AU2013222033B2 - Dyestuffs and hair dye compositions - Google Patents

Abstract

DYESTUFFS AND HAIR DYE COMPOSITIONS 5 The present invention refers to dyestuffs of the general Formula (1) wherein R, X, Y and Z are defined as given in claim 1, dyestuff mixtures and hair dye compositions comprising them, as well as a process for colouring hair.

Description

WO 2007/090799 PCT/EP2007/051041 Dyestuffs and Hair Dye Compositions 5 The present invention relates to anthraquinone hair dyes and hair dye compositions containing them. Hair dyes can be classified by the dye to be used therefore, or by whether they have bleaching action of melanin or not. Typical examples include a two-part permanent 10 hair dye composed of a first part containing an alkali agent, an oxidation dye and optionally a direct dye such as a nitro dye and a second part containing an oxidizing agent; and a one-part semi-permanent hair dye containing an organic acid or an alkali agent, and an acid dye, basic dye or direct dye such as a nitro dye. The above-described permanent hair dye is however accompanied by the drawback 15 that the color tone imparted by an oxidation dye is not so vivid and that they damage the hair. Use of a nitro dye or cationic dye for a two-component hair dye containing an oxidizing agent has been attempted in order to produce various color tones (refer to, for example, Japanese Patent Laid-Open No. 1994-271435 and EP 1 133 976 A2). A permanent hair dye formulation containing current direct dyes typically 20 develop a vivid color just after dyeing, but the color fades away quickly over time and which leads to a dull end result. Also the use of many direct dyes involves such problems as decomposition when mixed with a peroxide serving as an oxidizing agent and incompatibility with the formulation. The above described semi-permanent hair dye formulations are accompanied by the 25 drawback that the color imparted typically displays low durability. In addition, it is difficult to achieve violet, blue and ash tones since the number of dyes which can deliver these tones is extremely limited. Such dyes must be high performing and toxicologically safe. 30 It is known to use quaternized anthraquinone dyes to dye hairs, see for example DE 1 203 915, DE 1 248 865, DE 1 492 066, GB 1 205 365, US 3,531,502, EP 0 818 193 A2 and EP 0 852 136 Al. In addition, US 3,657,213, GB 1,270,107, GB 1,248,652, US, 2,888,467, US 2,737,517, US 4,246,172, CH 14851/71, DE 16 19 WO 2007/090799 PCT/EP2007/051041 2 365, CH 463666, FR 1,363,216, US 5,486,629 and GB 807 241 teach to dye textile materials with quaternized anthraquinone dyes. However, there is still a need for hair dyes which can effectively deliver blue, ash, violet or red tones to the hair without damaging and are toxicologically safe. 5 It was now surprisingly found that specific anthraquinone dyes according to the definition given below provide the required properties. Accordingly, the present invention provides dyestuffs of the general formula (1) o NHR z

-

X 10 O Y wherein R is hydrogen, alkyl, alkyl substituted by Q, aryl, Q-aryl, -OR 2 , -SR 3 or -NR R 4 , hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl, cycloalkyl substituted is by Q, aryl substituted by R 1 ", Q, R 11 0-alkyl, -OR, -SR 13 , -NR 4

R

5 , 15 16 1718 19 22 6 -CONR R , -C(O)OR 7 , -S0 2 -NR R19, -S02OR0, -C(O)R 21 or -S0 2 R, -C(O)R , -S0 2

NR

7

R

8 or -S0 2

R

9 ; X is hydrogen, -OR 23 , -SR24, -NR 2

R

2 , -SO 2

NR

27

R

28 , -CONR 2 9

R

30 , -SO 2

OR

3 1 20 -C(O)OR 3 2 , -C(O)R 3 3 , -SO 2

R

3 4 , alkyl, alkyl substituted by -OR 2 00 , -SR300 or 50 400 100 110 140 150 -NR O0R , aryl substituted by RO, R 0O-alkyl, -OR 2 , -SR 130 , -NR OR 150 160 1018020 21020 -CONR OR , -C(O)OR 70 , -S0 2 -NR 0R 190 , -SO 2

OR

201 , -C(O)R or -SO2R

-NHSO

2

R

3 6

R

37 , -CHO, -CH=NR 35 or NO 2 ; 25 Y is hydrogen, -NR 1

R

2 , -OR 3 , -SR 4 , -SO 2 NHR 5 , -NHC(O)R 6 , -SO 2

OR

57 ,

-NHSO

2

R

5 8 , -SO 2

R

5 9 , -NHSO 2 NR 6R 6, halogen or NO 2 ; Z is hydrogen, -NR 1

R

2 , -OR 3 , -SR4, -SO 2 NHR 5 , -NHC(O)R 6 , -S02OR 57 , 30 -NHSO 2

R

5 8 , -S0 2

R

5 9 , -NHSO 2 NR 6R 6, halogen or NO 2

;

WO 2007/090799 PCT/EP2007/051041 3 2 8 60 61 each of R to R , R and R , independently, is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, 5 cycloalkyl or cycloalkyl substituted by Q;

R

9 is alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 10 16 18 1921 each of R 10 to R , R , R19 and R , independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 15 17 20 22 each of R , R and R , independently, is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 23 30 35 20 each of R to R30 and R , independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or cycloalkyl substituted by -C(O)R 6 , -S0 2

R

9 , or aryl 1' 1'12' 13' 1' 1'5 6 17' substituted by R1 , R O-alkyl, -OR , -SR , -NR 1

R

1 , -CONR 5 R , -C(O)OR , S0 2

-NR

18

R

1 9 , -S0 2

OR

20 , -C(O)R 2 1 or -SO2R2; 25 R is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;

R

9 is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; 10' 16' 18' 19' 21' each of R to R , R , R and R , independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; 30 17' 20' 22' each of R , R and R , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; WO 2007/090799 PCT/EP2007/051041 4 36363 each of Ra and R37, independently, is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl and one of R and R37 can additionally be hydrogen; each of R 51 to R 4 , independently, is hydrogen, alkyl, alkyl substituted by Q, 5 hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, -C(O)R , -SO 2

R

9 , or aryl substituted by R 10 , R 11 O-alkyl, -OR, 1 14 15 5 1 71 20

SR

13 , -NR R 4, -CONR 5

R

6 , -C(O)OR 7 , -SO 2

-NR

8

R

19 , -SO 2 OR -C(O)R 21 or -SO2R2; 10 each of R 31 to R 33 , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl 10 1'12' 13' 14' 15' or aryl substituted by R1", R" O-alkyl, -OR , -SR , -NR R ,

-CONR

15

R

16 , -C(O)OR 1 1, -SO 2

-NR

18

R

19 , -SO 2

OR

20 , -C(O)R 21 or -SO 2

R

22 , and R 33 can additionally be hydrogen; 15

R

34 is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R 10 , 1'12' 1 ' 1 ' 1 '1 ' 1 17' 8 9 R" O-alkyl, -OR , -SR 1 , -NR 4

R

1 , -CONRR 6 , -C(O)OR , -SO 2

-NR

8

R

19 ,

-SO

2

OR

20 , -C(O)R 1 or-SO 2 R; 20 each of R 5 to R 57 , independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl 12 1 14 15 substituted by Q or aryl substituted by R1", R 11 O-alkyl, -OR, -SR 13 , -NR R, -CONR1 R 1, -C(O)OR 17, -SO 2 -NR1 R19, -SO 2 OR 20, -C(O)R 2 1 or -SO 2 R , and R 5 25 and R can additionally be hydrogen; each of R 58 and R 9 , independently, is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q or aryl 1 1112 13 14 1515 16 17 30 substituted by R1", R 0-alkyl, -OR , -SR , -NR R 15 , -CONR R , -C(O)OR

SO

2

-NR

18

R

1 9 , -SO 2

OR

20 , -C(O)R 2 1 or -SO2R2; each of R 200 , R 30 o, R 400 and R 00 , independently, is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; WO 2007/090799 PCT/EP2007/051041 5 10 120 130 140 150 160 180 190 210 each of R' 00 , R" , R , R , R , R , R , R , R and R , independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, or cycloalkyl; 10 201 220 each of R ", R , and R , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, 5 or cycloalkyl; and Q is a group of the general formula (11) R -\ R" N R (Ii) wherein 10 each of R', R" and R"', independently, is (C1-C 6 )-alkyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, either of which can be substituted by heteroatom containing groups or R' and R" form together with the nitrogen to which they are bonded a 5- or 6- membered satureated heterocyclic ring; and 15 A is a cosmetically acceptable, water solubilizing anion, and does not comprise arylsulfonate, phosponate and alkylphosphonate; whereby the dyestuff of the formula (1) contains exactly one group Q; whereby at least two of the groups X, Y and Z are groups other than hydrogen; and 51 52 23 51 20 whereby in case R and X are both hydrogen and Y is -NR 'R or -OR , wherein R 52 23 25 26 25 26 R and R are hydrogen, Z is not -NR R , wherein one of R and R is hydrogen and the other is alkyl substituted by Q. Alkyl groups may be straight-chain or branched and are preferably (C1-C 6 )-alkyl 25 groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, isopentyl or n-hexyl. Cycloalkyl is preferably (C 3

-C

8 )-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. 30 Aryl groups are preferably phenyl or naphthyl groups.

WO 2007/090799 PCT/EP2007/051041 6 Halogen is preferably chlorine, bromine and fluorine. A 5- or 6- membered saturated heterocyclic ring which is formed by R' and R" is preferably a pyrrolidine, piperidine, morpholine or piperazine ring. R', R" and R"' are 5 preferably benzyl or (C 1

-C

6 )-alkyl and especially preferably benzyl, methyl and ethyl. The dyestuffs of the general formula (1) may be salts of an organic or inorganic acid. Consequently, A may be for example chloride, bromide, iodide, hydroxide, hydrogenphosphate, phosphate, carbonate, hydrogencarbonate, hydrogensulfate, 10 perchlorate, fluoroborate, chlorozincate, methylsulfate, ethylsulfate, acetate, propionate, lactate or citrate or mixtures thereof. The meaning of A is generally given by the preparation method of the dyestuff of the general formula (1). Preferred meanings of A are chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate and lactate. 15 Especially preferred dyestuffs of the present invention are dyestuffs of the general formula (1) in which X is (C 1 -C)-alkyl, -OR 23 or -SR 24 , wherein R23 and R24 are hydrogen, (C 1 -C)-alkyl, 29 30 32 29 30 hydroxy-(C 1

-C

6 )-alkyl or phenyl, or -CONR 9R or -C(O)OR , wherein R29 and R 20 independently are hydrogen, (C 1

-C

6 )-alkyl, hydroxy-(C 1

-C

6 )-alkyl or phenyl and R32 is (C1-C)-alkyl, hydroxy-(C 1

-C

6 )-alkyl or phenyl; Z is hydrogen; R is hydrogen or (C 1 -C)-alkyl; Y is -NR51R52 or -OR 3, wherein R is hydrogen and R52 is (C1-C 6 )-alkyl substituted 25 by Q, phenyl substituted by Q or (C1-C 6 )-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q; and R 5 3 is (C1-C 6 )-alkyl substituted by Q, phenyl substituted by Q, (C1-C)-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q or (C1-C 6 )-alkyl NH-S0 2 -phenyl wherein the alkyl group is substituted by Q; Q is a tris-(C 1

-C

6 )-alkyl-ammonium group, a bis(C 1

-C

6 )-alkyl-benzyl-ammonium 30 group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and A is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.

WO 2007/090799 PCT/EP2007/051041 7 Examples of dyestuffs of this type are the dyestuffs of of the formulae (la), (Ib), (Id) (lh), (Ir), (Is) and (lx). O

NH

2 CH 0 NH 2 OMe "~ |N

CH

3 0SO 3 0 HN-

CH

3 0SO 3 (la) (Ib) 0 NHN2 O OH OMe

CH

3 0SO3 0 HN I 0 N+ 5 (Id) CH 3 0SO 3 (le) O

NH

2 O NH2

CONH

2 I I I O HN o o CH 3 0SO3

CH

3 0SO 3 ~ ( I+ (If)- (1g) WO 2007/090799 PCT/EP2007/051041 8 o

NH

2

COOC

2 H 0 NH 2 1 I CONHCH 2

CH

2 OH o HN

CH

3 0SO 3 0 HN N (lh) (Ir) 0 NH 2 0 SNN NH2 O HN CH30SO3 0 HN

CH

3 0SO 3 ~ (Is) (Ix) 5 Further especially preferred dyestuffs of the present invention are dyestuffs of the general formula (1) in which 51 52 565 152 53 Z is -NR R , -NHC(O)R 5 or -OR 3 , wherein R 51 is hydrogen R and R are hydrogen or (C 1 -C)-alkyl substituted by Q and R 56 is (C 1 -C)-alkyl or phenyl; X is hydrogen; 10 R is hydrogen or (C 1 -C)-alkyl; Y is -NR51R52 or -OR 5 3 , wherein R 51 is hydrogen, R 52 is hydrogen, (C 1

-C

6 )-alkyl, hydroxy-(C 1

-C

6 )-alkyl, (C 1 -C)-alkyl substituted by Q, phenyl, phenyl substituted by Q or (C 1

-C

6 )-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q; and R 5 3 is hydrogen, (C 1 -C)-alkyl, (C 1 -C)-alkyl substituted by Q, phenyl, phenyl substituted by 15 Q, (C 1

-C

4 )-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q or (C1-C4) alkyl-NH-S0 2 -phenyl wherein the alkyl group is substituted by Q; WO 2007/090799 PCT/EP2007/051041 9 Q is a tris-(C 1

-C

6 )-alkyl-ammonium group, a bis(C 1

-C

6 )-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to either Z or Y; and A is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, 5 formate, acetate or lactate. Examples of dyestuffs of this type are the dyestuffs of of the formulae (lj) to (In) and (It) to (lu) and (ly) O

NH

2 0 Nl 2

NH

2 0 HN NH O 0 CH30SO3

CH

3 0SO3 N N (lj) (1k) 10 0 NH2 0 NH 2 o o NH2 OH 0 N

CH

3 0SO 3 CH 3 0SO3 -N-- (II) (Im) O NH 2 0 NH 2 O NH 0 HN NH 2 0 HN

CH

3 0SO 3 +

CH

3 0SO N (In) (It) WO 2007/090799 PCT/EP2007/051041 10 0

NH

2 0 HIN

NH

2 0 HN OH 0 N Cl N

CH

3 0SO -N (lu) (ly) Further especially preferred dyestuffs of the present invention are dyestuffs of the general formula (1) in which 51 52 56 51 52 5 Z is -NR 'R , -NHC(O)R , wherein R is hydrogen and R is hydrogen or

(C

1 -C)-alkyl substituted by Q and R is (C 1 -C)-alkyl or phenyl; X is -OR 2 3 , -S0 2

NR

2 7

R

2 8 or -S0 2

OR

3 1 , wherein R 2 3 and R 3 1 are (C 1

-C

6 )-alkyl, hydroxy(C 1

-C

6 )-alkyl or phenyl; R27 is hydrogen, R28 is hydrogen (C 1 -C)-alkyl or hydroxy(C 1

-C

6 )-alkyl; 10 R is hydrogen or (C 1 -C)-alkyl; Y is -NR 5R 2, wherein R 51 is hydrogen, R 52 is (C 1

-C

6 )-alkyl, (C 1

-C

6 )-alkyl substituted by Q, hydroxy-(C 1

-C

6 )-alkyl, hydroxy-(C 1

-C

6 )-alkyl substituted in the alkyl group by Q, phenyl or phenyl substituted by Q; Q is a tris(C 1

-C

6 )-alkyl-ammonium group, a bis(C 1

-C

6 )-alkyl-benzyl-ammonium group, 15 a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to either Y or Z; and A is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate. 20 Examples of dyestuffs of this type are the dyestuffs of of the formulae (lv), (1w) and (lz): WO 2007/090799 PCT/EP2007/051041 11 0 NH 2 OMe 0 NH2 I1 1 0 NHl 0 HN 0 NH 0 HN

C

2

H

5 0SO 3 N+

NCH

3 0SO 3 ~ (lv) N(1w) 0 NHl 2 0

CH

3 OSO + N (lz) 5 The dyestuffs of the general formula (1) can be obtained by generally known methods, for instance via Ullmann type substitutions of anthraquinone derivatives which contain exchangeable atoms or groups such as halogen, sulfonic acid group or nitro group by aliphatic amines, aromatic amines, alcohols, phenols, thiols, thiophenols and sulfur containing reagents. General procedures are described, for 10 example, in "Ullmann's Encyclopedia of Industrial Chemistry", VCH Verlagsgesellschaft, Weinheim 1985, volume A2, Anthraquinone Dyes and Intermediates, pages 357-412. The preparing reactions of the dyestuffs can be carried out in an organic solvent such as dimethylformamide, dimethylacetamide, halogenobenzenes etc., in water or preferably in surplus reagent. It is of advantage 15 to carry out the reactions at elevated temperatures, preferably between 60 0C and 150 OC. Acid-binding agents must be added or an excess of amine is used. Adding usual catalysts such as copper or copper salts or mixtures thereof can be advantageously. The alkoxyanthraquinones of the general formula (1) can be obtained via the 20 conversion of anthraquinonesulfonic acids by alcoholic alkali at 50-130 C. The direct replacement of halogen to alkoxy- or aryloxyanthraquinones can be advantageously WO 2007/090799 PCT/EP2007/051041 12 carried out with e.g. alcoholate or phenolate generated in situ with alkali or advantageously with metallic sodium. It is advantageously to carry out these reactions under water free conditions with dried reagents. 5 The present invention also refers to dyestuff mixtures comprising one or more dyestuffs of the general formula (1) according to the present invention and one or more direct or oxidation dyestuff. Examples of such direct dyes include dyes from the publicly available dyestuff list issued by The European Cosmetic, Toiletry and Perfumery Association (COLIPA) 10 and especially Acid Yellow 1, Disperse Red 17, Basic Brown 17, Acid Black 1, 4 Nitro-o-phenylenediamine, Picramic acid, HC Red 13, N,N-bis(2-hyrdoxyethyl)-2 nitro-p-phenylenediamine, HC Red 7, HC Blue 2, HC Yellow 4, HC Yellow 2, HC Orange 1, HC Red 1, HC Red 3, 4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5 nitroanisole, 3-Nitro-p-hydroxyethylaminophenol, 3-Methylamino-4 15 nitrophenoxytheanol, 2-nitro-5-glyceryl methylaniline, HC Violet 1, HC Orange 2, HC Yellow 9, 4-Nitrophenylaminoethylurea, HC Red 10, HC Red 11, 2-Hydroxy-ethyl picramic acid, HC Blue 12, Hydroxyethyl-2-nitro-p-toluidine, HC Blue 11, HC Yellow 7, HC Yellow 10, 4-Amino-2-nitrophenylamine-2-carboxylic acid, 2-Chloro-6 ethylamino-4-nitrophenol, HC Violet 2, 2-Amino-6-chloro-4-nitrophenol, 4 20 Hydroxpropylamino-3-nitrophenol, HC Yellow 13, 2,6-Diamino-3-((pyridin-3 yl)azo)pyridine, N-(2-nitro-4-aminophenyl)-allylamine, Basic Violet 2, Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Red 76, Basic Brown 16, Basic Yellow 57, Acid Orange 7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Red 92, Acid Yellow 3, Acid Violet 43, Disperse Violet 1, Acid Blue 62, Disperse Black 9, 25 Hydroxyanthraquinoneaminopropylmethy morpholinium methosulfate, Lawsone, HC Blue 14, Curry Red, Acid Red 18, Acid Red 52, Acid Green 25, Disperse Blue 377, Pigment Red 57, HC Blue 15, Tetrabromophenol Blue, Basic Blue 7, Basic Blue 26, Basic Blue 99, Basic Violet 10, Basic Violet 14; cationic dyes as described in Japanese Patent Laid-Open Nos. 2204/1983, 118832/1997 and Japanese Laid 30 Open Publications (PCT) Nos. 501322/1996 and 507545/1996 (please check numbers); and methine type cationic dyes having a cyanine structure. The inventive dyestuff mixtures of the present invention usually contain one ore more dyestuffs of the general formula (1) in an amount 90 to 10 wt.% and one or more WO 2007/090799 PCT/EP2007/051041 13 direct or oxidation dyestuff in an amount of 10 to 90 wt.% based on the total weight of the dyestuff mixture. Preferably, the inventive dyestuff mixtures contain one ore more dyestuffs of the general formula (1) in an amount 80 to 20 wt.% and one or more direct or oxidation 5 dyestuff in an amount of 20 to 80 wt.% based on the total weight of the dyestuff mixture. Especially preferably, the inventive dyestuff mixtures contain one ore more dyestuffs of the general formula (1) in an amount 65 to 35 wt.% and one or more direct or oxidation dyestuff in an amount of 35 to 65 wt.% based on the total weight of the 10 dyestuff mixture. The dyestuffs of the general formula (1) as defined above, as well as dyestuff mixtures comprising one or more dyestuffs of the general formulae (1) and one or more direct or oxidation dyestuff can advantageously be used to dye hair, especially 15 human hair. The present invention also refers to hair dye compositions comprising one or more dyestuffs of the general formulae (1). Such hair dye compositions usually contain the dyestuffs of the general formulae (1) in amounts of 0.0001 to 20 wt.%, preferably 20 0.001 to 20 wt.%, more preferably from 0.01 to 10 wt.% and especially preferably from 0.05 to 5 wt.%, based on the weight of the hair dye composition. Furthermore, the present invention also refers to hair dye compositions comprising one or more dyestuffs of the general formulae (1) and one or more direct or oxidation 25 dyestuff. Hair dye compositions containing a dyestuff mixture as described above usually have a dyestuff content between 0.001 to 20 wt.%, preferably from 0.01 to 20 wt.%, more preferably from 0.05 to 10 wt.% and especially preferably from 0.1 to 5 wt.%, based on the weight of the hair dye composition. 30 In the hair dye compositions according to the present invention, the inventive dyestuffs of the general formula (1) exhibit a high storage stability within a wide pH range from 2 to 11, which is a pH range ordinarily employed for hair dyes, so that the hair dye composition of the present invention can be used at any pH in the above- WO 2007/090799 PCT/EP2007/051041 14 described pH range. Use in a pH range of from 2 or greater is however preferred from the viewpoint of dyeing property. Hair dye compositions of a pH range of 2 to 8 and hair dye compositions of a pH range of 8 to 12 are preferred. 5 The desired pH value is usually adjusted using an alkali agent. Examples of alkali agents include ammonia, alkanolamines such as monoethanolamine and isopropanolamine or salts thereof, guanidium salts such as guanidine carbonate and hydroxides such as sodium hydroxide. The inventive hair dye compositions contain an alkali agent preferably in an amount of from 0.01 to 20 wt.%, more preferably 10 from 0.1 to 10 wt.%, especially preferably from 0.5 to 5 wt.% based on the total weight of the composition. Since the inventive dyestuffs of the formula (1) have high stability against oxidizing agents, the inventive hair dye composition may also be applied to hair together with an oxidizing agent. In other words, it can be provided as a two-part composition 15 composed of a first part containing the dyestuff of the general formula (1) and a second part containing an oxidizing agent. In this case, hair dyeing and bleaching can be carried out simultaneously, which facilitates more vivid hair dyeing. Examples of oxidizing agent include hydrogen peroxide, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, perborates such 20 as sodium perborate, percarbonates such as sodium percarbonate and bromates such as sodium bromate and potassium bromate. Hydrogen peroxide is especially preferred from the viewpoints of hair bleaching property, stability and effectiveness of the inventive dyestuffs of the general formula (1). Hydrogen peroxide may be used in combination with another oxidizing agent. The oxidizing agent is preferably used in 25 an amount of from 0.5 to 10 wt.%, especially preferably from 1 to 8 wt.%, based on the hair dye composition. The first part containing the inventive dyestuff of the general formula (1) and the second part containing the oxidizing agent are mixed at a volume ratio preferably 30 ranging from 2:1 to 1:3. In the hair dye composition of the present invention, an oxidation dye can be used in combination with the inventive dyestuff of the general formula (1). Such combined use enables considerably vivid and intense dyeing which cannot be accomplished by WO 2007/090799 PCT/EP2007/051041 15 the single use of the oxidation dye. For the oxidation dye, known developers and couplers ordinarily employed for an oxidation type hair dye can be used. Examples of the developer include paraphenylenediamine, toluene-2,5-diamine, 2 chloro-paraphenylenediamine, N-methoxyethyl-paraphenylened iam ine, N,N-bis(2 5 hydroxyethyl)-paraphenylenediamine, 2-(2-hyd roxyethyl)-paraphenylened iam ine, 2,6 dimethyl-para-phenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2 hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,2,2' paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4 aminophenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4 10 aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6 tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino-1-(4' chlorobenzyl)pyrazole and salts thereof. 15 Examples of the coupler include metaphenylenediamine, 2,4 diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5 methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3 diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane, metaaminophenol, 2-methyl-5-aminophenol, 2 20 methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3 amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl metaaminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4 fluoro-5-aminophenol, resorcin, 2-methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5 dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2 25 isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7 hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5 methylenedioxyphenol, 3,4-methylenedioxyaniline, 1-(2-hydroxyethyl)amino-3,4 methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5 diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6 30 methoxypyridine, 2-amino-3-hydroxypyridine, and 2,6-diaminopyridine and salts thereof. As each of the developer and coupler, at least two of the above-described developers or couplers are usable. The content of each of them is preferably from WO 2007/090799 PCT/EP2007/051041 16 0.01 to 20 wt.%, especially preferably from 0.05 to 10 wt.% based on the hair dye composition. To the hair dye composition of the present invention, an autoxidation dye typified by 5 an indole or an indoline, or a known direct dye such as a nitro dye or a disperse dye can also be added. Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymer and/or silicone to the hair dye composition of the present invention is preferred, because the resulting composition can dye the hair uniformly and provides improved cosmetic 10 effects of the hair. In addition to the above-described components, those ordinarily employed as a raw material for cosmetics can be added to the hair dye composition of the present invention. Examples of such an optional component include hydrocarbons, animal or 15 vegetable fats and oils, higher fatty acids, organic solvents, penetration promoters, cationic surfactants, natural or synthetic polymers, higher alcohols, ethers, amphoteric surfactants, nonionic surfactants, anionic surfactants, protein derivatives, amino acids, antiseptics, chelating agents, stabilizers, antioxidants, plant extracts, crude drug extracts, vitamins, colorants, perfumes and ultraviolet absorbers. 20 The hair dye composition of the present invention can be prepared in a conventional manner to form a one-part composition or a two-part composition having a first part containing an alkali agent and a second part containing an oxidizing agent. The inventive dyestuff of the general formula (1) may be incorporated in at least one of 25 these parts of the two-part or three-part composition. When the hair dye composition of the present invention is of the one-part type, it is applied to the hair directly, while when it is of the two- or three-part type, these parts are mixed just before hair dyeing and the mixture is applied to the hair. In the case of preparation of a two-part type hair dye composition, the first part is 30 typically prepared by mixing the Inventive dyestuff of the general formula (1) and optionally an oxidation dye and adjusting the pH of the mixture to 8 to 12 with an alkali agent such as ammonia. The second part is prepared by incorporating about 2 to 6 wt.% of hydrogen peroxide, adjusting the mixture to weakly acidic with phosphoric.

WO 2007/090799 PCT/EP2007/051041 17 The hair dye composition of the present invention can be provided in the form of powder, transparent liquid, emulsion, cream, gel, paste, aerosol, aerosol foam or the like. It preferably has a viscosity of 2000 to 100000 mPa-s upon its application to the hair (after mixing of all the parts when the composition is a two-part or three-part 5 type). The above-described viscosity is measured at 200C by using a Brookfield rotary viscometer (No. 5 spindle, 5 rpm). The present invention also refers to a process for colouring hair characterized in that a hair dye composition as described above is applied onto hair, left for 1 to 45 10 minutes and than rinsed off from hair. In a preferred inventive process the hair dye composition is mixed with a composition comprising at least one oxidizing agent. In the following, embodiments of the invention are described in detail for the purpose 15 of illustrating only and not for the purpose of limiting the same. Example 1 Preparation of ([3-(4,8-diamino-9,10-dioxo-9,10-dihydro-anthracen-1-ylamino) propyl]-trimethyl-ammonium methylsulfate) 20 90 parts of 3-dimethylaminopropylamine, 10.0 parts of 1,5-diamino-4-chloro anthraquinone and 0.25 parts of Cu(II)acetate were heated together under nitrogen at 110 0C for 7% hours. After cooling at room temperature, the mixture was poured into 500 parts of cold water. The precipitate was filtered off, washed with water and 25 dried to yield 10.7 parts of a dark blue powder. For quaternisation 9.0 parts of the blue dye thus obtained were dispersed in 100 parts of ethyl alcohol and treated with 3.0 parts of dimethylsulfate. The reaction mixture was stirred for 3% hours at room temperature. The precipitate was filtered off and washed with acetone. Upon drying 10.7 parts of the dyestuff of the formula lj were obtained. The blue dye lj is very good 30 water-soluble. The analytic data are consistent with the assigned structure for dye lj.

1 H NMR (500 MHz, DMSO-d6): 8 = 2.08 (2H), 3.08 (9H), 3.23-3.54 (broad), 7.00 (1H), 7.09 (1H), 7.22 (1H), 7.31-7.53 (broad), 7.75 (2H), 8.19 (2H); Melting point: > 175 C; WO 2007/090799 PCT/EP2007/051041 18 Xmax (H 2 0) = 584 nm (12500), 626 nm (11600). Example 2 Preparation of ([3-(4-amino-3-methyl-9,10-dioxo-9,10-dihydro-anthracen-1-ylamino) 5 propyl]-trimethyl-ammonium methylsulfate) 85 parts of 3-dimethylaminopropylamine, 15.8 parts of 1-amino-4-bromo-2 methylanthraquinone and 0.17 parts of Cu(II)acetate were heated together under nitrogen at 94 0C for 2% hours. After cooling at room temperature, water was added 10 until the product precipitated. The product was filtered off, washed and dried to yield 14.0 parts of a dark violet powder. For quaternisation 10 parts of the violet dye thus obtained were dispersed in 100 parts of chlorobenzene and treated with 2.8 parts of dimethylsulfate. The temperature was increased up to 45 0C and the reaction mixture was kept for 3 hours at this temperature. The precipitate was filtered off at 30 0C and 15 washed with acetone. Upon drying 12 parts of the dye of formula Ia were obtained. The bluish violet dye Ia is very good water-soluble. The analytic data are consistent with the assigned structure for dye Ia. 1 H NMR (500 MHz, DMSO-d6): 8 = 2.10 (2H), 2.33 (3H), 3.09 (9H), 3.39 (3H), 3.42 (2H), 3.50 (2H), 7.32 (1H), 7.78 (2H), 8.23 (2H), 10.83 (1H); 20 Melting point: > 210 C; Xmax (H 2 0) = 564 nm (12600), 605 nm (13300). Example 3 Preparation of ([4-(4-amino-3-methoxy-9,10-dioxo-9,10-dihydro-anthracen-1 25 ylamino)-phenyl]-trimethyl ammonium methylsulfate) 21.4 parts of 1-amino-4-bromo-9,1 0-dioxo-9,1 0-dihydro-anthracene-2-sulfonic acid were dispersed in 100 parts of water at 50 C. Thereafter 9.8 parts of N,N-dimethyl p-phenylendiamine, 5.0 parts of NaHCO 3 , 2.7 parts of Na 2

CO

3 and 0.5 parts of CuCl 30 were added. The reaction mixture was kept at 50-60 0C for 2 hours. After cooling at room temperature, the mixture was poured into 700 parts of 2N HCI. The precipitate was filtered off, washed with water and dried to yield 18.8 parts of a dark blue powder. 9.4 parts of the dyestuff thus obtained were added to a 50 0C warm solution WO 2007/090799 PCT/EP2007/051041 19 of water-free KOH in methanol. The reaction mixture was kept at 50 0C for 6 hours. After cooling off, the mixture was poured into 200 parts of water and treated with conc. HCI to a pH value of 6.5-7.0. The precipitate was filtered off, washed with water and dried to yield 7.5 parts of a blue powder. To quaternisation 7.0 parts of this 5 dye dispersed in 95 parts of chlorobenzene were treated with 8.1 parts of dimethylsulfate and stirred at 80 0C for 7 hours. The reaction mixture was filtered off at room temperature, washed with chloroform and dried to obtain 9.05 parts of the dye of formula Ib, which dissolves in water with blue color. The analytic data are consistent with the assigned structure for dye lb. 10 1 H NMR (500 MHz, DMSO-d6): 8 = 3.25 (3H), 3.63 (9H), 3.88 (3H), 7.51 (1 H), 7.62 (2H), 7.83 (2H), 7.96 (2H), 8.23 (2H), 12.68 (1H); Melting point: > 166 C; Xmax (H 2 0) = 574 nm (9000), 605 nm (8000). 15 Example 4 Preparation of ([3-(4-amino-3-ethyl-9,10-dioxo-9,10-dihydro-anthracen-1-ylamino) propyl]-trimethyl-ammonium methylsulfate) 10.5 parts of 3-dimethylaminopropylamine, 15.0 parts of 1-amino-4-bromo-2-ethyl 20 anthraquinone, 6.2 parts of water free K 2

CO

3 and 0.20 parts of Cu(II)acetate in 55 parts of dimethylformamide were heated under nitrogen at 80 0C for 3% hours. After cooling at room temperature, the mixture was poured into 350 parts of cold water as the product precipitated. The product was filtered off, washed and dried to yield 14.10 parts of a dark violet powder. For quaternisation 13.0 parts of the violet dye 25 thus obtained were dispersed in 160 parts of chlorobenzene and treated with 2.3 parts of dimethylsulfate during 30 min. The temperature was increased up to 40-45 0C and the reaction mixture was kept for 3 hours at this temperature. The precipitate was filtered off at 30 0C and washed with warm chorobenzene. Upon drying 11.9 parts of the dye of formula Is were obtained. The bluish violet dye Is is very good 30 water-soluble. The analytic data are consistent with the assigned structure for dye Is. 1H NMR (500 MHz, DMSO-d6): 8 = 1.25 (3H), 2.12 (2H), 2.72 (2H), 3.10 (9H), 3.38 (3H), 3.44 (2H), 3.53 (2H), 7.24 (1H), 7.79 (2H), 8.24 (2H), 10.87 (1H); Melting point: > 117 0C; WO 2007/090799 PCT/EP2007/051041 20 Xmax (H 2 0) = 565 nm (10200), 605 nm (10600). Example 5 Preparation of ([2-(4-amino-3-methyl-9,10-dioxo-9,10-dihydro-anthracen-1-yloxy) 5 ethyl]-trimethyl-ammonium methylsulfate) 3.1 parts of 1-am ino-4-(2-d imethylamino-ethoxy)-2-methylanthraquinone prepared from 1-am ino-4-chloro-2-methylanthraquinone, N,N-dimethylaminoethanolamine and metallic sodium at 95 0C were dispersed in 40 parts of chlorobenzene and treated with 1.0 part of dimethylsulfate. The reaction mixture was kept for 1 hour at room 10 temperature. The precipitate was filtered off and washed with acetone. Upon drying 3.3 parts of the dye of formula If were obtained. The red dye If is very good water soluble. The analytic data are consistent with the assigned structure for dye If. 1H NMR (500 MHz, DMSO-d6): 8 = 2.30 (3H), 3.33 (9H), 3.38 (3H), 3.84 (2H), 4.50 (2H), 7.50 (1H), 8.07 (2H), 8.17 (2H); 15 Melting point: > 224 C; Xmax (H 2 0) = 501 nm (5600). Example 6 Preparation of ([2-(4,8-d iamino-9, 1 0-d ioxo-9, 1 0-d ihyd ro-anthracen- 1 -yloxy)-ethyl] 20 trimethyl-ammonium methylsulfate) 6.6 parts of 1, 5-d iam ino-4-(2-d imethylamino-ethoxy)-anthraquinone prepared from 1,5-diamino-4-chloro-anthraquinone, N,N-dimethylaminoethanolamine and metallic sodium at 95-120 0C were dispersed in 75 parts of chlorobenzene and treated with 25 1.4 parts of dimethylsulfate. The reaction mixture was kept for 1%/2 hours at room temperature. The precipitate was filtered off and stirred with 150 parts of water followed by filtration. The filtrate was evaporated in vacuo yielding 2.5 parts of the dye of formula Ik. The red dye Ik is very good water-soluble. The analytic data are consistent with the assigned structure for dye Ik. 30 1H NMR (500 MHz, DMSO-d6): 8 = 3.29 (9H), 3.38 (3H), 3.83 (2H), 4.42 (2H), 7.08 (1H), 7.18 (1H), 7.33 (1H), 7.43-7.48 (2H), 7.73 (2H), 7.92 (2H); Melting point: > 114 C; Xmax (H 2 0) = 508 nm (10000).

WO 2007/090799 PCT/EP2007/051041 21 Example 7 Preparation of ([3-(4-amino-3-carbamoyl-9,10-dioxo 9,10-dihydro-anthracen-1-ylamino)-propyl]-trimethyl-ammonium methylsulfate) 5 8.9 parts of 1-amino-4-(3-dimethylamino-propylamino)-9,1 0-dioxo-9,1 0-dihydro anthracene-2-carboxylic acid amide were dispersed in 85 parts of o-dichlorobenzene and treated with 2.1 parts of dimethylsulfate at 50 C. The reaction mixture was kept at this temperature for 2 hours. The precipitate was filtered off and washed with 10 warm o-dichlorobenzene and afterwards with ethyl acetate. Upon drying 10.8 parts of the dye of formula Ig were obtained. The blue dye Ig very good water-soluble. The analytic data are consistent with the assigned structure for dye Ig. 1H NMR (500 MHz, DMSO-d6): 8 = 2.13 (2H), 2.33 (3H), 3.10 (9H), 3.38 (3H), 3.42 (2H), 3.58 (2H), 7.63 (1H), 7.83 (2H), 8.23 (2H), 10.53 (1H); 15 Melting point: > 93 0C; Xmax (H 2 0) = 597 nm (11200), 621 nm (11300). Example 8 Preparation of ([3-(4,8-d iamino-3-methoxy-9, 1 0-d ioxo-9, 1 0-d ihyd ro-anthracen- 1 20 ylamino)-propyl]-trimethyl-ammonium methylsulfate) 2.44 parts of 1,5-diamino-4-(3-dimethylamino-propylamino)-2-methoxy anthraquinone prepared from 1,5-diamino-4-(3-dimethylamino-propylamino)-9,10 dioxo-9,10-dihydro-anthracene-2-sulfonic acid and methanolic potassium hydroxide at 95 0C were dispersed in 50 parts of diglyme and treated with 0.75 part of 25 dimethylsulfate. The reaction mixture was kept for 3 hours at room temperature. The precipitate was filtered off and washed with acetone. Upon drying 2.8 parts of the dye of formula lz were obtained. The blue dye lz is very good water-soluble. The analytic data are consistent with the assigned structure for dye Iz. 1H NMR (500 MHz, DMSO-d6): 8 = 2.12 (2H), 2.33 (3H), 3.10 (9H), 3.39 (3H), 3.43 30 (2H), 3.50 (2H), 4.02 (3H), 6.65 (1H), 6.99 (1H), 7.39 (2H), 10.75 (1H); Melting point: > 120 C; Xmax (H 2 0) = 569 nm (13300), 606 nm (11500).

WO 2007/090799 PCT/EP2007/051041 22 The inventive dyestuffs listed in Table 1 below were synthesized in analogy to the procedures described in examples 1 to 8. Q always denotes -N*(CH3)3. The dyestuffs were isolated in form of their methylsulfate salts. 5 Table 1 Example R X Y Z Colour (aqeous solution) 9 -CH 2

CH

2 OH -CH 3

-NH(CH

2

)

3 -Q H bright blue 10 -C 6

H

5 do. do. do. do. 11 -C 6

H

11 do. do. do. do. 12 -CH(CH 3

)

2 do. do. do. do. 13 -CH 2

CH

2 OH -CH 2

CH

3 do. do. do. 14 -C 6

H

5 do. do. do. do. 15 -C 6

H

11 do. do. do. do. 16 -CH(CH 3

)

2 do. do. do. do. 17 H -COCH 3 do. do. do. 18 H -CH 3

-NH-C

6

H

4

-CH

2 -Q do. reddish blue 19 -CH(CH 3

)

2 H -NH(CH 2

)

3 -Q 5-OH blue 20 -CH 2

CH

2 OH -CONH 2 do. H greenish blue 21 -(CH2) 3 -Q -CH 3

-NH-C

6

H

5 H blue 22 -(CH 2

)

3 -Q -CH 3

-NH-C

6

H

4

-CH

3 H greenish blue 23 H H -NH-C 6

H

4

-CH

2 -Q 5-NH 2 greenish blue 24 -CH 2

CH

2 OH -COOEt -NH(CH 2

)

3 -Q H greenish blue 25 H -CONH 2

-NH-C

6

H

4

-CH

2 -Q H greenish blue 26 H -COOEt do. H greenish blue 27 H -CONH 2

-O(CH

2

)

2 -Q H bluish red 28 H -COOEt -O(CH 2

)

2 -Q H bluish red 27 -CH(CH 3

)

2 H do. -5-OH red 28 H -SO 2 NHCH3 -NH(CH 2

)

3 -Q H greenish blue 29 H -SO 2

NH

2

-O(CH

2

)

2 -Q H bluish red 30 H -OMe -NH(CH 2

)

3 -Q 7-OMe reddish blue 31 H -OMe -NH-C 6

H

4

-CH

2 -Q H reddish blue 32 H -O(CH 2

)

2 OH do. H reddish blue 33 H -CH 3

-N(CH

3

)(CH

2

)

3 -Q H blue 34 H H -O(CH 2

)

2 -Q 5-NHAc red WO 2007/090799 PCT/EP2007/051041 23 Example R X Y Z Colour (aqeous solution) 35 H H do. 5-NH2 bluish red 36 -CH 3 H -NH(CH 2

)

3 -Q 5-NHCH 3 dark blue 37 -(CH 2

)

3 -Q -CH 3 -OH H bluish red 38 H -CN -NH(CH 2

)

3 -Q H blue 39 H -CH=N-C 6

H

5 do. H blue 40 H -CH=N-C 6

H

5

-O(CH

2

)

2 -Q H red 41 -CH 2

CH

2 OH H -NH(CH 2

)

3 -Q 5-NHC 2

H

4 0H blue Examples of Dyeing Performance of Dyestuffs 5 Example A The dyes listed in Table 2 were dissolved into the following Base Formulation 1: Dyestuff of general formula (1) 0.5g iso-Propanol 5.Og 10 Ammonium Hydroxide (25%) 5.Og Water up to 1O0g pH 10.2 Approximately 1.5 g of the Base Formulation I was applied to 1g of undamaged white 15 goat hair at 30 0 C for 30 mins. At the end of the processing time the tresses were rinsed with water, shampooed and then dried. The colour of the tresses was recorded by measuring L, a and b values of the tresses before and after the colouring using a hand held Datacolor Mercury colour measuring instrument and the value of delta E, which is a known measure for the 20 chroma, was calculated according to the well-known equation: AE = (AL 2 + Aa 2 + Ab2)1' 2 for each example (this will apply equally to every example hereinafter). The results are shown in Table 2: Dyeing effect of Examples (la), (Ib), (Id), (If), (lj), (Ik and (Im) on undamaged goat hair: 25 WO 2007/090799 PCT/EP2007/051041 24 Table 2 Dyestuff Color of Dyed Hair L a b Delta E Formula lj Vivid Cyan Blue 40.4 -3.0 -20.3 53.7 Formula la Intense Pure Blue 48.8 5.2 -24.6 50.4 Formula Id Violet Blue 40.4 5.5 -16.6 51.6 Formula lb Intense Ash Blue 47.4 -1.3 -14.7 44.7 Formula If Red Brown 46.4 21.9 7.7 42.9 Formula Ik Pure Red 44.0 39.5 8.1 54.9 Formula Im Dark Violet 43.5 10.7 -15.0 49.5 5 Example B The dyes listed in Table 3 were dissolved into the following Base Formulation 2, containing alkaline hydrogen peroxide: Dyestuff of general formula (1) 0.5g iso-Propanol 5.Og 10 Ammonium Hydroxide (25%) 5.0g Hydrogen Peroxide (50%) 6.0g Water up to loog pH 10.2 15 Approximately 1.5 g of the Base Formulation 2 was applied to 1g of undamaged white goat hair at 30 0 C for 30mins. At the end of the processing time the tresses were rinsed with water, shampooed and then dried. The color of the tresses was recorded as given in Example A above. 20 The results are shown in Table 3: Dyeing effect of Examples (Ia), (Ib), (Id), (If), (lj), (1k) and (Im) on undamaged goat hair in combination with alkaline peroxide: 25 -25 Table 3 Dyestuff Color of Dyed Hair L a b Delta E Formula lj Vivid Cyan Blue 40.4 -3.0 -20.3 53.7 Formula la Intense Pure Blue 48.8 5.2 -24.6 50.4 Formula Id Violet Blue 40.4 5.5 -16.6 51.6 Formula lb Intense Ash Blue 47.4 -1.3 -14.7 44.7 Formula If Red Brown 46.4 21.9 7.7 42.9 Formua Ik Pure Red 44.0 39.5 8.1 54.9 Formula Im Dark Violet 43.5 10.7 -15.0 49.5 Throughout this specification and the claims which follow, unless the context requires 5 otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 10 The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as, an acknowledgement or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (11)

1. Dyestuff of the general formula (1) o NHR z I O Y 5 wherein R is hydrogen, alkyl, alkyl substituted by Q, aryl, Q-aryl, -OR2, -SR3 or -NR R4, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl, cycloalkyl substituted by Q, aryl substituted by R 1 0 , Q, R 11 0-alkyl, -OR, -SR 13 , -NR 4 R 5 , 10 -CONR 1 R", -C(O)OR , -S0 2 -NR"R", -SO 2 OR 20, -C(O)R or -SO 2 R , -C(O)R', -SO 2 NR 7 R 8 or -S0 2 R 9 ; X is hydrogen, -OR 23 , -SR 24 , -NR 2 5 R 26 , -S0 2 NR 2 7 R 2 , -CONR 2 9 R 30 , -S02OR 31 -C(O)OR 32, -C(O)R 33, -SO 2 R 34, alkyl, alkyl substituted by -OR 200, -SR300 or 15 -NR 00 R 400 , aryl substituted by R 10 0 , R 11 00-alkyl, -OR 0 , -SR 130 , -NR 40 R 50 , 150 160 170 180 190 201 21020 -CONR R , -C(O)OR , -SO 2 -NR R , -SO 2 OR2, -C(O)R or -SO2R -NHSO 2 R 3 6 R 37 , -CHO, -CH=NR 35 or NO 2 ; 51 52 5 54 55 5657 Y is hydrogen, -NR R 2, -OR 3 , -SR , -SO 2 NHR , -NHC(O)R 56 , -SO 2 OR 20 -NHSO 2 R 8, -SO 2 R 9, -NHSO 2 NR 6R 6, halogen or NO 2 ; 51 52 53 54 55 56 57 Z is hydrogen, -NR 'R , -OR , -SR , -SO 2 NHR , -NHC(O)R , -SO 2 OR -NHSO 2 R 5 8 , -S0 2 R 5 9 , -NHSO 2 NR 60 R, 6 1 halogen or NO 2 ; 25 each of R to R , R 0 and R 61 , independently, is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; WO 2007/090799 PCT/EP2007/051041 27 R 9 is alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 5 each of R 10 to R 16 , R 18 , R 19 and R , independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 17 20 22 10 each of R , R and R , independently, is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; 23 30 35 each of R to R30 and Ra, independently, is hydrogen, alkyl, hydroxyalkyl, 15 polyhydroxyalkyl, cycloalkyl or cycloalkyl substituted by -C(O)R 6 , -S0 2 R 9 , or aryl 1' 1'12' 13' 1' 15' 15' 16' 17' substituted by R1", R O-alkyl, -OR , -SR , -NR4 R , -CONR R , -C(O)OR , S0 2 -NR 18 R 1 9 , -S0 2 OR 20 , -C(O)R 21 or -SO2R2; R 6 is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; 20 R 9 is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; each of R 10 to R 16 , R , R 19 and R 2 , independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; 25 17' 20 22' each of R , R 0'and R , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; 36 37 each of Ra and R37, independently, is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or 30 cycloalkyl and one of R and R37 can additionally be hydrogen; each of R 5 to R 4 , independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl WO 2007/090799 PCT/EP2007/051041 28 substituted by Q, -C(O)R , -SO 2 R 9 , or aryl substituted by R 0 , R 1 O-alkyl, -OR, SR , -NR4 R , -CONR1 R , -C(O)OR , -SO 2 -NR R19, -SO 2 OR 2, -C(O)R2 or -SO 2 R2; 5 each of R 31 to R 33 , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl 10 1'12' 13' 14' 15' or aryl substituted by R0 , R" O-alkyl, -OR , -SR , -NR R , -CONR 15 R 16 , -C(O)OR 1 1, -SO 2 -NR 18 R 19 , -SO 2 OR 20 , -C(O)R 2 1 or -SO 2 R 22 , and R 33 can additionally be hydrogen; 10 R 34 is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R 10 ', R" O-alkyl, -OR , -SR, 13 -NR 14 R 15 , -CONR 15 R 16 , -C(O)OR1 , -SO 2 -NR 18 R 1 9 , 20' 21' 22'. -SO 2 OR , -C(O)R or -SO 2 R each of R 5 to R 57 , independently, is hydrogen, alkyl, alkyl substituted by Q, 15 hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl 12 1 14 15 substituted by Q or aryl substituted by R10, R 11 O-alkyl, -OR, -SR, -NR R -CONR1 R , -C(O)OR 1, -SO 2 -NR R19, -SO 2 OR 20, -C(O)R or -SO 2 R , and R5 and R 56 can additionally be hydrogen; 20 each of R" and R 59 , independently, is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q or aryl 1 1112 13 14 15 substituted by R10, R 0-alkyl, -OR , -SR , -NR R , 25 -CONR 15 R 16 , -C(O)OR 1, -SO 2 -NR 18 R 19 , -SO 2 OR 20 , -C(O)R 21 or -SO 2 R2; each of R 200 , R 30 o, R 4 00 and R" 0 , independently, is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; each of R 100 , R 110 , R 1 0 , R 1 0 , R 140 , R 1 0 , R 1 0 , RI 0 , R 190 and R 2 0 , independently, is 30 hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, or cycloalkyl; 170 201 220 each of R , R , and R , independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, or cycloalkyl; and WO 2007/090799 PCT/EP2007/051041 29 Q is a group of the general formula (11) R R R (iI) wherein each of R', R" and R"', independently, is (C 1 -C 6 )-alkyl, aryl, arylalkyl, cycloalkyl, 5 cycloalkylalkyl, heteroaryl, heteroarylalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, either of which can be substituted by heteroatom containing groups or R' and R" form together with the nitrogen to which they are bonded a 5- or 6- membered satureated heterocyclic ring; and A is a cosmetically acceptable, water solubilizing anion, and does not comprise 10 arylsulfonate, phosponate and alkylphosphonate; whereby the dyestuff of the formula (1) contains exactly one group Q; whereby at least two of the groups X, Y and Z are groups other than hydrogen; and 51 52 23 51 whereby in case R and X are both hydrogen and Y is -NR 'R or -OR , wherein R R52 2325 2625 2 R and R 23 are hydrogen, Z is not -NR R 2 , wherein one of R and R 2 e is hydrogen 15 and the other is alkyl substituted by Q.

2. Dyestuff according to claim 1, wherein in the group of the formula (11) R', R" and R"' are (C 1 -C 6 )-alkyl or benzyl and A is chloride, bromide, iodide, hydroxide, hydrogenphosphate, phosphate, carbonate, hydrogencarbonate, hydrogensulfate, 20 perchlorate, fluoroborate, chlorozincate, methylsulfate, ethylsulfate, acetate, propionate, lactate or citrate or a mixture thereof.

3. Dyestuff according to claims 1 and/or 2, wherein X is (C 1 -C 6 )-alkyl, -OR 23 or -SR 24 , wherein R 23 and R24 are hydrogen, (C 1 -C 6 )-alkyl, 29 30 32 29 30 25 hydroxy-(C 1 -C 6 )-alkyl or phenyl, or -CONR 2R or -C(O)OR , wherein R and R independently are hydrogen, (C 1 -C 6 )-alkyl, hydroxy-(C 1 -C 6 )-alkyl or phenyl and R 32 is (C 1 -C)-alkyl, hydroxy-(C 1 -C 6 )-alkyl or phenyl; Z is hydrogen; R is hydrogen or (C 1 -C)-alkyl; 30 Y is -NR51R52 or -OR 5 3 , wherein R 51 is hydrogen and R52 is (C 1 -C 6 )-alkyl substituted by Q, phenyl substituted by Q or (C 1 -CO)-alkyl-SO 2 -phenyl wherein the alkyl group is WO 2007/090799 PCT/EP2007/051041 30 substituted by Q; and R 5 3 is (C 1 -C)-alkyl substituted by Q, phenyl substituted by Q, (C 1 -C)-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q or (C 1 -C)-alkyl NH-SO 2 -phenyl wherein the alkyl group is substituted by Q; Q is a tris-(C 1 -C 6 )-alkyl-ammonium group, a bis(C 1 -C 6 )-alkyl-benzyl-ammonium 5 group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and A is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.

4. Dyestuff according to claims 1 and/or 2, wherein 51 52 56 53 51 52 53 10 Z is -NR R , -NHC(O)R or -OR , wherein R is hydrogen R and R are hydrogen or (C 1 -C 6 )-alkyl substituted by Q and R is (C 1 -C)-alkyl or phenyl; X is hydrogen; R is hydrogen or (C 1 -C)-alkyl; Y is -NR51R52 or -OR 5 3 , wherein R 51 is hydrogen, R 52 is hydrogen, (C 1 -C 6 )-alkyl, 15 hydroxy-(C 1 -C 6 )-alkyl, (C 1 -C)-alkyl substituted by Q, phenyl, phenyl substituted by Q or (C 1 -C 6 )-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q; and R 5 3 is hydrogen, (C 1 -C)-alkyl, (C 1 -C)-alkyl substituted by Q, phenyl, phenyl substituted by Q, (C 1 -C 4 )-alkyl-SO 2 -phenyl wherein the alkyl group is substituted by Q or (C 1 -C 4 ) alkyl-NH-SO 2 -phenyl wherein the alkyl group is substituted by Q; 20 Q is a tris-(C 1 -C 6 )-alkyl-ammonium group, a bis(C 1 -C 6 )-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to either Z or Y; and A is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate. 25

5. Dyestuff according to claims 1 and/or 2, wherein 51 52 56 51 52 Z is -NR 'R , -NHC(O)R , wherein R is hydrogen and R is hydrogen or (C 1 -C 6 )-alkyl substituted by Q and R 56 is (C 1 -C 6 )-alkyl or phenyl; X is -OR 23, -SO 2 NR 2R 2 or -SO 2 OR 31, wherein R23 and R31 are (C 1 -C)-alkyl, 30 hydroxy(C 1 -C 6 )-alkyl or phenyl; R 27 is hydrogen, R 28 is hydrogen (C 1 -C 6 )-alkyl or hydroxy(C 1 -C 6 )-alkyl; R is hydrogen or (C 1 -C 6 )-alkyl; -31 Y is -NR 5R 5 2 , wherein R 51 is hydrogen, R 52 is (C 1 -C 6 )-alkyl, (C1-C 6 )-alkyl substituted by Q, hydroxy-(CI-C 6 )-alkyl, hydroxy-(CI-C 6 )-alkyl substituted in the alkyl group by Q, phenyl or phenyl substituted by Q; Q is a tris(CI-C 6 )-alkyl-ammonium group, a bis(C 1 -C 6 )-alkyl-benzyl-ammonium group, 5 a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to either Y or Z; and A- is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate. 10

6. Dyestuff mixture comprising one or more dyestuffs of the general formula (1) according to one or more of claims 1 to 5 and one or more direct or oxidation dyestuff.

7. Hair dye composition comprising one or more dyestuffs of the general formulae (1) according to one or more of claims 1 to 5 or a dyestuff mixture according to claim 6. 15

8. Hair dye composition according to claim 7 which comprises at least one oxidative dye precursor and/or at least one coupling compound.

9. Hair dye composition according to claims 7 and/or 8 which comprises an oxidizing 20 agent.

10. Hair dye composition according to one or more of claims 7 to 9 which has a pH value in the range of 2 to 11. 25

11. Process for colouring hair wherein a hair dye composition according to one or more of claims 7 to 9 is applied onto hair, left for 1 to 45 minutes and than rinsed off from hair.