AU737695B2

AU737695B2 - Hair colorants

Info

Publication number: AU737695B2
Application number: AU89780/98A
Authority: AU
Inventors: Horst Hoffkes; Bernd Meinigke; Hinrich Moller; David Rose
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-07-25
Filing date: 1998-07-21
Publication date: 2001-08-30
Anticipated expiration: 2018-07-21
Also published as: ATE304837T1; DE19732016A1; EP0988022A1; WO1999007334A1; JP2001513489A; AU8978098A; DE59813067D1; EP0988022B1

Abstract

The invention pertains to the use of methine dyes of formula (I) for colouring keratin fibers, especially in human hair. Hair colorants are also applied which contain methine dyes of formula (I). The compounds of formula (1) produce intensive lightproof and rub-fast colorations in the range of yellow, red and violet shades.

Description

1 Hair Colorants This invention relates to the use of methine dyes with a specific structure for colouring keratin fibres, more particularly human hair.

Besides oxidation dyes, which lead to particularly true permanent hair colours, substantive hair dyes in particular play an important part in the colouring of keratin fibres. These dyes produce semipermanent or temporary hair colours with relatively little resistance to washing. Compounds belonging to the group of nitrobenzene derivatives are mainly used as substantive dyes.

Unfortunately, compounds of this type often lack the solubility in water required for colouring from aqueous liquor. Other known substantive dyes are, for example, anthraquinone dyes, indophenols, triphenylmethane dyes and cationic azo dyes.

The cationic dyes have the advantage of good solubility in water and good absorptivity onto the mostly negatively charged protein fibres.

WO 95101772 Al and WO 95115144 Al describe, for example, cationic azo and azomethine dyes which are also suitable for colouring hair under physiologically acceptable temperature and residence time conditions. One problem of using dyes such as these for colouring hair is that the scalp is excessively stained.

Accordingly, there was a need to find dyes which would form intensive colour tones in short residence times at low temperatures and which would not overly stain the scalp. In addition, the dyes would be highly resistant to light, heat, perspiration and shampoos and to the chemicals used in the permanent waving of the hair. Finally, they would also be toxicologically and dermatologically safe.

They would also have to be highly compatible with other dyes and, for example, with oxidation dyes and the components normally found in oxidation colorants because substantive dyes of various types and oxidation dyes are often combined to modify colour tone. For this reason, high resistance to oxidising and reducing agents would also be necessary.

It has now been found that certain methine dyes satisfy the requirements stated above to a high degree.

Accordingly, the present invention relates to the use of methine dyes corresponding to formula n+ R 2

I(I)

RZ

for colouring keratin fibres, more particularly human hair.

In formula R 1 and R 2 independently of one another represent hydrogen, a C1-4 alkyl group, a C1i-4 alkoxy group, a hydroxy group, an amino group or a mono- or di-(C14-alkyl)-amino group, R 3 is hydrogen, a C14 alkyl group or a C2-4 hydroxyalkyl group, R 4 to R 7 independently of one another represent hydrogen or a C14 alkyl group, X is a group corresponding to formulae (11) to (IV): C08068 RIU (II) R R 2 CH-- m

R

R2 3

R

z CHRI4

(IV)

R

1 3 and y is an integer of 1 to 3, n is the number of positive charges in the cation and A is an m-valent physiologically compatible anion.

The invention also relates to a hair colourant which contains 0.01 to 10wt% of methine dye, based on the hair colourant as a whole, in a carrier suitable for colouring, wherein the methine dye corresponds to formula n+ 5 *R 4 f /-(CR-CR7)y-X nA m

(I)

in which R 1 and R 2 independently of one another represent hydrogen, a Cl- alkyl group, a C 1 4 alkoxy group, a hydroxy group, an amino group or a mono- or di-(C14-alkyl)-amino group, R 3 is hydrogen, a 10 C14 alkyl group or a C 2 4 'hydroxyalkyl group, R 4 to R 7 independently of one another represent hydrogen or a C 1 4 alkyl group, X is a group corresponding to formulae (II) to (IV):

R

1 o (II) R3 Aruo'4 (IV) [R:\L1BAA]08856.doc:sak where R 1 to R 5 stand for one of the groups mentioned under R 1 to R 5

R

8 and R 1 2 independently of one another represent hydrogen, a halogen atom, a hydroxy group, a C1-4 alkoxy group or a C2-4 hydroxyalkyl group, R 9 and R 1 1 represent hydrogen or, together with Ro 1 form a methylenedioxy group, R 1 0 additionally represents a C.4 alkoxy group, a C24 hydroxyalkyl group or a group corresponding to formula -NR15R16

(V)

in which R 15 and R 16 independently of one another represent a C1-4 alkyl group, a C24 hydroxyalkyl group or, together with the nitrogen atom, form a pyrrolidine, piperidine or piperazine ring, two adjacent substituents R 8 to R 1 2 together form a fused benzene ring or the substituent corresponding to formula (II) is a 2,3,6,7-tetrahydro-lH,5H-pyrido[3.2.1-ij]-quinoline residue. R 13 stands for hydrogen, a halogen atom, a C14 alkyl group or a C14 alkoxy group, R 1 4 is a phenyl or naphthyl group substituted by C14 alkyl groups, C14 alkoxy groups, a hydroxy group, a carboxy group or a mono- or di-(Cl4-alkyl)-amino group, the alkyl groups optionally forming one or two fused heterocycles with the phenyl or naphthyl group or one heterocycle with the amine nitrogen, and for pyridyl, quinolyl, furyl, thienyl groups or the group (III), Z is a direct bond, a methylene group, a dimethyl methylene group or an ethylene group, y is an integer of 1 to 3, n is the number of positive charges in the cation and A is an m-valent physiologically compatible anion.

In substituents corresponding to formula R 8 and R 1 2 independently of one another represent hydrogen, a halogen atom, a hydroxy group, a C1-4 alkoxy group or a C2.4 hydroxyalkyl 20 group, R 9 and R 11 represent hydrogen or, together with R 1 0 form a methylenedioxy group, R 10 additionally represents a C1-4 alkoxy group, a C24 hydroxyalkyl group or a group corresponding to formula .n -NR 15

R

16

(V)

in which R 1 5 and R 1 6 independently of one another represent a C14 alkyl group, a C2-4 hydroxyalkyl group or, together with the nitrogen atom, form a pyrrolidine, piperidine or piperazine ring, two adjacent substituents R 8 to R 12 form a fused benzene ring or the substituent corresponding to formula (II) is a 2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]-quinoline residue.

In compounds corresponding to formula in which X is a substituent of formula (III), the substituent R 1 corresponds to the substituent R 1 or one of the other meanings of R 1 The same 30 applies to R 2 and R 2

R

3 and R 3

R

4 and R 4 and to R 5 and R 5 In compounds corresponding to formula in which X is a substituent corresponding to formula

R

1 3 stands for hydrogen, a halogen atom, a C14 alkyl group or a C14 alkoxy group, R 14 is a phenyl or naphthyl group substituted by C1- alkyl groups, C14 alkoxy groups, a hydroxy group, a carboxy group or a mono- or di-(C14-alkyl)-amino group, the alkyl groups optionally forming one or two fused heterocycles with the phenyl or naphthyl group or one heterocycle with the amine nitrogen, and for pyridyl, quinolyl, furyl, thienyl groups or the group (III) and Z is a direct bond, a methylene group, a dimethyl methylene group or an ethylene group.

0 Providing the substances according to the invention are amino compounds, they may be nverted into the corresponding quaternary compounds by protonation, depending on the pH value.

[R:\LBAA]08856.doc:sak 2b Accordingly, all statements in this specification and hence the claimed scope of protection relate both to the compounds of formula present in free form and to their protonated derivatives.

0*

S

S S

S

0* .5 S. S

SS

S.

S S [R:\LIBAA]08856.doc:sak Keratin fibres in the context of the invention are understood to be pelts, wool, feathers and, in particular, human hair.

Examples of the C 1 4 alkyl groups mentioned as substituents in the compounds according to the invention are the methyl, ethyl, propyl, isopropyl and butyl groups. Ethyl and methyl groups are preferred alkyl groups. Other substituents may be C1iA alkoxy groups, for example a methoxy or an ethoxy group. According to the invention, examples of a C 14 hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. Halogen atoms suitable as substituents are, for example, an F, a CI or a Br atom.

A suitable anion Am- is, for example, chloride, bromide, iodide, sulfate, perchlorate, tetrafluoroborate, tetraphenyl borate and tetrachlorozincate.

One particular advantage of the methine dyes of formula to be used in accordance with the invention lies in their high level-dyeing capacity, ie. the dye is absorbed more or less equally onto the hair shafts and the hair ends so that the more heavily stressed hair ends are not coloured any more intensively than the smooth hair shafts at the hair line.

5Some of the dyes corresponding to formula are known from the literature; those that are not can be produced by methods known from the literature. The production of two dyes of formula not known from the literature is described in detail in the Examples.

Particularly suitable dyes corresponding to formula are those in which R 3 is a methyl group.

According to the invention, other preferred dyes corresponding to formula are those in which

R

4 and R 5 are methyl groups.

The dye does not have to be present as a single compound; mixtures of various dyes corresponding to formula may also be used as the dye. The compounds corresponding to formula give intensive yellow, red and violet tones fast to light and rubbing, somewhat darker tones being obtained in the neutral and alkaline pH range than in the acidic pH range.

The present invention also relates to hair colorants containing the methine dyes of formula (I) S• above in a quantity of 0.01 to 10wt%, based on the hair colorant as a whole, in a carrier suitable for colouring.

According to the invention, colorants in an aqueous carrier or in powder form are particularly preferred.

s o 30 In a first preferred embodiment, the compositions according to the invention are compositions which are intended to produce only temporary colouring of the fibres. Such compositions are often referred to as tints. This embodiment also encompasses, for example, hair treatment compositions with which the hair is not only to be temporarily coloured, but also styled in a certain way. Such products are often referred to as tinting gels.

Since compositions of the type in question are normally formulated without the aid of oxidising components, especially hydrogen peroxide, the compositions according to this embodiment the invention are free from oxidation dye precursors of the primary and secondary intermediate type.

Although the compounds corresponding to formula may also be used sole dye component, "AjRAL, the compositions according to this embodiment preferably contain at least one other dye of the substantive type. Substative dyes are normally nitrophenylenediamines, nitroaminophenols, azo C08068 dyes, anthraquinones or indophenols. Preferred substantive dyes are the compounds known under the International names or commercial 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.

In the context of the invention, substantive dyes also include 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 present in the colorants according to the invention may be indoles and indolines and physiologically compatible salts thereof. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4aminoindole. Other preferred examples are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, Nethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

The other substantive dyes are present in the colorants according to the invention in quantities of preferably 0.01 to 20wt%, based on the colorant as a whole.

In a second preferred embodiment, the claimed colorants are hair colorants for the permanent dyeing of hair. These colorants may contain at least one oxidation dye precursor of the primary intermediate type. These generally colourless compounds react under the effect of oxidising agents or atmospheric oxygen, optionally in the presence of special enzymes or metal ions as catalyst, to form the required dyes. However, combinations of several primary intermediates are generally used, particularly for forming natural hair colours. In addition, at least one so-called secondary intermediate is used. Secondary intermediates react with the primary intermediates under the influence of oxidising agents to form new colours or shades. According to the invention, one or more secondary intermediates may be used either individually or in combination with one or more primary intermediates.

The primary intermediates normally used are 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, C08068 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 94108970, for example 4,5-diamino-1-(2'-hydroxyethyl)pyrazole.

According to the invention, particularly preferred primary intermediates are p-aminophenol, 1- (2'-hydroxyethyl)-2,5-diaminobenzene, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1 -(2-hydroxyethyl)-pyrazole, ptoluylenediamine, 2-aminomethyl-4-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, pphenylenediamine, 3-methyl-p-aminophenol and The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable secondary intermediates 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-dichioro-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, 2,6bis-(2-hydroxyethylamino)-toluene, 2,4-diaminophenoxyethanol, 1 -methoxy-2-amino-4-(2hydroxyethylamino)-benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-i ,2,3,4tetrahydroquinoxaline, 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.

Particularly preferred secondary intermediates are 1-naphthol, 2,7- and 1,7dihydroxynaphthalene, resorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-diaminopyridine, maminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2-methylaniline, 3-amino-2methylamino-6-methoxypyridine, 2,6-dimethyl-3-aminophenol, 2,4-diaminophenoxyethanol, 6-methyl- 1,2,3,4-tetrahydroquinoxaline, 2-methyl-4-chloro-5-aminophenol, 3;4-methylenedioxyaniline, 2methylresorcinol, 5-methyiresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 2-amino-3hydroxypyridine and 2-chloro-6-methyl-3-aminophenol.

According to the invention, primary and secondary intermediates which do not require any oxidising agents other than atmospheric oxygen to develop the colour may be preferred.

The hair colorants according to the invention contain both the primary intermediates and the secondary intermediates in a quantity of preferably 0.005 to 2Owt%, based on the colorant without the oxidising agent. The primary intermediates and secondary intermediates are generally used in substantially equimolar quantities. Although the equimolar quantities of primary and secondary intermediates have proven expedient, a certain excess of individual oxidation dye precursors is not a disadvantage, so that the primary intermediates and secondary intermediates may be present in a molar ratio of 1:0.5 to 1:2.

C08068 Besides the compounds corresponding to formula the primary and/or secondary intermediate, the colorants according to this embodiment of the invention may optionally contain other substantive dyes for nuancing. Reference is made here to the foregoing list.

The dyes and dye precursors do not have to be single compounds. Instead, the hair colorants according to the invention due to the processes used for producing the individual dyes may contain small quantities of other components providing they do not adversely affect the colouring result or have to be ruled out for other reasons, for example toxicological reasons.

With regard to the dyes suitable for use in the hair colouring and tinting formulations according to the invention, reference is also specifically made to Ch. Zviak's work The Science of Hair Care, Chapter 7 (pages 248-250; Substantive Dyes) and Chapter 8, pages 264-267; Oxidation Dye Precursors), published as Vol. 7 of the Series "Dermatology" (Editors: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986 and to the "Europiische Inventar der Kosmetik- Rohstoffe" published by the Europaische Gemeinschaft and available in diskette form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fOr Arzneimittel, Reformwaren und K6rperpflegemittel Mannheim, Germany.

In one preferred embodiment, the colorants according to the invention additionally contain anionic, nonionic or more particularly cationic polymers, particularly if they are also intended to have conditioning or setting properties.

Cationic polymers suitable as conditioning agents contain cationic groups within the polymer chain. These groups may be part of the polymer chain although they may also be positioned in side chains attached to a main chain by intermediate links. Typical cationic groups contain quaternary nitrogen or phosphorus atoms. Groups containing quaternary nitrogen atoms are preferred. The quaternary nitrogen atoms may carry four different substituents or partly identical substituents and may be part of a ring system. Preferred cationic groups are ammonium and imidazolinium groups.

The following are examples of such polymers: Quaternised cellulose derivatives commercially available under the names of Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat@ L 200 and Polymer JR®400 are preferred quartemised cellulose derivatives.

Quaternised guar derivatives commercially available under the names of Cosmedia Guar@ and Jaguar®. Preferred guar derivatives are, for example, Cosmedia Guar@ C-261 and Jaguar® C 13-S.

Copolymers of vinyl pyrrolidone with quaternised derivatives of dialkylaminoacrylate and methacrylate, such as vinyl pyrrolidone/dimethylaminomethacrylate copolymers quatemised, for example, with diethyl sulfate and the copolymer of vinyl pyrrolidone and methacrylamidopropyl trimethyl ammonium chloride. Compounds such as these are commercially available under the names of Gafquat@734, Gafquat@755 and Gafquat® HS100.

Copolymers of vinyl pyrrolidone with vinyl imidazolium methochloride which are commercially available under the name of Luviquat®.

Polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of arylic acid and methacrylic acid. The products commercially available under the names of C08068 Merquat®100 (poly(dimethyl diallyl ammonium chloride)) and Merquat@550 (dimethyl diallyl ammonium chloride/acrylamide copolymer) are examples of such cationic polymers.

Cationically derivatised 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 hydroxylamino-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, Chitosan and derivatives thereof.

The cationic polymers are preferably present in the compositions according to the invention in quantities of 0.1 to 5wt%, based on the composition as a whole.

The following are examples of suitable nonionic polymers: Vinyl pyrrolidone/vinyl ester copolymers of the type marketed for example under the trade mark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, both vinyl pyrrolidone/vinyl acetate copolymers, are preferred nonionic polymers.

Cellulose ethers, such as the hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose marketed under the trade marks Culminal® and Benecel® (AQUALON).

Shellac.

Polyvinyl pyrrolidones of the type marketed under the name Luviskol® (BASF).

The following are examples of suitable anionic polymers: Copolymers of acrylic acid and/or methacrylic acid or esters thereof with C 10 -30 alkyl acrylates of the type marketed, for example, under the name of Pemulen®.

Polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate/crotonic acid and vinyl acetate/vinyl propionate/crotonic acid copolymers.

Compounds of this type are marketed under the names Resyn® (NATIONAL STARCH), Luviset@ (BASF) and Gafset® (GAF). The products Luviset@ CA-66 and Luviset® CAP may be preferable.

Vinyl pyrrolidone/vinyl acrylate copolymers obtainable, for example, under the trade mark Luviflex® (BASF). A preferred polymer is the vinyl pyrrolidone/acrylate terpolymer obtainable under the name of Luviflex® VBM-35 (BASF).

Acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers marketed, for example, under the name of Ultrahold® strong (BASF) and methacrylic acid/ethyl acrylate/t-butyl acrylate terpolymers marketed under the name Luvimer 100P (BASF).

It may be preferred to use anionic, nonionic or cationic polymers in hair colorants which are free from oxidation dye precursors.

To produce the colorants according to the invention, the substantive dyes and the oxidation dye precursors, if any, 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 may also contain any of the known active substances, Sadditives and auxiliaries typical of such formulations. In many cases, the colorants contain at least o\ one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being C08068 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.

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, ether and amide and hydroxyl 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 fatty acids containing 10 to 22 carbon atoms (soaps), ether carboxylic acids corresponding to the formula R-O-(CH 2 -CH20)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, 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 C8-2 2 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 molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl- C08068 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 INCI name of Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H 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 012-18 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 30 moles of ethylene oxide and/or 0 to 5 moles 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, 012-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide onto glycerol, C8-22 alkyl mono- and oligoglycosides and ethoxylated analogues thereof, products of the addition of 5 to 60 moles of ethylene oxide onto castor oil and hydrogenated castor oil, products of the addition of ethylene oxide onto sorbitan fatty acid esters and products of the addition of ethylene oxide onto fatty acid alkanolamides.

Examples of cationic surfactants suitable for use in the compositions 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.

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 C08068 methosulfates marketed under the name of Stepantex® and the products marketed under the name of Dehyquart®, such as Dehyquart AU-46, 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 (INCI 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.

The surfactants are present in the compositions according to the invention in quantities of preferably 1 to 20wt% and more preferably about 6 to 10wt%, based on the composition as a whole, where the composition according to the invention is a colouring shampoo. By contrast, in the case of colouring lotions or colouring gels, quantities of 1 to 10wt% are preferred, quantities of 2 to 4wt% based on the composition as a whole being particularly preferred.

Other active substances, auxiliaries and additives are, for example, thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, 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 and maleic 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, other substances for adjusting the pH value, C08068 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, opacifiers, such as latex, pearlisers, such as ethylene glycol mono- and distearate, propellents, such as propane/butane mixtures, N20, dimethyl ether, CO 2 and air, 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 compositions according to the invention may be formulated in such a way that they may either remain on the hair or may be rinsed out. In a preferred embodiment, the compositions according to the invention are formulated to remain on the hair. This is the case with socalled tinting compositions in particular, but also with compositions which are additionally intended to have a setting effect.

The present invention also relates to the use of a composition according to the invention for colouring and tinting keratin fibres, more especially human hair.

The following Examples are intended to illustrate the invention.

Examples I. Dyes The following methine dyes were prepared: Example 1

R

3

R

4

R

5

CH

3

R

10

OCH

3

R

12 CI; R 1

R

2

R

6

R

7

R

8

R

9

R

11 H; y=1; n 1, m 2, A ZnCl 4 Q CHCH Q OCH 3 0,5 ZnCl4

CH

3 C08068 Preparation: 0.05 mole of 2-methylene-1,3,3-trimethylindoline were dissolved in 24mL of glacial acetic acid at 2000. 0.05 mole of 2-chloro-4-methoxybenzaldehyde was added to the solution which was then heated for 4 hours to 80*C. After cooling to 2000, the solution was diluted with 500mL- of water and a solution of 7.5 g (0.055 mole) of ZnCl2 in 5OmL- of conc. hydrochloric acid was added. The product precipitated was filtered off and dried in vacuo at ca. 6000. Red crystals were obtained.

Example 2 R 4 R 5

CH

3

R

10

R

11

O-CH

2

R

1 R 2 R 6 R 7 R 8

R

9 R 12 y=1; n =1, m 2, A ZnC1 4

CH

3 o Q CH=CH- Q 0,5Zn4

CH

3 Preparation was carried out as in Example 1 except that 3,4-methylenedioxybenzaldehyde (Piperonal) was used instead of 2-chloro-4-methoxybenzaldehyde.

Example 3 R 3 R 4 R 5 R 15 R 16

CH

3

R

1 0 NR 15

R

16

R

2 R 6 R 7

R

8

R

9

R

1 1 R 12 y=1; n nn= 1, A =Im 2, A =ZnC14

CR

3

CH

3

CR

3 Q e'CH=CH Q N-CH 3

CR

3

H

(according to Aus. J. Chem. (1977), 30, 689) Example 4 R 3 R 4 R 5

CH

3 R 15 R 16

C

2

H

5

R

1 0

NR

5 R 16

R

1 R 2 R 6 R 7

R

8

R

9

R

11 R 12 H; y=1;n =2,mnn=1, A =Clmnn=2, A =ZnC 4

CR

3

CH

3 Q H Q /CH=CH QO 2H

CH

3

H

(according to DE 32 10 596 Al) Example R 3 R 4 R 5

OH

3

R

1 0 pyrrolidino; R 1

R

2 ,R 6 R 7 R 8

R

9 R R 12 H;y 1; n1 a)m=1,A=I b)m=2,A=ZnC 4 C08068

CH

3 CR 3 Q CH=CH Q N<)

CH

3 (according to J. Soc. Dyers/Colour. (1974), 90, 97) Example 6 R 3 R 4 R 5 R 15 R 16

CH

3

R

1 0 NR 15

R

16

R

12

OCH

3

R

1 R 2 R 6 R 7 R 8

R

9

R"~

H; y=1; n 2,m A =ZnC 4

CR

3 CR

CH

3 O

R

Q

CH=CHQ)NH

CR

3

H

Preparation was carried out as in Example 1 using 2-methoxy-4-dimethylaminobenzaldehyde.

Green crystals 95-100*C) were obtained.

Example 7 R 4 R 5

OH

3 X is a 2,3,6,7-tetrahydro-H,5H-pyrido[3,2,1-ij]quinoline residue;

R

1 R 2 R 6 R 7 R 8 R 12 H; y n 1, a) m 1, A CIO 4 b) m 2, A =ZnCI 4

CR

3 CH 3 Q CH=CH Q N

CR

3 (according to Khim. Geterotsikl. Soedn. (1982), 450 Example 8 R 3 R 4 R 5 R 3 R 4 R 5

OH

3 X= Rest der Formel (111); R 1 R 2 R, R 2 'R 6 R 7

H;

y=2; n 1, m 1, A 1.

CR

3

CH

3

CR

3

CR

3

Q

CH

3

CR

3 (an Aldrich product) Example 9 R 3 R 4 R 5

R

1 5 R 16

OH

3

R

10 NR 15

R

16 R 2 R 6 R 7 R R 8

R

9

R

11 R 12 H; y= 2 n 1, m 1, A p-toluene sulfonate.

C08068 CH3 ®\CH=CH-CH=CH N/ CH3CH

CH

3 (an Acros product) Example

R

3

R

4 R CH 3

R

10

NR

15

R

16

R

1

R

2

R

6

R

7

R

8

R

9

R

11 H; R 12 OH; R 15

R

16

=C

2

H

5 y=l; n 2, m 2, A ZnCI 4

CH

3 HO /CH3 H C 2

H

CH=CH Q N-C 2 HS ZnC14

H

CH

3 Example 11

R

3

R

4

R

5

CH

3

R

10

R

12

OCH

3

R

1

R

2

R

6

R

7

R

8

R

9

R

11 H; y=l; n 1, m 2, A ZnCl 4 CH3

CH

3 CH 3

O

CH=CH OCH3 S.0 0,5 ZnC14*

CH

3 Example 12 3

R

4

R

5

R

15

R

16

CH

3

R

10

NR

15

R

16

R

1

R

2

R

6

R

7

R

11

R

12 H; R 8 forms a fused benzene ring with R 9 y n 2, m 2, A ZnCl 4 CH3

C

3

CH

3

CH

3 CH=CH O N-ZnClCH 05V N- ZnC4

H

CH3 15 2. Hair colouring tests Hair colouring creams with the following composition were prepared: Anionic basis

C

1 2- 18 fatty alcohol C12-18 fatty alcohol 2EO sulfate, Na salt 25 g Water 55 g Methine dye (Examples 1-9) 1 g Ammonium sulfate 1g Water and NH 3 or NH 4 HS0 4 for pH adjustment 8 g [R:\LIBAA]08856.doc:sak The constituents were mixed together in the order listed above. After addition of the methine dye, the pH was adjusted to the required value 7 or 9) with conc. ammonia solution or with

NH

4

HSO

4 solution and water was added to 100 g.

Nonionic basis Mixture A Hydrenol®D 1 6 g Lorol® techn.

2 2 g Cremophor@ A25 3 2 g 1 C 1 6 1 8 fatty alcohol (INCI name: Cetearylalcohol) (HENKEL) 2 C 1 2- 18 fatty alcohol (INCI name: Coconut alcohol) (HENKEL) 3 Tallow alcohol 25 EO (INCI name: Ceteareth-25) (BASF) Mixture B Ammonium sulfate 1 g Methine dye 1 g Ammonia solution, 25% q.s.

Mixture A was melted, mixed with 60 g water (80°C) and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring.

Mixture B was dissolved in 10 g water Mixture B was then added to emulsion A and the pH was adjusted as required with a 25% ammonia solution. Stirring was then continued until the temperature reached room temperature.

The colouring creams were applied to 5 cm long tresses of standardised 90% grey, but not specially pretreated human hair and left thereon for 30 minutes at 27 0 C. After colouring, the hair was rinsed, washed with a standard shampoo and then dried.

The results of the colouring tests are shown in the following Table: Table Dye Basis pH Hair colour Example 1 Anionic 9 Dark magenta Example 1 Nonionic 7 Cerise Example 2 Anionic 5 Yellow Example 2 Nonionic 7 Yellow-orange Example 3a Anionic 7 Deep magenta Example 3b Nonionic 7 Grey-magenta Example 4a Anionic 7 Deep magenta Example 4a Nonionic 7 Grey-magenta Example 5a Anionic 7 Orchid purple Example 5b Nonionic 7 Orchid purple Example 6 Anionic 7 Violet-red Example 6 Nonionic 7 Magenta Example 7a Anionic 5-9 Deep violet Example 7b Nonionic 7 Deep violet Example 8 Nonionic 9 China blue Example 9 Nonionic 7 Deep blue Example 10 Nonionic 7 Magenta ALq 4 ,xample 11 Nonionic 7 Orange-yellow ample 12 Nonionic 5 Dark blue

LU

C08068

Claims

1. A hair colourant which contains 0.01 to 10wt% of methine dye, based on the hair colourant as a whole, in a carrier suitable for colouring, wherein the methine dye corresponds to formula n+ CR )y-X nA- R2 m in which R 1 and R 2 independently of one another represent hydrogen, a Cl-4 alkyl group, a C14 alkoxy group, a hydroxy group, an amino group or a mono- or di-(Ci-4-alkyl)-amino group, R 3 is hydrogen, a C14 alkyl group or a C24 hydroxyalkyl group, R 4 to R 7 independently of one another represent hydrogen or a Ci4 alkyl group, X is a group corresponding to formulae (II) to (IV): R 1 2 R 11 R R R R R(II) *R 9 R 4 CH (IV) 2 9 R 10 where Rl- to R 5 stand for one of the groups mentioned under R 1 to R 5 R 8 and R 12 independently of one another represent hydrogen, a halogen atom, a hydroxy group, a C14 alkoxy group or a C24 hydroxyalkyl group, R 9 and R 1 1 represent hydrogen or, together with R lo form a methylenedioxy .group, R 1 0 additionally represents a C14 alkoxy group, a C24 hydroxyalkyl group or a group corresponding to formula 16 (V) in which R 1 5 and R 1 6 independently of one another represent a C14 alkyl group, a C2-4 hydroxyalkyl group or, together with the nitrogen atom, form a pyrrolidine, piperidine or piperazine ring, two adjacent substituents Rs to R 1 2 together form a fused benzene ring or the substituent corresponding to formula (1I) is a 2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]-quinoline residue. R 13 stands for hydrogen, a halogen atom, a C14 alkyl group or a C1-4 alkoxy group, R 14 is a phenyl or naphthyl group substituted by C14 alkyl groups, C14 alkoxy groups, a hydroxy group, a carboxy group or a mono- or di-(Ci4-alkyl)-amino group, the alkyl groups optionally forming one or two fused heterocycles with the [R:\LIBAA]08856.doc:sak phenyl or naphthyl group or one heterocycle with the amine nitrogen, and for pyridyl, quinolyl, furyl, thienyl groups or the group (III), Z is a direct bond, a methylene group, a dimethyl methylene group or an ethylene group, y is an integer of 1 to 3, n is the number of positive charges in the cation and A is an m-valent physiologically compatible anion.

2. A colourant as claimed in claim 1, characterised in that R 3 is a methyl group.

3. A colourant as claimed in claim 1 or 2, characterised in that R 4 and R 5 are methyl groups.

4. A colourant as claimed in any one of claims 1 to 3, characterised in that A is an anion from the group consisting of chloride, bromide, iodide, sulfate, perchlorate, tetrachlorozincate, tetrafluoroborate or tetraphenyl borate.

5. A hair colourant which contains 0.01 to 10wt% of methine dye, based on the hair colourant as a whole, in a carrier suitable for colouring, wherein the methine dye corresponds to any one of Examples 1 to 12.

6. A hair colouring cream colourant substantially as hereinbefore described with reference to any one of the examples under the heading Hair colouring tests".

7. A colourant as claimed in any one of claims 1 to 4, characterised in that it is free from oxidation dye precursors.

8. A colourant as claimed in claim 7, characterised in that it remains on the hair.

9. A colourant as claimed in claim 7 or claim 8, characterised in that it is a hair-setting Scolorant.

10. A colourant as claimed in claim 6, characterised in that it contains at least one primary intermediate and/or at least one secondary intermediate.

11. A colourant as claimed in claim 10, characterised in that the primary intermediate is selected from p-aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1-(2- hydroxyethyl)-pyrazole, p-toluylenediamine, 2-aminomethyl-4-aminophenol, N,N-bis-(2-hydroxyethyl)- p-phenylenediamine, p-phenylenediamine, 3-methyl-p-aminophenol and aminophenyl)-methane.

12. A colourant as claimed in claim 10 or 11, characterised in that the secondary intermediate is selected from the group consisting of 1-naphthol, 2,7- and 1,7- 30 dihydroxynaphthalene, resorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-diaminopyridine, m- aminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2-methylaniline, 3-amino-2- methylamino-6-methoxypyridine, 2,6-dimethyl-3-aminophenol, 2,4-diaminophenoxyethanol, 6-methyl- 1,2,3,4-tetrahydroquinoxaline, 2-methyl-4-chloro-5-aminophenol, 3,4-methylenedioxyaniline, 2- methylresorcinol, 5-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 2-amino-3- hydroxypyridine and 2-chloro-6-methyl-3-aminophenol.

13. A colourant as claimed in any one of claims 6 to 12, characterised in that it additionally coritains an anionic, nonionic or cationic polymer. t

14. The use of the colourant claimed in any one of claims 1 to 13 for colouring and tinting ir. [R:\LIBAA]08856.doc:sak The use of methine dye for colouring keratin fibres, wherein the methine dye corresponds to formula n+ R 5 R R 4 R 3 I- (CR 6-CR 7)y-X_ _n (I) RR in which R 1 and R 2 independently of one another represent hydrogen, a C14 alkyl group, a C 1 4 alkoxy group, a hydroxy group, an amino group or a mono- or di-(Ci14-alkyl)-amino group, R 3 is hydrogen, a C1-4 alkyl group or a C 2 4 hydroxyalkyl group, R 4 to R 7 independently of one another represent hydrogen or a C14 alkyl group, X is a group corresponding to formulae (II) to (IV): R 1 2 R 11 R R" SR 1 0 (II) RI R S(III) R C H R 2* R CHR 1 4 (IV) *13 where R 1 to R 5 stand for one of the groups mentioned under R 1 to R 5 R 8 and R 1 2 independently of one another represent hydrogen, a halogen atom, a hydroxy group, a C14 alkoxy group or a C2-4 hydroxyalkyl group, R 9 and R 1 1 represent hydrogen or, together with Ro 1 form a methylenedioxy group, R 1 0 additionally represents a C1 4 alkoxy group, a C 2 4 hydroxyalkyl group or a group corresponding to formula -NRsR 1 6 (V) 15 in which R 1 5 and R 1 6 independently of one another represent a C1 4 alkyl group, a C24 hydroxyalkyl group or, together with the nitrogen atom, form a pyrrolidine, piperidine or piperazine ring, two adjacent substituents R 8 to R 1 2 together form a fused benzene ring or the substituent corresponding to formula (II) is a 2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]-quinoline residue.

R 1 3 stands for hydrogen, a halogen atom, a C 14 alkyl group or a C14 alkoxy group, R 14 is a phenyl or naphthyl group substituted by C 14 alkyl groups, C 14 alkoxy groups, a hydroxy group, a carboxy group or a mono- or di-(C14-alkyl)-amino group, the alkyl groups optionally forming one or two fused heterocycles with the phenyl or naphthyl group or one heterocycle with the amine nitrogen, and for pyridyl, quinolyl, furyl, thienyl groups or the group (111), Z is a direct bond, a methylene group, a dimethyl methylene group or [R:\LIBAA]08856.doc:sak 19 an ethylene group, y is an integer of 1 to 3, n is the number of positive charges in the cation and A is an m-valent physiologically compatible anion, for colouring keratin fibres.

16. The use of methine dye of formula as claimed in claim 15, characterised in that R 3 is a methyl group.

17. The use of methine dye of formula as claimed in claim 15 or claim 16, characterised in that R 4 and R 5 are methyl groups.

18. The use of methine dye of formula as claimed in any one of claims 15 to 17, characterised in that A is an anion from the group consisting of chloride, bromide, iodide, sulfate, perchlorate, tetrachlorozincate, tetrafluoroborate or tetraphenyl borate.

19. The use of methine dye of formula as claimed in any one of claims 15 to 18 for colouring human hair.

A method of colouring keratin fibres, which method comprises applying to the fibres methine dye corresponding to formula as defined in the use of any one of claims 15 to 19.

21. The method of claim 20 wherein the keratin fibres are human hair.

22. A method of colouring human hair, which method comprises applying to the hair a hair colourant as claimed in any one of claims 1 to 13.

23. A process of preparing a methine dye, the process being substantially as hereinbefore described with reference to any one of Examples 1 to 12.

24. A process of preparing a hair colouring cream, the process being substantially as 20 hereinbefore described with reference to any one of the examples under the heading Hair colouring tests". Dated

25 June 2001 HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN .*Patent Attorneys for the Applicant/Nominated Person 25 SPRUSON FERGUSON 0*oo o *o [R:\LIBAA]08856.doc:sak