroxyethyl)-amino-2- nitrobenzene; 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-chloro-5-nitro-N-hydroxyethyl-p- phenylenediamine; HC Red No. 3; 4-amino-3-nitrophenol; 2-hydroxyethylamino-5- nitroanisole; 3-nitro-p- hydroxyethylaminophenol; 2-amino-3-nitrophenol; 6-nitro-o- toluidine; 3-methylamino-4- nitrophenoxyethanol; 2-nitro-5-glycerylmethylaniline; HC Yellow No. 1 1 ; HC Violet No. 1 ; HC Orange No. 2; HC Orange No. 3; HC Yellow No. 9; 4-nitrophenyl aminoethylurea; HC Red No. 10; HC Red No. 1 1 ; 2- hydroxyethyl picramic acid; HC Blue No. 12; HC Yellow No. 6; hydroxyethyl-2- nitro-p-toluidine; HC Yellow No. 12; HC Blue No. 10; HC Yellow No. 7; HC Yellow No. 10; HC Blue No. 9; N-ethyl-3-nitro PABA; 4-amino-2-nitrophenyl-amine-2'- carboxylic acid; 2-chloro-6-ethylamino-4-nitrophenol; 6-nitro-2,5-pyridinediamine; HC Violet No. 2; 2-amino-6-chloro-4-nitrophenol; 4-hydroxypropylamino-3- nitrophenol; HC Yellow No. 13; l,2,3,4-tetrahydro-6-nitrochinoxalin; HC Red No. 14; HC Yellow No. 15; HC Yellow No. 14; 3-amino-6-methylamino-2-nitropyridine; 2,6-diamino-3-((pyridine-3-yl)azo)pyridine; Basic Red No. 1 18; Basic Orange No. 69; N-(2-nitro-4-aminophenyl)-allylamine; 4-[(4-amino-3- methylphenyl)(4-imino-3- methyl-2,5-cyclohexadien-l-ylidene) methyl] -2-methyl- benzeneamine- hydrochloride; 2- [ [4-(dimethyl- amino)phenyl] azo] -1 ,3 -dimethyl- 1 H- imidazolium chloride; l-methyl-4-[(methylphenyl-hydrazono)methyl]- pyridinium, methyl sulfate; 2-[(4- aminophenyl) azo] -1 , 3 -dimethy 1 -1 H-imidazolium chloride; Basic Red 22; Basic Red 76; Basic Brown 16; Basic Yellow 57; 7-(2',4'-dimethyl- 5'-sulfophenylazo)-5-sulfo-8- hydroxynaphthalene; Acid Orange 7; Acid Red 33; I- (3'-nitro-5'-sulfo-6'-oxophenylazo)-oxo- naphthalene chromium complex; Acid Yellow 23; Acid Blue 9; Basic Violet 14; Basic Blue 7; Basic Blue 26; sodium salt of mixture of mono- and disulfonic acids (mainly the latter) of quinophthlanone or 2-quinolylindandione; Basic Red 2; Basic Blue 99; Disperse Red 15; Acid Violet 43; Disperse Violet 1 ; Acid Blue 62; Pigment Blue 15; Acid Black 132; Basic Yellow 29; Disperse Black 9; l-(N-methylmorpholinium-propylamino)-4-hydroxy- anthraquinone methylsulfate; HC Blue No. 8; HC Red No. 8; HC Green No. 1 ; HC Red No. 9; 2-hydroxy-l,4- naphthoquinone; Acid Blue 199; Acid Blue 25; Acid Red 4; Henna Red; Indigo; Cochenille; HC Blue No. 14; Disperse Blue 23; Disperse Blue 3; Disperse Blue 377; Basic Red 51 ; Basic Orange 31 ; Basic Yellow 87; and mixtures thereof. Preferred direct dyes include but are not limited to: Disperse Black 9; HC Yellow 2; HC Yellow 4; HC Yellow 15; 4-nitro-o- phenylenediamine; 2-amino-6-chloro-4-nitrophenol; HC Red 3; Disperse Violet 1 ; HC Blue 2; Disperse Blue 3; Disperse Blue 377; Basic Red 51 ; Basic Orange 31 ; Basic Yellow 87; and mixtures thereof.

Particularly preferred direct dyes include further comprising Acid red 92, HC yellow no2 and 2-amino-6-chloro-4-nitrophenol, most preferably Acid red 92.

Solvent

The dying composition and colorant composition may comprise a solvent comprising water or a mixture of water and at least one organic solvent to dissolve the compounds present in the dyeing composition or colorant composition that would not typically be sufficiently soluble in water. Suitable organic solvents for use herein include, but are not limited to: Ci to C₄ lower alkanols (e.g., ethanol, propanol, isopropanol), aromatic alcohols (e.g. benzyl alcohol and

phenoxyethanol); polyols and polyol ethers (e.g., carbitols, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, monomethyl ether, hexylene glycol, glycerol, ethoxy glycol), and propylene carbonate. When present, organic solvents are typically present in an amount ranging from about 1 percent to about 30 percent, by weight of the dyeing composition or the colorant composition. In some embodiments, the solvent comprises water, ethanol, propanol, isopropanol, glycerol, 1 ,2-propylene glycol, hexylene glycol, ethoxy diglycol, or mixtures thereof. Oxidizing Composition

The oxidizing composition is separate from the dyeing composition, which contains the developers, couplers and inhibiting system. The colorant

compositions may comprise an oxidizing composition comprising an oxidizing agent, present in an amount sufficient to bleach melanin pigment in hair and/or oxidize dye precursors (developers).

Typically, such an amount ranges from about 1 percent to about 20 percent, in some embodiments, from about 3 percent to about 15 percent, in other

embodiments, from about 6 percent to about 12 percent by weight of the oxidizing composition.

Suitable oxidizing agents include inorganic peroxygen materials capable of yielding hydrogen peroxide in an aqueous medium are suitable and include, but are not limited to: hydrogen peroxide; inorganic alkali metal peroxides (e.g.

sodium periodate and sodium peroxide); organic peroxides (e.g. urea peroxide, melamine peroxide); inorganic perhydrate salt bleaching compounds (e.g. alkali metal salts of perborates, percarbonates, perphosphates, persilicates, and persulphates, in some embodiments, sodium salts thereof), which may be incorporated as monohydrates, tetrahydrates, etc.; alkali metal bromates;

enzymes; and mixtures thereof. In a preferred embodiments, the oxidizing agent is hydrogen peroxide. Thickeners

The dyeing compositions or colorant compositions may comprise a thickener in an amount sufficient to provide the colorant 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 about 0.1 percent, in some embodiments, at least about 0.5 percent, in other embodiments, at least about 1 percent, by weight of the colorant composition.

Suitable 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), 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), acrylates/steareth-20 methacrylate crosspolymer (available as ACULYN(TM) 88), acrylates/vinyl neodecanoate crosspolymer (available as ACULYN(TM) 38), acrylates/beheneth- 25 methacrylate copolymer (available as ACULYN(TM) 28), acrylates/C10- 30 alkyl acrylate crosspolymer (available as Carbopol(R) ETD 2020), 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, and blends of Ceteth - 10 phosphate, Di- cetyl phosphate and Cetearyl alcohol (available as CRODAFOS(TM) CES). pH Modifiers and Buffering Agents

The dyeing compositions may further comprise a pH modifier and/or buffering agent in an amount that is sufficiently effective to adjust the pH of the colorant composition to fall within a range from about 3 to about 13, in some embodiments, from about 8 to about 12, in certain embodiments, from about 9 to about 1 1 .

Suitable pH modifiers and/or buffering agents for use herein include, but are not limited to: ammonia, alkanolamides such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, tripropanolamine, 2-amino-2-methyl- 1 -propanol, and 2-amino-2-hydroxymethyl- 1,3,-propandiol and guanidium salts, alkali metal and ammonium hydroxides and carbonates, in some embodiments, sodium hydroxide and ammonium carbonate, and acidulents such as inorganic and inorganic acids, e.g., phosphoric acid, acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloric acid, and mixtures thereof.

Additional Composition Components The dyeing compositions may further comprise additional components, e.g., formulation components, known, conventionally used, or otherwise effective for use in colorant compositions such as carbonate ion sources;

peroxymonocarbonate ion sources; anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof; anionic, cationic, chelants, nonionic, amphoteric or zwitterionic, amino sugars, antifoams, antioxidants, esters of amino acids or mixtures thereof, buffers; dispersing agents; peroxide stabilizing agents; natural ingredients, e.g. proteins and protein derivatives, and plant extracts;

silicones (volatile or non-volatile, modified or non-modified), film-forming agents, ceramides, preserving agents; and opacifiers Further suitable compounds are amino acids, in particular arginine, lysine, proline, glutamine, histidine, sarcosine, taurine, serine, glutamic acid, tryptophan, or mixtures thereof, or the salts, such as the potassium, sodium, or ammonium salts thereof, or mixtures thereof.

These compounds may be present in the dyeing compositions and colorant compositions at a concentration of from about 0.01 percent to about 10 percent by weight of the total colouring composition, more preferably from about 0.1 percent to about 7 percent by weight .

The invention will now be illustrated by the following non-limiting Examples Example 1

The activator solution used was a 6wt% solution of hydrogen peroxide.

Claims

1 . A hair colouring composition comprising:

i) at least 0.05 wt% of the total composition of beeswax and

at least 0.01 wt%, of the total composition of a 4, 5-diaminopyrazole. A hair colouring composition in which the level of 4,5-diaminoprazole ^' from 0.1 to 3.5 wt% of the total composition

A hair colouring composition according to any preceding claim in which 4,5- diaminopyrazole is 4,5-diamino-1 -(2'hydroxyethyl)-1 H pyrazole.

A hair colouring composition according to any preceding claim further comprising couplers selected from the group consisting of : 2- methylresorcinol, 2,4-diaminophenoxyethananol. Resorcinol, 1 -napthol, 2- methhyl-5-hydroxyethylaminophenol, 4-amino-2-hydroxytoluene, meta- aminophenol and 2-amino-4-hydroxyethylaminoanisole sulphate..

A hair colouring composition according to any preceding claim further comprising meta amino-phenol.

A hair colouring composition according to any preceding claim further comprising an oxidation base selected from toluene 2-5 diamine sulphate and para-amino-phenol.

A hair colouring composition according to any preceding claim further comprising a direct dye.

A hair colouring composition according to any preceding claim further comprising acid red 92, HC yellow no2, 2-amino-6-chloro-4-nitrophenol, preferably Acid red 92.

9. A hair colouring composition according to claim 8 in which the direct dye comprises Acid red 92.

10. A hair colouring composition according to claim 9 in which the composition further comprises HC yellow No 2.

1 1 . A hair colouring composition according to any preceding claim in which the level of direct dye is the total composition is from 0.1 to 0.5 wt% 12. A hair colouring composition according to any preceding claim in which the weight ratio of beeswax to 4,5 diaminopyrazole is from 10: 1 to 1 :2.

13. A method of colouring hair comprising the steps of applying to the hair a composition comprising

i) at least 0.1 wt% beeswax and

ii) at least 0.01 wt% of a 4, 5-diaminopyrazole.

14. Use of beeswax to enhance the colour intensity of hair colour arising from treatment of the hair with a composition comprising a 4, 5-diaminopyrazole.

15. Use of beeswax to prolong the colour intensity of hair coloured with with a composition comprising a 4, 5-diaminopyrazole.