AU731724B2 - Oxidation colorants - Google Patents

Abstract

Dyes with brilliant copper and gold shades can be obtained by using oxidation colorants, containing 2-aminophenol as a coupling constituent and a compound of formula (I) as a developing agent, wherein X stands for a hydroxyl group or a group NR<3>R<4>, R<3> and R<4> independently stand for hydrogen, a hydroxyalkyl or alkyl group with 1 to 4 carbon atoms each, or stand for a heterocyclic ring system in combination with the nitrogen atom carrying them, and Y, Z and T independently stand for a hydroxyl group or an amino group with the proviso that a maximum of two of the substituents X, Y, Z and T are hydroxyl groups.

Description

Oxidation Colorants This invention relates to oxidation colorants containing special combinations of primary and secondary intermediates for colouring keratin fibres.

By virtue of their intensive colours and good fastness properties, so-called oxidation colorants play a prominent role in the colouring of keratin fibres, particularly human hair. Oxidation colorants contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates in the presence of oxidising agents or atmospheric oxygen.

Good oxidation dye precursors are expected to satisfy above all the following requirements: they must form the required colour tones with sufficient intensity and fastness during the oxidative coupling reaction. In addition, they must be readily absorbed onto the fibres with no significant differences particularly in the case of human hair between damaged and freshly regrown hair (levelling behaviour). They must be resistant to light, heat and the effect of chemical reducing agents, for example permanent wave lotions. Finally, if they are used to colour hair, they should not overly stain the scalp and, above all, should be toxicologically and dermatologically safe.

The primary intermediates used are, for example, primary aromatic amines containing another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Special representatives are, for example, p-phenylenediamine, p-toluylenediamine, paminophenol, o-aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-pphenylenediamine, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4'-diaminodiphenylamine, 4-amino- 3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4aminophenylamino))-2-propanol, 4-amino-2-(2-hydroxyethoxy)-phenol and derivatives according to EP 0 740 741 or WO 94/08970, for example 4,5-diamino-1-(2'-hydroxyethyl)pyrazole.

The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives.

Special representatives are 1-naphthol, pyrogallol, 2,7- and 1,7-dihydroxynaphthalene, oaminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, mphenylenediamine, 1 -phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4diaminophenoxy)-propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4amino-2-hydroxytoluene, 2,6-bis-(2-hydroxyethylamino)-toluene, 2,4-diaminophenoxyethanol, 1methoxy-2-amino-4-(2-hydroxyethylamino)-benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl- C07891 1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2methyl-5-(2-hydroxyethylamino)-phenol and 2,6-dihydroxy-3,4-dimethyl pyridine.

So far as the dyes suitable for use in the hair colorants and tinting formulations according to the invention are concerned, reference is also expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264-267; oxidation dye precursors), published as Volume 7 of the Series "Dermatology" Ch. Culnan and H.

Maibach), Marcel Dekker Inc., New York/Basel, 1986, and to the "Europaische Inventar der Kosmetik- Rohstoffe" published by the Europaische Gemeinschaft and available in disk form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel Mannheim.

In general, natural colour tones cannot be obtained with a single primary intermediate/secondary intermediate combination. In practice, therefore, a combination of various primary intermediates and secondary intermediates is needed to obtain a natural-looking colour.

Thus, gold and copper tones with the primary intermediate 2,4,5,6-tetraaminopyrimidine can normally only be obtained by combination with two different secondary intermediates, one red and one yellow. Suitable red secondary intermediates are, for example, resorcinol, resorcinol derivatives and m-diaminobenzene derivatives while suitable yellow secondary intermediates are, for example, 2,7dihydroxynaphthalene, 2,6-dihydroxy-4-methyl pyridine and 2,6-dihydroxy-3,4-dimethyl pyridine.

However, the use of these three-component combinations is generally attended by problems such as, for example, the different reaction rates of the two secondary intermediates and the different washing resistances of the products formed which leads to unwanted colours or changes in colour. In addition, unwanted nuances can occur according to the exact natural colour of the hair to be dyes.

Accordingly, there is a constant need for new improved primary intermediate/secondary intermediate combinations.

Accordingly, the problem addressed by the present invention was to provide new primary intermediate/secondary intermediate combinations which would satisfy the requirements oxidation dye precursors are expected to meet to a particular degree.

It has now surprisingly been found that special combinations of primary and secondary intermediates known per se lead to particularly intensive colours. Thus, not only are certain shades obtainable by combining a single secondary intermediate with a single primary intermediate, particularly brilliant copper and gold tones can also be obtained by combining this secondary and primary intermediate component with special other secondary or primary intermediate components.

These colours are distinguished inter alia by particularly good fastness to light, washing and rubbing and by unexpectedly high levelling power.

Accordingly, the present invention relates to oxidation colorants for colouring keratin fibres, more especially human hair, containing at least one secondary intermediate and at least one primary intermediate in a water-containing carrier, characterised in that the secondary intermediate is 2-aminophenol or a salt thereof with an inorganic or organic acid and C07891 the primary intermediate is selected from compounds corresponding to formula

Y

T N X(l) in which X is a hydroxy group or a group NR 3

R

4 where R 3 and R 4 independently of one another represent hydrogen, a hydroxyalkyl or alkyl group containing 1 to 4 carbon atoms or, together with the nitrogen atom carrying them, form a heterocyclic ring system, and Y, Z and T independently of one another represent a hydroxy group or an amino group, with the proviso that at most two of the substituents X, Y, Z and T are hydroxy groups, and salts thereof with an inorganic or organic acid.

Keratin fibres in the context of the present invention include pelts, wool, feathers and, more particularly, human hair. Although the oxidation colorants according to the invention are particularly suitable for colouring keratin fibres, there is basically nothing to prevent them from being used in other fields, particularly in colour photography.

The colorants according to the invention contain 2-aminphenol or a physiologically compatible salt of this compound with an inorganic or organic acid as a first compulsory component.

Another compulsory component is a primary intermediate corresponding to formula In this connection, a "heterocyclic ring system" in the context of the invention is understood to be any nitrogen-containing ring system, whether saturated or unsaturated. Preferred ring systems are, for example, the piperidine and the morpholine system.

These pyrimidine derivatives such as, for example, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy- 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2-dimethylamino-4,5,6-triaminopyrimidine are compounds well-known to the expert. DE-OS 23 59 399 is cited here as representative of the various publications which disclose these compounds.

Reference is expressly made to the content of this document, particularly where it discloses the production of these compounds.

Particularly preferred pyrimidine derivatives, used either individually or in combination, are 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.

The primary and secondary intermediates present in the colorants according to the invention may be used both as free bases and in the form of their salts with inorganic or organic acids, for example hydrochlorides, sulfates and hydrobromides.

In a first preferred embodiment, the colorants according to the invention contain no oxidation so dye precursors other than 2-aminophenol and the compounds of formula Thus, intensive redorange tones with good levelling behaviour, even after several washes, are obtained, for example, by combining 2-aminophenol and 2,4,5,6-tetraaminopyrimidine.

In a second preferred embodiment, the colorants according to the invention contain at least one other primary intermediate. This primary intermediate is selected from the group consisting of 1,4diaminobenzene, 3-methyl-1,4-diaminobenzene, 2,5-diaminotoluene, 1-(2'-hydroxyethyl)-2,5diaminobenzene, 2-(2,5-diaminophenoxy)-ethanol, N,N-bis-(2'-hydroxyethyl)-1,4-diaminobenzene, 3- C07891 methyl-4-aminophenol and 2-methylamino-4-aminophenol. The tones obtained in this embodiment have a specifically attenuated brilliance.

In a third preferred embodiment, the colorants according to the invention contain at least one other secondary intermediate selected from resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, dimethylresorcinol and 4-chlororesorcinol. This three-component combination according to the invention gives particularly warm copper and golden blond tones distinguished by very good fastness properties and, in particular, by excellent fastness to washing on damaged hair.

The hair colorants according to the invention contain both the primary intermediates and the secondary intermediates in a quantity of preferably 0.01 to 20wt% and more preferably 0.5 to based on the oxidation colorant as a whole. The primary intermediates and secondary intermediates are generally used in a substantially equimolar ratio to one another. Although it has proved to be of advantage to use the primary and secondary intermediates in an equimolar ratio, there is no disadvantage in using individual oxidation dye precursors in a certain excess so that primary intermediates and secondary intermediates may be present in a molar ratio of preferably 1:0.5 to 1:2.

Besides the primary intermediate/secondary intermediate combinations according to the invention, the hair colorants may optionally contain other primary and/or secondary intermediates to obtain special shades.

In addition, the hair colorants according to the invention may contain typical substantive dyes in addition to the oxidation dye precursors to further modify the shades.

Substantive dyes are normally nitrophenylendiamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the compounds known under the International names or trade names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

The colorants according to the invention of this embodiment preferably contain the substantive dyes in a quantity of preferably 0.01 to 20wt%, based on the colorant as a whole.

The colorants according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet.

Other dye components which may be present in the colorants according to the invention are indoles and indolines and physiologically compatible salts thereof. Preferred examples are 5,6dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6dihydroxyindole, N-butyl-5,6-dihydroxyindole, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6aminoindoline and 4-aminoindoline.

C07891 The oxidation dye precursors or the substantive dyes optionally present do not have to be single compounds. On the contrary, other components may be present in small quantities in the hair colorants according to the invention due to the processes used to produce the individual dyes providing these other components do not adversely affect the colouring result or have to be ruled out for other reasons, for example toxicological reasons.

To produce the colorants according to the invention, the oxidation dye precursors are incorporated in a suitable water-containing carrier. For colouring hair, such carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair.

The colorants according to the invention are adjusted to a pH of preferably 6.5 to 11.5 and more preferably 9 to The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be of particular advantage.

Suitable anionic surfactants for the hair colorants according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterised by a water-solubilising anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, amide and hydroxy groups and generally ester groups may also be present in the molecule. The following are examples of suitable anionic surfactants in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group: linear and branched fatty acids containing 8 to 22 carbon atoms (soaps), ether carboxylic acids corresponding to the formula R-O-(CH 2

-CH

2 0)x-CH 2 -COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x 0 or 1 to 16, acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, acyl taurides containing 10 to 18 carbon atoms in the acyl group, acyl isethionates containing 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates containing 12 to 18 carbon atoms, linear a-olefin sulfonates containing 12 to 18 carbon atoms, a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R-O(CH 2

-CH

2 0)x-

SO

3 H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x 0 or 1 to 12, C07891 6 mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C8-22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one or group in the is molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl- N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, Nacylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate.

A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C8- 1 8 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, Nhydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacyl aminoethyl aminopropionate and C12-1 8 acyl sarcosine.

Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are products of the addition of 2 to 30mol of ethylene oxide and/or 0 to 5mol of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group,

C

1 2- 2 2 fatty acid monoesters and diesters of products of the addition of 1 to 30mol of ethylene oxide onto glycerol, C8-2 2 alkyl mono- and oligoglycosides and ethoxylated analogues thereof, products of the addition of 5 to 60mol of ethylene oxide onto castor oil and hydrogenated castor oil, C07891 products of the addition of ethylene oxide onto sorbitan fatty acid esters, products of the addition of ethylene oxide onto fatty acid alkanolamides.

Examples of cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternised protein hydrolysates.

Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxyamino-modified silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM- 55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid®S 18, are distinguished not only by their favourable conditioning effect, but also and in particular by their ready biodegradability.

Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@, are also readily biodegradable.

One example of a quatemary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat® 100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).

The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained.

The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homologue distribution and products with a narrow homologue distribution. Products with a "normal" homologue distribution are mixtures of homologues which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homologue distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homologue distribution can be of advantage.

Other active substances, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, C07891 cationic polymers, such as quaternised cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quaternised with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternised polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/ isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers, thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, carob bean flour, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, structurants, such as glucose, maleic acid and lactic acid, hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils, protein hydrolysates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and quaternised protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins, solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, antidandruff agents, such as Piroctone Olamine and Zinc Omadine, akalising agents such as, for example, ammonia, monoethanolamine, 2-amino-2-methyl propanol and 2-amino-2-methyl-1,3-propanediol, other substances for adjusting the pH value, active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, cholesterol, UV filters, consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides, complexing agents, such as EDTA, NTA and phosphonic acids, swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, C07891 opacifiers, such as latex, pearlescers, such as ethylene glycol mono- and distearate, propellents, such as propane/butane mixtures, N20, dimethyl ether, C02 and air and antioxidants.

To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30wt% while thickeners are used in concentrations of 0.1 to 25wt%, based on the colorant as a whole.

In principle, the colour can be oxidatively developed with atmospheric oxygen. However, a chemical oxidising agent is preferably used, particularly when human hair is to be not only coloured, but also lightened. Particularly suitable oxidising agents are hydrogen peroxide and addition products thereof with urea, melamine or sodium borate. Oxidation may also be carried out with enzymes. In this case, the enzymes may be used both to produce oxidising per compounds and to enhance the effect of an oxidising agent present in small quantities. One example of an enzymatic process is the procedure whereby the effect of small quantities (for example 1% and less, based on the formulation as a whole) of hydrogen peroxide is enhanced by peroxidases.

The preparation of the oxidising agent is preferably mixed with the preparation of the oxidation dye precursors immediately before colouring of the hair. The ready-to-use hair colouring preparation formed should preferably have a pH value in the range from 6 to 10. In a particularly preferred embodiment, the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 40 0 C. After a contact time of about 5 to 30 minutes, the hair colorant is removed from the hair to be coloured by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant content, for example a colouring shampoo, has been used.

In the particular case of hair which is difficult to colour, the preparation containing the oxidation dye precursors may be applied to the hair without being mixed with the oxidation component beforehand. The oxidation component is applied after a contact time of 20 to 30 minutes, optionally after rinsing. After another contact time of 10 to 20 minutes, the hair is rinsed and optionally shampooed.

The invention is illustrated by the following Examples.

Examples Colorants with the compositions shown in Table 1 were prepared [all quantities are in grams unless otherwise indicated]. Immediately before use, the colorant was mixed with a commercial 6% hydrogen peroxide preparation in a ratio by weight of 1:1.

The colorants were applied to natural white hair tresses (Kerling), the mixture applied remaining on the hair tresses for 30 minutes at a temperature of 230C. The colouring results are set out in Table 2.

Table 1: formulations Component Formulation I Formulation 21 Formulation 3 Formulation4 Texapon® N281 20.0 20.0 20.0 20.0 C07891 Component Formulation I Formulation 2 Formulation 3 Formulation 4 DehytonOK 2 12.5 12.5 12.5 12.5 Lorol@ techn.

3 2.0 2.0 2.0 Hydrenol 4 8.5 8.5 8.5 EumulginO B2 5 0.75 0.75 0.75 0.75 Ascorbic acid 0.1 0.1 0.1 0.1 Sodium sulfite 0.1 J0.1 0.1 0.1 2-Am inophenol 1.1 J1.1 2.2 4-Hydroxy-2,5,6-triaminopydmidine sulfate 2.6 j-- 2,4,5,6-tetraamino- pyrimidine sulfate J2.4 1 4.8 Ammonia t W ater tol100 2 3 4 Sodium lauryl ether sulfate (ca. 28% active substance; CTFA name: Sodium Laureth Sulfate) (HENKEL) Fatty acid amide derivative of betaine structure with the formula R-CONH(CH 23

N'(CH

3 2

CH

2 CO&- (ca.

active substance; CTFA name Cocoamidopropyl Betaine) (HENKEL)

C

1 21 8 Fatty alcohol C,6-, 8 Fatty alcohol (HENKEL) Cetylstearyl alcohol with ca. 2Omol EQ (CTFA name: Ceteareth-20) (HENKEL) Table_2:_colours -Formulation Result 1 -Flat yellow tone with very little red 2 Red-orange 3 Yellow-orange 4 Luminous yellow-orange C07891

Claims (9)

1. An oxidation colorant for colouring keratin fibres, containing at least one secondary intermediate and at least two primary intermediates in a water-containing carrier, characterised in that the secondary intermediate is 2-aminophenol or a salt thereof with an inorganic or organic acid and a first primary intermediate is selected from compounds corresponding to formula Y z T N X(I) l0 in which X is a hydroxy group or a group NR3R 4 where R 3 and R 4 independently of one another represent hydrogen, a hydroxyalkyl or alkyl group containing 1 to 4 carbon atoms or, together with the nitrogen atom carrying them, form a heterocyclic ring system, and Y, Z and T independently of one another represent a hydroxy group or an amino group, with 00 the proviso that at most two of the substituents X, Y, Z and T are hydroxy groups, and 15 salts thereof with an inorganic or organic acid and a second primary intermediate is selected from 1,4-diaminobenzene, 3- methyl-1,4-diaminobenzene, 2,5-diaminotoluene, 1-(2'-hydroxyethyl)-2,5- diaminobenzene, 2-(2,5-diaminophenoxy)-ethanol, N,N-bis-(2'-hydroxyethyl)-1,4- diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol. 20

2. An oxidation colorant as claimed in claim 1, characterised in that the fibres are human hair.

3. An oxidation colorant as claimed in claim 1 or claim 2, characterised in that the compound corresponding to formula is selected from 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.

4. An oxidation colorant as claimed in any one of claims 1 to 3, characterised in that the colorant contains another secondary intermediate selected from resorcinol, 2- methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol and 4-chlororesorcinol.

An oxidation colorant as claimed in any one of claims 1 to 4, characterised in that the secondary intermediate(s) are present in a quantity of 0.01 to 20wt% and the primary intermediates are present in a quantity of 0.01 to 20wt% based on the oxidation Scolorant as a whole. [IADAYLIB\LIBAA]08560.doc:ACR I I f 12

6. An oxidation colorant as claimed in claim 5, characterised in that the secondary intermediate(s) are present in a quantity of 0.5 to

7. An oxidation colorant as claimed in claim 5 or claim 6, characterised in that the primary intermediates are present in a quantity of 0.5 to

8. An oxidation colorant for colouring keratin fibres, containing at least one secondary intermediate and at least two primary intermediates in a water-containing carrier, said oxidation colorant being substantially as hereinbefore described with reference to formulation 1 or formulation 2 of the examples.

9. The use of the oxidation colorant claimed in any one of claims 1 to 8, for colouring human hair. A method of colouring human hair, the method comprising applying to human hair the oxidation colorant claimed in any one of claims 1 to 8. Dated 31 January 2001 HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN 15 Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON oo* *o*0 o [I:\DAYLIB\LIBAA]08560.do:ACR