US 201200 12128A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0012128 A1 Fröhling (43) Pub. Date: Jan. 19, 2012 (54) HAIR DYEING COMPOSITION C-Calkoxy-, halogen-, amino-, C-C-mono or -dialky lamino-Substituted C-C alkyl; Rs is hydrogen; or (75) Inventor: Beate Fröhling, Neustadt (DE) C-C alkyl; R is hydrogen; C-C alkyl, or CN; R is unsubstituted or OH- or CN-substituted C-C alkyl; R is hydrogen; or C-C alkyl; R and R independently from (73) Assignee: BASFSE, LUDWIGSHAFEN (DE) each other are hydrogen; C-C alkyl; or C-C alkoxy, or Rs and R together with the nitrogen and carbon atoms joining (21) Appl. No.: 13/148,690 them togetherform a 5- or 6-membered ring; Rs is hydrogen; or C-C alkyl, and An is a colorless anion; and (c) a qua (22) PCT Filed: Feb. 19, 2010 ternary ammonium salt. (86). PCT No.: PCT/EP2010/052099 (1) R6 N Rs S371 (c)(1), 21 (2), (4) Date: Sep. 30, 2011 R DC ICC R4 An: (30) Foreign Application Priority Data S-S-S-N- R2 R3 Feb. 25, 2009 (EP) ................................... 09 1535807 (2) D-N -- Publication Classification V An; and (51) Int. Cl. N-K A6 IK 8/49 (2006.01) (3) A61O 5/10 (2006.01) / f (52) U.S. Cl. .................................. 132/208; 8/426; 8/.407 R-/ \ \ Ji? o N-N An: (57) ABSTRACT VR 14 Disclosed is a hair dyeing composition comprising (a) a dye of formula (1); (b) at least one dye selected from the com () pounds of formulae (2); wherein D is the radical of a diazo R13 component of the formula (2a); K is the radical of a coupling (2a) component selected from aniline derivatives; phenol deriva R7: tives; and a radical of a heterocyclic coupling component; X is O—; —S ; or N(Rs)—;Y is CH=; —CRs—; or N=: R. R. R. and R independently from each other are hydro gen; or C-C alkyl; Rs and Reindependently from each other are hydrogen; C-C alkyl; or C-Calkoxy; R, and R inde pendently from each other are unsubstituted or OH- . US 2012/0012128 A1 Jan. 19, 2012 HAR DYEING COMPOSITION 0007 wherein 0008 D is the radical of a diazo component of the for mula 0001. The present invention relates to a composition for dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in an appropriate dyeing (2a) 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 Nt 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. 0002. It is known, for example, from WO95/01772, WO 0009 K is the radical of a coupling component selected 95/15144, EP 714954 and EP318294 that cationic dyes can from aniline derivatives; phenol derivatives; and a radi be used to dye organic material, for example keratin, silk, cal of a heterocyclic coupling component; cellulose or cellulose derivatives, and also synthetic fibres, for 0010 X is —O ; – S ; or - N(Rs)—: example polyamides. Cationic dyes exhibit very brilliant shades. A disadvantage is their unsatisfactory fastness to 0011 Y is -CH=; CR =; or - N=: hydrolysis and to light, their frequently inadequate stability 0012 R. R. R. and R independently from each other under reducing or oxidizing conditions, and their frequently are hydrogen; or C-C alkyl; unsatisfactory storage stability (see: John F. Corbett: “The 0013 Rs and R independently from each other are Chemistry of Hair-Care Products', JSCD August 1976, page hydrogen; C-C alkyl, or C-Calkoxy; 290). 0014) R, and R independently from each other are 0003. The actual technical problem of the present inven unsubstituted or OH- , C-C alkoxy-, halogen tion was to provide brilliant dyes that are distinguished by amino-, C-C-mono or -dialkylamino-substituted deep dying having good fastness properties with respect to C-C alkyl, washing, light, shampooing and rubbing, and that preferably 0.015 Rs is hydrogen; or C-C alkyl: exhibit satisfactory stability under reducing or oxidizing dye ing conditions, for the dyeing of organic material. 0016 Rio is hydrogen; C-C alkyl: or CN: 0004. Accordingly, the present invention relates to a hair 0017 R is unsubstituted or OH- or CN-substituted dye composition, comprising C-C alkyl: 0005 (a) a dye of formula 0.018 R2 is hydrogen; or C-C alkyl: 0.019 R and R independently from each other are hydrogen; C-C alkyl, or C-Calkoxy; or (1) R6 N Rs 0020 RandR together with the nitrogen and carbon 21 atoms joining them together form a 5- or 6-membered r1ng, R R4 0021 Rs is hydrogen; or C-C alkyl; and s -N-s- 0022. An is a colorless anion; and R2 R 3 0023 (c) a quaternary ammonium salt selected from 0024 (c) quaternary ammonium salts of the formula 0006 (b) at least one dye selected from the compounds of formulae (4) (2) D-N -- V An; and N-K (3) R10 0025 wherein 0026 R and Ro, independently from each other are a R-N+/h \ \ Ji? Saturated or unsaturated, linear or branched, aliphatic o N-N C-Coalkyl, or an alkoxy, alkoxycarbonylalkyl, poly An: oxyalkylene, alkylamido, alkylamidoalkyl, hydroxy V-R 14 alkyl, aromatic, aryl or alkylaryl radical comprising from about 12 to about 30 carbonatoms, with at least one radical among R. R.17, R1s and Rio denoting a radical (). comprising from 8 to 30 carbon atoms; R13 0027. An is an anion selected from the group com prising halides, phosphates, acetates, lactates and alkyl Sulphates; US 2012/0012128 A1 Jan. 19, 2012 0028 (c) imidazolium salts of the formula 0041 More preferred is a hair dye composition, wherein component (a) corresponds to formula (7) N O-CH n C. (5) H -- N NN1 0042. More preferably, in formula (2a) 0.043 R, and R independently from each other are C-C alkyl, and even more preferred are hair dye com 0029 wherein positions, wherein 0044 X is NH; and 0030 Ro is C-C alkyl or C-C alkenyl, derived 0.045 Y is CH-. from tallow fatty acids; 0046 Even more preferred are hair dye compositions, 0031 (c) quaternary diammonium salts of the formula wherein in formula (2) 0047 K is the radical of formula (2b) (6) | s s 2 R--cis--Rs 2 An3; R23 R25 0048 wherein 0049 R, is hydrogen; hydroxy; C-C alkyl, C-Calkoxy; amino; mono-C-C-alkylamino; or di-C- Calkylamino. 0050 Most preferred are hair dye compositions compris 0032 in which ing 0033 R is C-C alkyl: 0051 (a) a dye of formula (1), 0.052 (b) at least one dye selected from the compounds 0034 R. R. R. Ras and R2 are selected from of formulae hydrogen; or C-C alkyl; and 0035) An is an anion selected from halides, acetates, phosphates and Sulphates. 0036 C-Coalkyl is for example, methyl, ethyl, propyl, \ \ (8) isopropyl. n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, /N { NV N 3-penty1, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, N Q. n-hexyl, n-octyl, 1,1,3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tredecyl, tetradecyl, pentade y cyl, haxadecyl or eicosyl. 0037 C-Coalkenyl is for example allyl, methallyl, iso / (9) N propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-di V enyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso NF dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl. 0038 Aryl is for example naphthyl and preferably phenyl. 0039 Heterocyclic organic radical is, for example, a five membered nitrogen-containing hetero-cyclic radical Such as FN imidazolyl pyrazolyl, triazolyl pyrrolyl, pyrrolidinyl, N. and oxazolyl or thiazolyl, a six-membered nitrogen-containing / (10) heterocyclic radical such as piperazinyl, piperidinyl, pyridi nyl or morpholinyl, or a bicyclic radical which possesses a fused-on five-membered nitrogen-containing heterocycle M v and a six-membered aromatic ring, Such as benzoxazolyl, NX \ NH2; and indolyl, benzothiazolyl, benzimidazolyl or benzotriazolyl. 0040 Preferred is a hair dye composition, wherein in for mula (1) of component (a) R. R. R. and R independently 0.053 (c) a quaternary ammonium salt as defined as in from each other are hydrogen; or C-C alkyl. claim 1. US 2012/0012128 A1 Jan. 19, 2012 0054 Examples for quaternary ammonium salt according 0060 Direct dyes are of natural origin or may be prepared to component (c), there may be mentioned, for example, synthetically. They are uncharged, cationic oranionic, such as (c) the dialkyl dimethylammonium or alkyltrimethylam acid dyes. monium salts in which the alkyl radical comprises from about 0061 The hair dye composition according to the present 12 to about 22 carbon atoms, such as the distearyl dimethy invention of may be used in combination with at least one lammonium, cetyltrimethylammonium or behenyltrimethy single direct dye different from the dyes of component (a) and lammonium chlorides, (c) the di(C-C alkyl) (C2 (b). Calkyl)hydroxy(C-C alkyl)ammonium salts such as 0062) Examples of direct dyes are described in “Derma oleocetylhydroxyethylammonium chloride, or alternatively tology', edited by Ch. Culnan, H. Maibach, Verlag Marcel (c) the Stearamidopropyldimethyl (myristyl acetate) Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The ammonium chloride of formula: Science of Hair Care, chapter 7, p.