# Patent

## Title
Hair dyeing composition

## Abstract

The invention relates to hair dyeing composition comprising (a) a dye of formula (1); (b) a least one dye selected from the compounds of formulae (2) and (3), wherein D is the radical of a diazo component of the formula (2a) and (c) a quaternary ammonium salt selected from (c1) quaternary ammonium salts of the formula (4); (c2) imidazolium salts of the formula (5) and (c3) quaternary diammonium salts of the formula (6). The invention also relates to the dyeing methods for dyeing keratinous fibers comprising such dyeing composition.

## Background
The present invention relates to a composition for dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in an appropriate dyeing medium, at least a mixture of at least 2 cationic direct dyes of a given formula, and at least one quaternary ammonium salt mixtures of cationic dyes, compositions thereof, to processes for their preparation and to their use in the dyeing of organic material, such as keratin fibers, wool, leather, silk, cellulose or polyamides, especially keratin-containing fibres, cotton or nylon, and preferably hair, more preferably human hair.
It is known, for example, from WO 95/01772, WO 95/15144, EP 714 954 and EP 318 294 that cationic dyes can be used to dye organic material, for example keratin, silk, cellulose or cellulose derivatives, and also synthetic fibres, for example polyamides. Cationic dyes exhibit very brilliant shades. A disadvantage is their unsatisfactory fastness to hydrolysis and to light, their frequently inadequate stability under reducing or oxidizing conditions, and their frequently unsatisfactory storage stability (see: John F. Corbett: “The Chemistry of Hair-Care Products”, JSCD August 1976, page 290).
The actual technical problem of the present invention was to provide brilliant dyes that are distinguished by deep dying having good fastness properties with respect to washing, light, shampooing and rubbing, and that preferably exhibit satisfactory stability under reducing or oxidizing dyeing conditions, for the dyeing of organic material.
Accordingly, the present invention relates to a hair dye composition, comprising

    
    
        (a) a dye of formula
    
    






    
    
        (b) at least one dye selected from the compounds of formulae
    
    






    
    
        
        
            wherein
        
        
        D is the radical of a diazo component of the formula
    
    






    
    
        K is the radical of a coupling component selected from aniline derivatives; phenol derivatives; and a radical of a heterocyclic coupling component;
        X is —O—; —S—; or —N(R8)—;
        Y is —CH═; —CR15═; or —N═;
        R1, R2, R3 and R4 independently from each other are hydrogen; or C1-C4alkyl;
        R5 and R6 independently from each other are hydrogen; C1-C4alkyl; or C1-C4alkoxy;
        R7 and R9 independently from each other are unsubstituted or OH—, C1-C4alkoxy-, halogen-, amino-, C1-C4-mono or -dialkylamino-substituted C1-C4alkyl;
        R8 is hydrogen; or C1-C4alkyl;
        R10 is hydrogen; C1-C4alkyl; or CN;
        R11 is unsubstituted or OH— or CN-substituted C1-C4alkyl;
        R12 is hydrogen; or C1-C4alkyl;
        R13 and R14 independently from each other are hydrogen; C1-C4alkyl; or C1-C4alkoxy; or
        R13 and R14 together with the nitrogen and carbon atoms joining them together form a 5- or 6-membered ring;
        R15 is hydrogen; or C1-C4alkyl; and
        An1− is a colorless anion; and
        (c) a quaternary ammonium salt selected from
        (c1) quaternary ammonium salts of the formula
    
    






    
    
        
        
            wherein
        
        
        R16 and R19, independently from each other are a saturated or unsaturated, linear or branched, aliphatic C1-C30alkyl; or an alkoxy, alkoxycarbonylalkyl, polyoxyalkylene, alkylamido, alkylamidoalkyl, hydroxyalkyl, aromatic, aryl or alkylaryl radical comprising from about 12 to about 30 carbon atoms, with at least one radical among R16, R17, R18 and R19 denoting a radical comprising from 8 to 30 carbon atoms;
        An2− is an anion selected from the group comprising halides, phosphates, acetates, lactates and alkyl sulphates;
        (c2) imidazolium salts of the formula
    
    






    
    
        
        
            wherein
        
        
        R20 is C13-C31alkyl or C13-C31alkenyl, derived from tallow fatty acids;
        (c3) quaternary diammonium salts of the formula
    
    






    
    
        
        
            in which
        
        
        R21 is C6-C31alkyl;
        R22, R23, R24, R25 and R26 are selected from hydrogen; or C1-C4alkyl; and
        An3− is an anion selected from halides, acetates, phosphates and sulphates.
    
    


C1-C30alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tredecyl, tetradecyl, pentadecyl, haxadecyl or eicosyl.
C2-C30alkenyl is for example allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
Aryl is for example naphthyl and preferably phenyl.
Heterocyclic organic radical is, for example, a five-membered nitrogen-containing hetero-cyclic radical such as imidazolyl, pyrazolyl, triazolyl, pyrrolyl, pyrrolidinyl, oxazolyl or thiazolyl, a six-membered nitrogen-containing heterocyclic radical such as piperazinyl, piperidinyl, pyridinyl or morpholinyl, or a bicyclic radical which possesses a fused-on five-membered nitrogen-containing heterocycle and a six-membered aromatic ring, such as benzoxazolyl, indolyl, benzothiazolyl, benzimidazolyl or benzotriazolyl.
Preferred is a hair dye composition, wherein in formula (1) of component (a) R1, R2, R3 and R4 independently from each other are hydrogen; or C1-C2alkyl.
More preferred is a hair dye composition, wherein component (a) corresponds to formula




More preferably, in formula (2a)

    
    
        R7 and R9 independently from each other are C1-C4alkyl; and even more preferred are hair dye compositions, wherein
        X is —NH; and
        Y is —CH═.
    
    


Even more preferred are hair dye compositions, wherein in formula (2)

    
    
        K is the radical of formula
    
    






    
    
        
        
            wherein
        
        
        R27 is hydrogen; hydroxy; C1-C4alkyl; C1-C4alkoxy; amino; mono-C1-C4alkylamino; or di-C1-C4alkylamino.
    
    


Most preferred are hair dye compositions comprising

    
    
        (a) a dye of formula (1),
        (b) at least one dye selected from the compounds of formulae
    
    






    
    
        (c) a quaternary ammonium salt as defined as in claim 1.
    
    


Examples for quaternary ammonium salt according to component (c1), there may be mentioned, for example, (c11) the dialkyl dimethylammonium or alkyltrimethylammonium salts in which the alkyl radical comprises from about 12 to about 22 carbon atoms, such as the distearyl dimethylammonium, cetyltrimethylammonium or behenyltrimethylammonium chlorides, (c12) the di(C1-C2alkyl) (C12-C22alkyl)hydroxy(C1-C2alkyl)ammonium salts such as oleocetylhydroxyethylammonium chloride, or alternatively (c13) the stearamidopropyldimethyl (myristyl acetate) ammonium chloride of formula:




sold under the trademark CERAPHYL 70 by the company VAN DYK.

According to the present invention, the quaternary ammonium salts of formula (6) are preferred in which R21 to R26, which are identical or different, denote alkyl or hydroxyalkyl radicals comprising from about 12 to about 22 carbon atoms, and in particular behenyltrimethylammonium chloride, cetyltrimethylammonium chloride and oleocetyldimethylhydroxyethylammonium chloride.
The quaternary ammonium salt(s) according to component (c) used according to the invention preferably represent from 0.01 to 10% by weight approximately of the total weight of the dyeing composition and still more preferably from 0.05 to 5% by weight approximately of this weight.
The hair dye compositions according to the invention are suitable for dyeing organic materials, such as keratin-containing fibers, wool, leather, silk, cellulose or polyamides, cotton or nylon, and preferably human hair. The dyeings obtained are distinguished by their depth of shade and their good fastness properties to washing, such as, for example, fastness to light, shampooing and rubbing. The stability, in particular the storage stability of the hair dye compositions according to the invention are excellent.
The multiplicity of shades of the dyes can be increased by combination with other dyes.
Therefore the hair dye compositions of the present invention may be combined with dyes of the same or other classes of dyes, especially with direct dyes, oxidative dyes; disulfide dyes, pigments or mixtures thereof.
Direct dyes are of natural origin or may be prepared synthetically. They are uncharged, cationic or anionic, such as acid dyes.
The hair dye composition according to the present invention of may be used in combination with at least one single direct dye different from the dyes of component (a) and (b).
Examples of direct dyes are described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, and in “Europäisches Inventar der Kosmetikrohstoffe”, 1996, published by The European Commission, obtainable in diskette form from the Bundesverband der deutschen Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim.
Furthermore, cationic nitroaniline and anthraquinone dyes are useful for a combination with the hair dyeing composition according to the present invention.
The hair dye composition according to the present invention may also be combined with acid dyes, for example the dyes which are known from the international names (Color index), or trade names.
These acid dyes may be used either as single component or in any combination thereof.
The hair dye composition according to the present invention may also be combined with uncharged dyes, for example selected from the group of the nitroanilines, nitrophenylene-diamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, bispyrazolons, bispyrazol aza derivatives and methines.
Furthermore, the hair dye composition according to the present invention may also be used in combination with sulfide dyes. Examples for sulfide dyes are disclosed for example in WO 05/097051.
Furthermore, the hair dye composition according to the present invention may also be used in combination with color pigments.
The organic pigments are preferably selected from D&C Red 30 (Vat Red 1); D&C Red 36 (Pigment Red 4); Carmine; D&C Red 6 Ba Lake; D&C Red 7 Ca Lake; D&C Red 30 Al Lake; D&C Red 30 Talc Lake; D&C Red 27 Al Lake; D&C Red 28 Al Lake; D&C Red 33 Al Lake; D&C Red 21 Al Lake.
Of specific interest are the pigments/colours listed in Table 1 below:












Table 1a: Examples of pigments/colours (component (b))









Color index

CAS registry


number
Official and common name
number





10006
Pigment Green 8
16143-80-9 


10020
Acid Green 1
19381-50-1 


10316 (2)
Ext. D & C Yellow No. 7; Acid Yellow 1; Naphthol Yellow S
 846-70-8


11680
Pigment Yellow 1
2512-29-0


11710
Pigment Yellow 3
6486-23-3


11725
Pigment Orange 1
6371-96-6


11920
Solvent Orange 1
2051-85-6


12010
Solvent Red 3
6535-42-8


12085 (2)
D & C Red No. 36; Pigment Red 4; Flaming Red
2814-77-9


12120
Pigment Red 3
2425-85-6


12150
Solvent Red 1
1229-55-6


12370
Pigment Red 112
6535-46-2


12420
Pigment Red 7
6471-51-8


12480
Pigment Brown
6410-40-8


12490
Pigment Red 5
6410-41-9


12700
Disperse Yellow 16
4314-14-1


13015
E 105; Acid Yellow 9
2706-28-7


14270
E 103; Acid Orange 6
 547-57-9


14700
FD & C Red No. 4; Food Red 1; Ponceau SX
4548-53-2


14720
E 122; Acid Red 14; Food Red 3; Azorubine; Carmoisine
3567-69-9


14815
E 125; Food Red 2
3257-28-1


15510 (2)
D&C Orange No. 4; Acid Orange 7; Orange II
 633-96-5


15525
Pigment Red 68
5850-80-6


15580
Pigment Red 51
227-459-1


15620
Acid Red 88
1658-56-6


15630
Pigment Red 49
1248-18-6


15800:1
D&C Red No. 31; Pigment Red 64:1; Brilliant Lake Red R
6371-76-2


15850
D&C Red No. 6; Pigment Red 57; Lithol Rubin B
5858-81-1


15850:1 (2)
D&C Red No. 7; Pigment Red 57:1; Lithol Rubin B Ca
5281-04-9


15865 (2)
Pigment Red 48
3564-21-4


15880:1
D&C Red No. 34; Pigment Red 63:1; Deep Maroon; Fanchon
6417-83-0



Maroon; Lake Bordeaux B



15980
E 111; Food Orange 2
2347-72-0


15985 (2)
FD&C Yellow No. 6; E 110; Food Yellow 3; Sunset Yellow;
2783-94-0



Sunset Yellow FCF; Orange Yellow S



16035
FD&C Red No. 40; Food Red 17; Allura Red; Allura Red AC
25956-17-6 


16230
Acid Orange 10
1936-15-8


16255 (2)
E 124; Acid Red 18; Food Red 7; Ponceau 4R; Cochineal Red
2611-82-7



A



16290
E 126; Acid Red 41
5850-44-2


17200 (2)
D&C Red No. 33; Acid Red 33; Acid Fuchsine
3567-66-6


18050
Acid Red 1
3734-67-6


18130
Acid Red 155
10236-37-0 


18690
Acid Yellow 121
5601-29-6


18736
Acid Red 180
6408-26-0


18820
Acid Yellow 11
6359-82-6


18965
Acid Yellow 17
6359-98-4


19140 (2)
FD&C Yellow No. 5; E 102; Acid Yellow 23; Tartrazine
1934-21-0


20040
Pigment Yellow 16
5979-28-2


20170
D&C Brown No. 1; Acid Orange 24; Resorcin Brown
1320-07-6


20470
Noir W 699
1064-48-8


21100
Pigment Yellow 13
5102-83-0


21108
Pigment Yellow 83
5567-15-7


21230
Solvent Yellow 29
6706-82-7


24790
Acid Red 163
13421-53-9 


26100
D&C Red No. 17; Solvent Red 23; Sudan III; Toney Red
 85-86-9


27290 (2)
Acid Red 73
5413-75-2


27755
E152; Food Black 2
2118-39-0


28440
E 151; Brilliant Black 1; Food Black 1; Brilliant Black BN; Black PN
2519-30-4


40215
Direct Orange 34
1325-54-8


40800
Beta Carotene (synthetic); Food Orange 5
7235-40-7


40820
E 160e; Food Orange 6; β-Apo-8′ Carotenal (C 30)
1107-26-2


40825
E 160f; Food Orange 7; Ethyl Ester of β-Apo-8′ Carotenic Acid 
1109-11-1



(C 30)



40850
Canthaxanthin; E 161g; Food Orange 8
 514-78-3


42045
Acid Blue 1
 129-17-9


42051 (2)
E 131; Acid Blue 3; Patent Blue V
3536-49-0


42053
FD&C Green No. 3; Food Green 3; Fast Green FCF
2353-45-9


42080
Acid Blue 7
3486-30-4


42090
FD&C Blue No. 1; Acid Blue 9 (Sodium salt); Food Blue 2;
3844-45-9



Brilliant Blue FCF; Patent Blue AC




FD&C Blue No. 4; Acid Blue 9 (Ammonium salt); Alphazurine
6371-85-3



FG; Erioglaucine



42100
Acid Green 9
4857-81-2


42170
Acid Green 22
5863-51-4


42510
Basic Violet 14
 632-99-5


42520
Basic Violet 2
3248-91-7


42735
Acid Blue 104
6505-30-2


44045
Basic Blue 26
2580-56-5


44090
E142; Acid Green 50; Green S
3087-16-9


45100
Acid Red 52
3520-42-1


45190
Acid Violet 9
6252-76-2


45220
Acid Red 50
5873-16-5


45350
D&C Yellow No. 8; Acid Yellow 73; Uranine
 518-47-8


45350:1
D&C Yellow No. 7; Solvent Yellow 94; Fluorescein
2321-07-5


45370 (2)
Acid Orange 11



45370:1
D&C Orange No. 5; Solvent Red 72; Dibromofluorescein
 596-03-2


45380 (2)
D&C Red No. 22; Acid Red 87; Eosin Y
17372-87-1 


45380:2
D&C Red No. 21; Solvent Red 43; Tetrabromofluorescein
15086-94-8 


45396
Solvent Orange 16
24545-86-6 


45405
Acid Red 98
6441-77-6


45410 (2)
D&C Red No. 28; Acid Red 92; Phloxine B
18472-87-2 


45410:1
D&C Red No. 27; Solvent Red 48; Tetrabromotetrachloro-;
13473-26-2 



Fluorescein



45425
D&C Red No. 11; Acid Red 95; Erythrosine Yellowish Na
33239-19-9 


45425:1
D&C Orange No. 10; Solvent Red 73; Diiodofluorescein
38577-97-8 


45430 (2)
E 127; FD&C Red No. 3; Acid Red 51; Erythrosine; Food Red
16423-68-0 



14



47000
D&C Yellow No. 11; Solvent Yellow 33; Quinoline Yellow SS
8003-22-3


47005
D&C Yellow No. 10; E104; Acid Yellow; Food Yellow 13;
8004-92-0



Quinoline Yellow; Canary Yellow



50325
Acid Violet 50
 229-951-1


50420
Acid Black 2
8005-03-6


51319
Pigment Violet 23
6358-30-1


58000
Pigment Red 83; Alizarin
 72-48-0


59040
D&C Green No. 8; Solvent Green 7; Pyranine Concentrated
6358-69-6


60724
Disperse Violet 27
19286-75-0 


60725
D&C Violet No. 2; Solvent Violet 13; Alizurol Purple SS
 81-48-1


60730
Ext D&C Violet No. 2; Acid Violet 43
4430-18-6


61565
D&C Green No. 6; Solvent Green 3; Quinizarin Green SS
 128-80-3


61570
D&C Green No. 5; Acid Green 25
4403-90-1


61585
Acid Blue 80
4474-24-2


62045
Acid Blue 65
4368-56-3


69800
E 130; Vat Blue 4
 81-77-6


69825
D&C Blue No. 9; Vat Blue 6; Indanthrene Blue; Carbanthrene
 130-20-1



Blue



71105
Vat Orange 7; Pigment Orange 43
4424-06-0


73000
Vat Blue 1; Indigo
 482-89-3


73015
FD&C Blue No. 2; E 132; Food Blue 1; Indigotine; Indigo
 860-22-0



Carmine



73360
D&C Red No. 30; Vat Red 1; Helindone Pink CN
2379-79-0


73385
Vat Violet 2
5462-29-3


73900
Pigment Violet 19
1047-16-1


73915
Pigment Red 122
16043-40-6 


74100
Pigment Blue 16
 547-93-6


74160
Pigment Blue 15
 147-14-8


74180
Direct Blue 86
1330-38-7


74260
Pigment Green 7
1328-53-6


75100
Natural Yellow 6
27876-94-4 


75120
Annatto extract; E 160b; Natural Orange 4
1393-63-1


75125
E 160d; Lycopene
 502-65-8


75130
Beta Carotene (Natural); E 160a; Natural Browns 5; Natural
7235-40-7



Yellow 26



75135
E 161d; Natural Yellow 27; Rubixanthin
3763-55-1


75170
Guanine; Natural White 1
 73-40-5


75300
E 100; Natural Yellow 3; Turmeric Yellow; Curcumin; Indian
 458-37-7



Saffron



75470
Cochineal extract; E120; Natural Red 4; Cochineal; Carmine;
1343-78-8



Carminic Acid . . . 
1390-65-4




1260-17-9


75480
Henna
 83-72-7


75810
E 140 & E 141; Chlorophyll; Copper complexes of chlorophyll
11006-34-1 



and chlorophyllins; Potassium sodium copper; Chlorophyllin;




Natural Green 3



77000
Aluminum Powder; E 173; Pigment Metal 1; Aluminum
4729-90-5


77002
Alumina; Pigment White 24
1332-73-6


77004
Pigment White 19; Bentonite
1302-78-9


77007
Ultramarine Blue; Pigment Blue 29
1317-97-1



Ultramarine Red
1345-00-2



Ultramarine Violet; Pigment Violet 15
12769-96-9 


77013
Ultramarine Green; Pigment Green 24



77015
Pigment Red 101; Pigment Red 102



77019
Mica; Pigment White 20
12001-26-2 



Talc; Pigment white 26
14807-96-9 


77120
Pigment White 21; Pigment White 22
7727-43-7


77163
Bismuth oxychloride; Pigment White 14
7787-59-9


77220
Calcium carbonate; E 170; Pigment White 18
 471-34-1


77231
Pigment White 25; Calcium Sulfate
7778-18-9


77288
Chromium Oxide Greens; Pigment Green 17
1308-38-4


77289
Chromium hydroxide Green; Pigment Green 18; Guignet Green;
12001-99-9 



Veridian



77346
Cobalt Blue; Pigment Blue 28
1345-16-0


77400
Bronze powder; Copper powder; Pigment Metal 2
7440-50-8


77400




77480
E 175; Gold; Pigment Metal 3
7740-57-5


77489
E 172; Ferrous oxide
1345-25-1


77491
Ferric oxide; E 172; Pigments Red 101 & 102; Pigments Brown
1309-37-1



6 & 7



77492
Hydrated Ferric oxide; E 172; Pigments Yellow 42 & 43;
20344-49-4 



Pigments Brown 6 & 7



77499
Ferrous Ferric oxide; E 172; Pigment Black 11; Pigments Brown
1317-61-9



6 & 7



77510
Ferric ferrocyanide; Pigment Blue 27; Prussian Blue
14038-43-8 


77520




77713
Magnesium Carbonate; Pigment White 18
 546-93-0


77742
Manganese Violet; Pigment Violet 16
10101-66-3 


77745
Manganous Phosphate
10124-54-6 


77820
Silver; E 174
7440-22-4


77891
Titanium Dioxide; E 171; Pigment White 6
13463-67-7 


77947
Zinc Oxide; Pigment White 4
1317-13-2



Acid red 195
12220-24-5 



Aluminum distearate
 300-92-5



Anthocyanins; E 163
11029-12-2 



Beetroot red; E 162
89957-89-1 




7659-95-2



Bismuth citrate




Bromocresol green
 76-60-8



Bromothymol blue
 76-59-5



Calcium stearate
1592-23-0



Capsanthin, Capsorubin; E 160c; Paprika extract
 465-42-9



E 150; Natural Brown 10; Caramel
8028-89-5



Ferric ammonium ferrocyanide
25869-00-5 



E 101; Lactoflavin; Riboflavin
 83-88-5



Lead acetate
 301-04-2



Magnesium Stearate
 557-04-0



Zinc Stearate
 557-05-1










Table 1b: Structure of the Lakes:













structure of corresponding


Lakes (FDA name)
CI No
name
dye





D&C Red #6 Ba Lake
15850
Pigment Red 57 Sodium Salt






 


D&C Red #7
15850:1
Pigment Red 57.1 Calcium Salt






 


D&C Red #21 Al Lake
45380:2
Solvent Red 43






 


D&C Red #22 Al Lake
45380
Acid Red 87






 


D&C Red #27 Al Lake
45410:1
Solvent Red 48






 


D&C Red #28 Al Lake
45410
Acid Red 92






 


D&C Red #30 Al & Talk Lake
73360
Vat Red 1 = Pigment Red 181






 


D&C Red #33 Al & Zr Lake
17200
Acid Red 33






 


D&C Yellow #10 Al Lake
47005
Food Yellow 13






 











 


FD&C Yellow #5 Al Lake
19140
Acid Yellow 23 Na Salt






 


FD&C Yellow #6 Al Lake
15985
Food Yellow 3 Na Salt






 


FD&C Blue #1 Al Lake
42090
Acid blue 9










Table 1c: Calisha colour pigments (Ciba):








Name
INCI Name










Treated Pearls








Calisha Romance Silver Pearl OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Romance Glamour Violet OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Romance Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Romance Glamour Green OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Romance Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide



and Cetyl Dimethicone


Calisha Romance Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Romance Orange Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Romance Red Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Contemporary Starlight Pearl OD 
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Contemporary Glamour Blue Pearl 
Mica and Titanium Dioxide and Cetyl


OD
Dimethicone


Calisha Contemporary Glamour Gold Pearl 
Mica and Titanium Dioxide and Cetyl


OD
Dimethicone


Calisha Contemporary Glamour Violet OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Contemporary Claret Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide



and Cetyl Dimethicone


Calisha Contemporary Sienna Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide



and Cetyl Dimethicone


Calisha Contemporary Black Pearl OD
Mica and Titanium Dioxide and Black Iron



Oxide and Cetyl Dimethicone


Calisha Contemporary Sable Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide



Carmine and Cetyl Dimethicone


Calisha Contemporary Green Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide



and Ferric Ferrocyanide and Cetyl Dimethicone


Calisha Contemporary Silver Pearl OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Contemporary Glamour Green OD
Mica and Titanium Dioxide and Tin Dioxide and



Cetyl Dimethicone


Calisha Contemporary Gold Pearl OD
Mica and Titanium Dioxide and Red Iron Oxide



and Cetyl Dimethicone


Calisha Contemporary Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Contemporary Rose Red Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Art Deco Silver Pearl OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Art Deco Glamour Violet OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Art Deco Glamour Blue Pearl OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Art Deco Glamour Green OD
Mica and Titanium Dioxide and Cetyl



Dimethicone


Calisha Art Deco Gold Pearl OD
Mica and Red Iron Oxide and Titanium Dioxide



and Cetyl Dimethicone


Calisha Art Deco Bronze Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Art Deco Orange Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone


Calisha Art Deco Red Pearl OD
Mica and Red Iron Oxide and Cetyl



Dimethicone







Untreated Pearls








Calisha Romance Silver Pearl CL
Mica and Titanium Dioxide


Calisha Romance Glamour Violet CL
Mica and Titanium Dioxide


Calisha Romance Glamour Blue Pearl CL
Mica and Titanium Dioxide


Calisha Romance Glamour Green CL
Mica and Titanium Dioxide


Calisha Romance Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide


Calisha Romance Bronze Pearl CL
Mica and Red Iron Oxide


Calisha Romance Orange Pearl CL
Mica and Red Iron Oxide


Calisha Romance Red Pearl CL
Mica and Red Iron Oxide


Calisha Contemporary Starlight Pearl CL
Mica and Titanium Dioxide


Calisha Contemporary Glamour Blue Pearl
Mica and Titanium Dioxide


CL



Calisha Contemporary Glamour Gold Pearl
Mica and Titanium Dioxide


CL



Calisha Contemporary Glamour Violet CL
Mica and Titanium Dioxide


Calisha Contemporary Claret Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide


Calisha Contemporary Sienna Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide


Calisha Contemporary Black Pearl CL
Mica and Titanium Dioxide and Black Iron



Oxide


Calisha Contemporary Sable Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide



and Carmine


Calisha Contemporary Green Pearl CL
Mica and Titanium Dioxide Red Iron Oxide



Ferric Ferrocyanide


Calisha Contemporary Silver Pearl CL
Mica and Titanium Dioxide


Calisha Contemporary Glamour Green CL
Mica and Titanium Dioxide and Tin Dioxide


Calisha Contemporary Gold Pearl CL
Mica and Titanium Dioxide and Red Iron Oxide


Calisha Contemporary Bronze Pearl CL
Mica and Red Iron Oxide


Calisha Contemporary Rose Red Pearl CL
Mica and Red Iron Oxide


Calisha Art Deco Silver Pearl CL
Mica and Titanium Dioxide


Calisha Art Deco Glamour Violet CL
Mica and Titanium Dioxide


Calisha Art Deco Glamour Blue Pearl CL
Mica and Titanium Dioxide


Calisha Art Deco Glamour Green Pearl CL
Mica and Titanium Dioxide


Calisha Art Deco Gold Pearl CL
Mica and Red Iron Oxide and Titanium Dioxide


Calisha Art Deco Bronze Pearl CL
Mica and Red Iron Oxide


Calisha Art Deco Orange Pearl CL
Mica and Red Iron Oxide


Calisha Art Deco Red Pearl CL
Mica and Red Iron Oxide







Inorganic Pigments








Calisha Contemporary Salmon Red Oxide
Red Iron Oxide


Calisha Contemporary Medium Red Oxide
Red Iron Oxide


Calisha Contemporary Deep Red Oxide
Red Iron Oxide


Calisha Contemporary Black Oxide
Black Iron Oxide


Calisha Contemporary Jet Black Oxide
Black Iron Oxide


Calisha Contemporary Sun Yellow Oxide
Yellow Iron Oxide


Calisha Contemporary Yellow Oxide
Yellow Iron Oxide


Calisha Contemporary Ultramarine Blue
Ultramarine Blue


Calisha Contemporary Ultramarine Violet
Ultramarine Violet


Calisha Art Deco Hydroxide Chrome Green
Chromium Hydroxide Green


Calisha Art Deco Chrome Oxide Green
Chromium Oxide Greens







Lakes








Calisha Art Deco Blue 1 Lake
FD&C Blue No. 1 Al Lake


Calisha Art Deco Red 21 Lake
D&C Red No. 21 Al Lake


Calisha Art Deco Red 27 Lake
D&C Red No. 27 Al Lake


Calisha Art Deco Red 30 AL. Lake
D&C Red No. 30 Al Lake


Calisha Art Deco Red 30 Talc Lake
D&C Red No. 30 Talc Lake


Calisha Art Deco Red 33 Lake
D&C red No. 33 Al Lake


Calisha Art Deco Red 40 AL. Lake
FD&C Red No. 40 Al lake


Calisha Art Deco Red 6 Lake HD
D&C Red No. 6 Ba Lake


Calisha Art Deco Red 7 Lake HD
D&C Red No. 7 Ca lake


Calisha Art Deco Yellow 5 Lake HD
FD&C Yellow No. 5 Al Lake


Calisha Art Deco Yellow 6 AL. Lake
FD&C Yellow No. 6 Al lake









The interference pigments as used in the present invention are platelet particulates. The platelet particulates preferably have a thickness of no more than about 5 micrometers, more preferably no more than about 2 micrometers, still more preferably no more than about 1 micrometer. The platelet particulates preferably have a thickness of at least about 0.02 micrometers, more preferably at least about 0.05 micrometers, even more preferably at least about 0.1 micrometers, and still more preferably at least about 0.2 micrometers.
Furthermore, the hair dye composition according to the present invention may also be used in combination with oxidation dye systems.
Oxidation dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer and coupler compounds.
Suitable oxidation dyes are described for example in

    
    
        DE 19 959 479, especially in col 2, I. 6 to col 3, I. 11;
        “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264-267 (oxidation dyes).
    
    


Preferred developer compounds are for example primary aromatic amines, which are substituted in the para- or ortho-position with a substituted or unsubstituted hydroxy- or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives or 2,4,5,6-tetraminopyrimidine derivatives.
Furthermore, developer compounds in their physiological compatible acid addition salt form, such as hydrochloride or sulfate can be used. Developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a base, such as alkali metal-phenolates.
Preferred developer compounds are disclosed in DE 19959479, p. 2, I. 8-29.
Preferred coupler compounds are m-phenylenediamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and most preferably the coupler compounds disclosed in DE 19959479, p. 1, I. 33 to p. 3, I. 11.
Furthermore, autooxidizable compounds may be used in combination with the hair dye composition according to the present invention.
Autooxidizable compounds are aromatic compounds with more than two substituents in the aromatic ring, which have a very low redox potential and will therefore be oxidized when exposed to the air. The dyeings obtained with these compounds are very stable and resistant to shampoo.
Autooxidizable compounds are for example benzene, indole, or indole, especially 5,6-dihydroxyindol or 5,6-dihydroxyindol.
The hair dye composition according to the present invention may also be used in combination with naturally occurring dyes, such as henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre and alkanet root.
Furthermore, the hair dye composition according to the present invention may also be used in combination with capped diazotized compounds.
Suitable diazotized compounds are for example the compounds of formulae (1)-(4) in WO 2004/019897 (bridging gages 1 and 2) and the corresponding water-soluble coupling components (I)-(IV) as disclosed in the same reference.
The present invention also relates to formulations, which are used for the dyeing of organic materials, preferably keratin-containing fibers, and most preferably human hair, comprising the hair dye composition according to the present invention.
The appropriate dyeing medium (or carrier) generally consists of water or of a mixture of water and of at least one organic solvent for solubilizing the compounds which would not be sufficiently soluble in water. As organic solvent, there may be mentioned for example the C1-C4 lower alkanols such as ethanol and isopropanol, the aromatic alcohols such as benzyl alcohol as well as similar products and mixtures thereof.
The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and still more preferably between 5 and 30% by weight approximately.
Preferably the hair dye composition according to the present invention is incorporated into the composition for treating organic material, preferably for dyeing in amounts of 0.001-5% b.w. (hereinafter indicated merely by “%”), particularly 0.005-4%, more particularly 0.2-3%, based on the total weight of the composition.
The pH of the dyeing composition in accordance with the invention is generally between 2 and 11 approximately, and preferably between 5 and 10 approximately. It may be adjusted to the desired value by means of acidifying or alkalinizing agents normally used in dyeing keratinous fibres.
The formulations may be applied on the keratin-containing fiber, preferably the human hair in different technical forms.
Technical forms of formulations are for example a solution, especially a thickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo, powder, gel, or emulsion.
Customary the dyeing compositions are applied to the keratin-containing fiber in an amount of 50 to 100 g.
Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or ‘kits’ or any of the multi-compartment packaging systems with compartments as described for example in U.S. Pat. No. 6,190,421, col 2, I. 16 to 31.
The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10.
One preferred embodiment of the present invention relates to the formulation of dyes, wherein the hair dye composition according to the present invention is in powder form.
Powder formulations are preferably used if stability and/or solubility problems as for example described in DE 197 13 698, p. 2, I. 26 to 54 and p. 3, I. 51 to p. 4, I. 25, and p. 4, I. 41 to p. 5 I. 59.
Suitable cosmetic hair-care formulations are hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations or leave-on products such as sprays, creams, gels, lotions, mousses and oils, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.
For use on human hair, the dyeing compositions of the present invention can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example W/O, O/W, O/W/O, W/O/W or PIT emulsions and all kinds of microemulsions, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers. Such forms of use are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in U.S. Pat. No. 3,369,970, especially col 1, I. 70 to col 3, I. 55. The dyeing compositions according to the invention are also excellently suitable for the dyeing method described in DE-A-3 829 870 using a dyeing comb or a dyeing brush.
The constituents of the aqueous carrier are present in the dyeing compositions of the present invention in the customary amounts, for example emulsifiers may be present in the dyeing compositions in concentrations of from 0.5 to 30% b.w. and thickeners in concentrations of from 0.1 to 25% b.w. of the total dyeing composition.
Further carriers for dying compositions are for example described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially on p. 243, I. 1 to p. 244, I. 12.
The hair dye composition according to the present invention may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.
When the dyes and adjuvants are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the compounds.
The dyeing compositions according to the invention may comprise any active ingredients, additives or adjuvants known for such preparations, like surfactants, solvents, bases, acids, perfumes, polymeric adjuvants, thickeners and light stabilizers.
The following adjuvants are preferably used in the hair dyeing compositions of the present invention: non-ionic polymers, cationic polymers, acrylamide/dimethyldiallylammonium chloride copolymers, quaternised polyvinyl alcohol, zwitterionic and amphoteric polymers, anionic polymers, thickeners, structuring agents, hair-conditioning compounds, protein hydrolysates, perfume oils, dimethyl isosorbitol and cyclodextrins, solubilizers, anti-dandruff active ingredients, substances for adjusting the pH value; panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins; cholesterol; light stabilizers and UV absorbers, consistency regulators, fats and waxes, fatty alkanol-amides, polyethylene glycols and polypropylene glycols, complexing agents, swelling and penetration substances, opacifiers, such as latex; pearlising agents, propellants, antioxidants; sugar-containing polymers, quaternary ammonium salts, or bacteria inhibiting agents.
The dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are zwitterionic or ampholytic, or more preferably anionic, non-ionic and/or cationic surfactants.
Suitable anionic surfactants are characterized by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C8-C22-carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Ampholytic surfactants are surface-active compounds that, in addition to a C8-C18-alkyl or -acyl group and contain at least one free amino group and at least one —COOH or —SO3H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-C18acylsarcosine.
Suitable non-ionic surfactants are described in WO 00/10519, especially p. 45, I. 11 to p. 50, I. 12. Non-ionic surfactants contain as hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups.
Examples of cationic surfactants that can be used in the dyeing compositions according to the invention are especially quaternary ammonium compounds.
Alkylamidoamines, especially fatty acid amidoamines, such as the stearylamidopropyldimethylamine obtainable under the name Tego Amid® 18 are also preferred as surfactants in the present dyeing compositions. They are distinguished not only by a good conditioning action but also especially by their good biodegradability.
A further preferred embodiment of the present invention relates to a method of treating keratin-containing fibers with the hair dye composition according to the present invention.
The method comprises treating the hair in the presence of a reduction agent.
Usually, the dyeing compositions are applied to the keratin-containing fiber in an amount of from 50 to 100 g.
The oxidizing agents described above can also be used as lightening composition for lightening of the hair before the intrinsic dyeing process.
Therefore, the present invention also relates to a method for simultaneous dyeing and waving of keratinous fibers, comprising the steps of

    
    
        (a) treating the hair with a lightening composition,
        (b) optionally treating the hair with a reductive wave agent; and
        (c) treating the hair with a hair dyeing composition according to the present invention.
    
    


Moreover, this method is also suitable for the smoothing of hair.
The hair dye composition according to the present invention is suitable for all-over dyeing of the hair, that is to say when dyeing the hair on a first occasion, and also for re-dyeing subsequently, or dyeing of locks or parts of the hair, for example for the dyeing of eyebrows, eyelashes, body hair and or beards.
The hair dye composition according to the present invention is applied on the hair for example by massage with the hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle.
In the processes for dyeing according to the invention, whether or not dyeing is to be carried out in the presence of a further dye will depend upon the color shade to be obtained.
Further preferred is a process for dyeing keratin-containing fibers which comprises treating the keratin-containing fiber with the hair dye composition according to the present invention, a base and an oxidizing agent.
The oxidation dyeing process usually involves lightening, that is to say that it involves applying to the keratin-containing fibers, at basic pH, a mixture of bases and aqueous hydrogen peroxide solution, leaving the applied mixture to stand on the hair and then rinsing the hair. It allows, particularly in the case of hair dyeing, the melanin to be lightened and the hair to be dyed.
In general, the oxidizing agent containing composition is left on the fiber for 0 to 15 minutes, in particular for 0 to 5 minutes at 15 to 45° C., usually in amounts of 30 to 200 g.
Oxidizing agents are for example persulfate or diluted hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides, such as urea peroxides, melamine peroxides, or alkalimetalbromate fixations are also applicable if a shading powder on the basis of semi-permanent, direct hair dyes is used.
Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration from about 2 to 30%, more preferably about 3 to 20% by, and most preferably from 6 to 12% b.w. the corresponding composition.
The oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount from 0.01% to 6%, especially from 0.01% to 1%, based on the total dyeing composition.
In general, the dyeing with an oxidative agent is carried out in the presence of a base, for example ammonia, alkali metal carbonates, earth metal (potassium or lithium) carbonates, alkanol amines, such as mono-, di- or triethanolamine, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula




wherein

R is a propylene residue, which may be substituted with OH or C1-C4alkyl,

R3, R4, R5 and R6 are independently or dependently from each other hydrogen, C1-C4alkyl or hydroxy-(C1-C4)alkyl.

The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 2 to 5.
One preferred method of applying formulations comprising the hair dye composition according to the present invention on the keratin-containing fiber, preferably the hair is by using a multi-compartment dyeing device or “kit” or any other multi-compartment packaging system, as described for example in WO 97/20545 on p. 4, I. 19 to I. 27.
The following Examples serve to illustrate the processes for dyeing without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being colored.


APPLICATION EXAMPLES
Combination of Basic Blue 124 with Basic Red 51, Basic Yellow 87 and Basic Orange 31 and a Quaternary Ammonium Salt for Dyeing Hair
To determine the wash fastness two sets of hair tresses are dyed under the same conditions. One set of the dyed tresses is washed with a commercial shampoo (GOLDWELL definition Color & Highlights, color-conditioner shampoo) using approx. 0.5 g shampoo for each tress under tap water (water temperature: 37° C.+/−1° C.; flow rate 5-6 l/min). Finally the tresses are rinsed under tap water, pressed out with a paper towel, combed and dried with a hair dryer or at room temperature. This procedure was repeated 10 times.
Then the color loss of the set of washed tresses relative to the set of unwashed tresses was evaluated using the Grey Scale according to: Industrial Organic Pigments by Herbst&Hunger, 2nd ed., p. 61, Nr 10: DIN 54 001-8-1982, “Herstellung and Bewertung der Änderung der Farbe”, ISO 105-A02-1993.
Example 1
A conditioner containing














INGREDIENTS
w/w %



















Cetyl Alcohol
3.00%



Ceterareth-25
0.50%



Distearyldimonium Chloride
1.00%



Quaternium-80
0.50%



Citric Acid
Ad pH = 5



Basic Blue 124
0.025



Basic Yellow 87
0.060



Basic Orange 31
0.010



Basic Red 51
0.015



Perfumes; Preservatives
q.s.



Water
Ad 100%










is applied to a tress of shampooed middle blond and gray hair. After 15 min the tress is rinsed and dried.

The tress has been dyed brown with good gray coverage.
Example 2
A conditioner containing














INGREDIENTS
w/w %



















Cetyl Alcohol
3.00%



Ceterareth-20
0.50%



Hydroxypropyl Guar, Hydroxypropyl
1.00%



trimonium chloride



Quaternium-80
0.50%



Citric Acid
Ad pH = 5



Octocrylene
0.1



Butyl Methoxydibenzoylmethane
0.1



Perfumes; Preservatives
q.s.



Basic Blue 124
0.1



Basic Orange 31
0.1



Water
Ad 100%










is applied to a tress of shampooed blond hair. After 5 min the tress is rinsed and dried. The tress has been dyed brown.

Example 3
A conditioner containing 0.1%














INGREDIENTS
w/w %



















Cetearyl Alcohol, Sodium Cetearyl Sulfate
3.00%



Ceterareth-25
0.50%



Distearoylethyl Diammonium Chloride
1.00%



Quaternium-80
0.50%



Citric Acid
Ad pH = 5



Camphor Benzalkonium Methosulfate
0.1



Ethyl Salicylate
0.1



Basic Blue 124
0.5



Basic Red 51
0.5



Perfumes; Preservatives
q.s.



Water
Ad 100%










is applied to a tress of shampooed blond hair. After 5 min the tress is rinsed and dried. The tress has been dyed violet.

Example 4
A conditioner containing














INGREDIENTS
w/w %









Cetyl Alcohol
3.00%



Ceterareth-25
0.50%



Behentrimmonium Chloride
1.00%



Polyquaternium-10
0.50%



Citric Acid
Ad pH = 5



Dimethicone
0.9



Phenyltrimethicone, Silicone Quaternium-15,
2.5



Laureth-4 (Polysil 1849)



Polysilicone-15
0.8



Basic Blue 124
0.1



Basic Blue 151
0.1



Basic Yellow 87
0.4



Perfumes; Preservatives
q.s.



Water
Ad 100%










is applied to a tress of shampooed bleached hair. After 5 min the tress is rinsed and dried. The tress has been dyed green.

Example 5
A conditioner containing














INGREDIENTS
w/w %









Cetyl Alcohol
3.00%



Ceterareth-25
0.50%



Behentrimmonium Chloride
1.00%



Polyquaternium-10
0.50%



Citric Acid
Ad pH = 5



Dimethicone
0.9



Phenyltrimethicone, Silicone Quaternium-15,
2.5



Laureth-4 (Polysil 1849)



Polysilicone-15
0.8



Basic Blue 124
0.1



Basic Blue 151
0.1



Basic Yellow 87
0.4



Perfumes; Preservatives
q.s.



Water
Ad 100%










is applied to a tress of shampooed bleached hair. After 5 min the tress is rinsed and dried. The tress has been dyed green.

Example 6
A dye emulsion with pH=6.4, containing
0.05% of the dye Basic Blue 124
0.15% Basic Blue 99
0.07% Basic Brown 17
0.04% Basic Yellow 57
0.15% Basic Brown 16
0.01% Basic Red 76
0.01% Basic Red 51
0.01% HC Red BN
0.01% HC Red 3
0.01% 3-Nitro-p-Hydroxyethylaminophenol
0.05% HC Blue 2
3.5% Cetearyl alcohol
1.5% Henna
10.5% Walnut
1.0% Ceteareth 30
0.5% Glycol Distearate
3.0% Stearamide DEA
1.0% Sodium Oleoamphohydroxypropyl Sulfonate
0.5% Polyquarternium-10
0.1% Tinovis CD (Dimethylacrylamide/Ethyltrimonium Chloride Methacrylate Copolymer, Propylene Glycol Dicaprylate/Dicaprate, PPG-1 Trideceth-6, C10-11 Isoparaffin)
0.5% Aminopropyl Dimethicone
water ad 100%.
is applied for 30 minutes, at room temperature to bleached human hair, and rinsed. The result is a reddish brown dyeing with good fastnesses.
Example 7
A dye emulsion with pH=6.4, containing
0.05% of the dye Basic Blue 124
0.15% Basic Blue 99
0.07% Basic Brown 17
0.04% Basic Yellow 57
0.15% Basic Brown 16
0.01% Basic Red 76
0.01% Basic Red 51
0.01% HC Red BN
0.01% HC Red 3
0.01% 3-Nitro-p-Hydroxyethylaminophenol
0.05% HC Blue 2
0.01% Basic Blue 26
0.01% Basic Blue 75
3.5% Cetearyl alcohol
1.5% Henna
10.5% Walnut
1.0% Ceteareth 30
0.5% Glycol Distearate
3.0% Stearamide DEA
1.0% Sodium Oleoamphohydroxypropyl Sulfonate
0.5% Polyquarternium-10
0.1% Tinovis CD (Dimethylacrylamide/Ethyltrimonium Chloride Methacrylate Copolymer, Propylene Glycol Dicaprylate/Dicaprate, PPG-1 Trideceth-6, C10-11 Isoparaffin)
0.5% Aminopropyl Dimethicone
water ad 100%.
is applied for 30 minutes, at room temperature to bleached human hair, and rinsed. The result is a reddish brown dyeing with good fastnesses.

## Claims

1. Hair dyeing composition comprising
(a) a dye of formula




(b) at least one dye selected from the compounds of formulae





wherein

D is the radical of a diazo component of the formula




K is the radical of a coupling component selected from aniline derivatives; phenol derivatives; and a radical of a heterocyclic coupling component;
X is —O—; —S—; or —N(R8)—;
Y is —CH═; —CR15═; or —N═;
R1, R2, R3 and R4 independently from each other are hydrogen; or C1-C4alkyl;
R5 and R6 independently from each other are hydrogen; C1-C4alkyl; or C1-C4alkoxy;
R7 and R9 independently from each other are unsubstituted or OH—, C1-C4alkoxy-, halogen-, amino-, C1-C4-mono or -dialkylamino-substituted C1-C4alkyl;
R8 is hydrogen; or C1-C4alkyl;
R10 is hydrogen; C1-C4alkyl; or CN;
R11 is unsubstituted or OH— or CN-substituted C1-C4alkyl;
R12 is hydrogen; or C1-C4alkyl;
R13 and R14 independently from each other are hydrogen; C1-C4alkyl; or C1-C4alkoxy; or
R13 and R14 together with the nitrogen and carbon atoms joining them together form a 5- or 6-membered ring;
R15 is hydrogen; or C1-C4alkyl; and
An1− is a colorless anion; and
(c) a quaternary ammonium salt selected from
(c1) quaternary ammonium salts of the formula





wherein

R16 and R19, independently from each other are a saturated or unsaturated, linear or branched, aliphatic C1-C30alkyl; or an alkoxy, alkoxycarbonylalkyl, polyoxyalkylene, alkylamido, alkylamidoalkyl, hydroxyalkyl, aromatic, aryl or alkylaryl radical comprising from about 12 to about 30 carbon atoms, with at least one radical among R16, R17, R18 and R19 denoting a radical comprising from 8 to 30 carbon atoms;
An2− is an anion selected from the group comprising halides, phosphates, acetates, lactates and alkyl sulphates;
(c2) imidazolium salts of the formula





wherein

R20 is C13-C31alkyl or C13-C31alkenyl, derived from tallow fatty acids;
(c3) quaternary diammonium salts of the formula





in which

R21 is C6-C31alkyl;
R22, R23, R24, R25 and R26 are selected from hydrogen; or C1-C4alkyl; and
An3− is an anion selected from halides, acetates, phosphates and sulphates.

2. Composition according to claim 1, wherein in formula (1) of component (a) R1, R2, R3 and R4 independently from each other are hydrogen; or C1-C2alkyl.

3. Composition according to claim 1, wherein component (a) corresponds to formula

4. Composition according to claim 1, wherein
R8 is hydrogen; or C1-C4alkyl.

5. Composition according to claim 1, wherein in formula (2a)
R7 and R9 independently from each other are C1-C4alkyl.

6. Composition according to claim 1, wherein in formula (2a)
X is —NH; and
Y is —CH═.

7. Composition according to claim 1, wherein in formula (2)
K is the radical of formula





wherein

R27 is hydrogen; hydroxy; C1-C4alkyl; C1-C4alkoxy; amino; mono-C1-C4alkylamino; or di-C1-C4alkylamino.

8. Composition according to claim 1 comprising
(a) a dye of formula (1),
(b) at least one dye selected from the compounds of formulae





and

(c) a quaternary ammonium salt as defined as in claim 1.

9. Composition according to claim 1 comprising as additional component a colorant selected from
(d) a direct dye;
(e) an oxidative dye;
(f) a disulfide dye;
(g) a pigment;
or mixtures thereof.

10. A method for dyeing keratinous fibers, comprising applying the dyeing composition according to claim 1 to said keratinous fibers.

11. A method for dyeing keratinous fibers, comprising the steps of
(a) treating the hair with a lightening composition,
(b) optionally treating the hair with a reductive wave agent; and
(c) treating the hair with a hair dyeing composition according to claim 1.