GB2440219A - Polymeric dye having cationic dyestuff linked to polymeric backbone - Google Patents

Abstract

Disclosed are polymeric dyes of formula A and B represent a polymer backbone; X1 and X2 is a linkage group or a direct band; R1 and R2 are hydrogen; C1- C14 alkyl, C2-C1 alkenyl; Y1 and Y2 are an organic dye; or hydrogen; wherein at least one of Y1 and Y2 is a residue of an organic dye; An1 and An2 are an anion; a and b are a number from 1 to 3; m and n is a number from 0 to 1000; p is a number from 1 to 1000; the sum of m, n, p is & 3. Compositions comprising the dyestuff are used for dying keratin-containing fibers such as hair. The composition can comprise further dyes and oxidative agents and can be formulated as a shampoo, a conditioner, a gel or an emulsion.

Description

<p>Polymeric hair dyes The present invention relates to novel polymeric

dyes and compositions compnsing these compounds, to a process for their preparation and to their use for dyeing of organic materials, such as keratin-containing fibers, wool, leather, silk, cellulose or polyamides.</p>

<p>It is well known that cationic compounds have a good affinity to negative charged hair, These characteristics have been used to contact the hair With small molecules, but also with polymers.</p>

<p>Numerous cationic polymeric dyes have been disclosed foruseas a colorant for human hair, for example in US 4,228,259,; US 4182,612 or FR 2 456 764, These references teach that the polymer moiety has the cationic charge.</p>

<p>SurprisIngly it was found that very good dyeing results are obtainend with polymeric hair dyes wherein the cationic charge is located in dye moiety.</p>

<p>Theretore the present invention relates to polymeric dyes of formula (la)</p>

<p>----</p>

<p>(Ib) --A---B --A---* ;or aAn1' I " -..m aAn l's.,-' (ya') --(I --p (ic) (Y,)__XdA][ B_Uj_[Aj_x2_(Y2h*) ; wherein A and B independently from each other represent a polymer backbone; X1 and X2 independently from each other are a linkage group selected Irom--C1-C10alkylene-, -C2-C2alkenylene-; -C5-C,0cycloaWylene-: C5-C1arylene; -CrC1 0arylene-(Ci -C10alky-lene)-; -C(O)-; -(CH2CH2-O)ia-; -C(O)O-; -OCO-; -N(R1)-; -CON(R1)-; -(R,)NC(O)-; -0-, -5-; -5(0)-; -S(O)r; -S(0)2-N(R1R2)-; or the direct bond: R1 and R2 independentPy from each other hydrogen; or unsubstituted or substituted, straight- chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C-C14alky1; C2-C14alkenyI; C6-C10aryl; C6-Grna ryl-C1-C1 0alkyl; or CrC 10alkyl(C5-C 10aryI); Y, and V2 independently from each other are a residue of an organic dye; or hydrogen; wherein at least one of V1 and V2 is a residue of an organic dye: An,, An2 and An3, independently from each other are an anion; a and b independently from each other are a number from 1 to 3; rn is a number from 0 to 1000; and n is a number from 0 to 1000; p isanumbertromltol000; wherein the sum of m tntp = 3.</p>

<p>C1-C14a1ky1 is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-panty], 2-pentyl, 3-pentyl. 2,2'-dlniethylpropyl, cyclopentyl, cyclohexyl, n-he xyl, n-octyl, 1,1',3,3'-tetramethylbutyl or 2-ethyihexyl, nonyl, decyl, uridecy, dodecyl, tredecyl or tetradecyl.</p>

<p>C2-C14alkeny[ is for example allyl, rnethallyl, 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.</p>

<p>C5-C10aryl is for example phenyl or naphthyl.</p>

<p>C1-C10alkylene is for example methylerie, ethylene, propylene, isopropylene, ri-butylene, sec-butylene, tert-butylene, n-pa ntylene, 2-pentyle rte 3-pentylene. 2,2'-dimethylpropylene, cyclopentyene, cyciohexylene, n-hexylene, n-octylene, 1,1,3,3'-tetramethylbutylene. 2-ethylhexylene, nonylene or decylene-In formulae (la), (Ib) and (ic) preferably V1 and V2 independently from each other are selected from the group of anthraq uinone, acri-dine1 no, azamethine, hydrazoniethine. triphenylmethane, benzodifuranone, cournarine, diketopyrrolopyrrol, dioxazine, diphenylmethane, formazane, indigoid indophenol, na ph-thaliniide, naphttioquinone, nitroaryl, merocyanine, methine oxazine, perinone, perylene, pyrenequinone, phialocyanine, phenazine, quinoneirrrine, quinacridone, quinopl-italone, styryl. stilbene xanthene, thiazne and thioxanthene dyes.</p>

<p>More preferably, V'1 and 4 independently frorri each other are selected from azo, azornethirie, hydrazomethine, merocyanine, methirie and styryl dye& Most preferably V1 and V2 have the same meaning.</p>

<p>Preferably in fornulae (is), (ib) and (ic) A and B, independently from each other are selected from polymers of monoolef ins and di-oLefins; mixtures of polymers of monoolefins and diolefins; copolymers of nionoolefins and diolefins with each other or with other vinyl monomers; polystyrene. poly(p-methyl-styrene), poly(a-niethylstyrene); aromatic homopolyrners and copolymers derived from vinyl aromatic monomers; copolymers and hydrogenated copolymers of vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles. acids, maleic an hydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof; graft copolyrners of vinyl aromatic monomers; halogen-containing poly-mers; polymers derived from rtjl-unsaturated acids and derivatives thereof; copolyrners derived from aji-unsaturated acids and derivatives thereof with other unsaturated mo-nomers; polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof; homopolyrners and copolymers of cyclic ethers; polyacetSs; poly- phenylene oxides and sull ides, and mixtures of polyphenylene oxides with styrene poly- rners or polyamides; Polyurethanes derived from hydroxyl- termninated polyathers, poly-esters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof; polyam ides and copolyamides derived from di-arnines and dicarboxylic acids andlor from aminocarboxylic acids or the corresponding lactams; polyureas. polylrriides, polyamide-inides, polyetherimids, polyesterimids, poly-hydantoins and polybenzirnidazoles; polyesters derived from chcarboxylic acids and dials and/or from hydroxycarboxylic acids or the corresponding lactones, polycarbonates and polyester carbonates; polyketones; polysulfones, polyether sulfones and polyether Ice-tones; Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melarnines on the other hand; polysiloxaries; natural polymers; and blends of the mentioned polymers.</p>

<p>Examples for polymers of monoolefins and diolefins are polypropylene, polyisobutylene, p0-lybut-I -ene, poly-4-methylpent-1-s ne, polyvlnylcyclohexane, polyisoprerie or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked). for example high density polyethylene (F-IDPE), high density and high molecular weight polyethylene (l-IDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-IJHMW), medium density polyethylene (MDPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE)I (VLDPE) and (ULDPE).</p>

<p>Polyolefuns, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe-rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under hIgh pressure and at elevated temperature) b) catalytic polynerisation using a catalyst that norniairy contains one or more than one metal of groups P/b, Vb Vib or VIII of the Periodic Table. These metals usually have one or more than one ligarid, typIcally oxides, halides, alcoholates, esters, ethers, arnines, alkyls, alkenyls and/or awls that may be either a-or a-coordinated. These metal com-plexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titaniurn(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hy-drides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, lIe and/or lIla of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).</p>

<p>Mixtures of the polymers mentioned above are for example mixtures of polypropylene with polyisobutylene, polypropylene wLth polyethylene (for example PP/HOPE, PP/LOPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).</p>

<p>Examples of copolyrners of monoolefins and diolefins with each other or with other vinyl mo-nomers are ethylene/propylene copolyniers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copotymers, propyle neltsobutylene copolyrri ers ethyl erie/but-1-en e copolyni ers, ethylene/hexene cc pa-lymers, ethyl ene/rnethylpentene copolymers, ethylene/heptene copolyni ers, ethylene/octene copolymers, ethylene/yin ylcyclohe xane copolymers, ethylene/cyclooletin copolymers (e.g ethylene/norbomene Like COO), ethylene/1-olefins copolymers, where the 1-olefin is gene- rated in -it U; propylene/butadiene copo I yrners, isobutylenefisoprene copolymers, ethyle ne/vi-nylcyclohexene copolymers, ethylene/alkyl acrylate copoIyrners ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolyrriers or ethylenelacrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a there such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in above, far example polypropylene/ethy-lene-propylene copolymers, LflPElethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EM)) LLDPE/EVA, LLDPEIEAA and alternating or random polyal-kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.</p>

<p>Romopolymers and copolyniers mentioned above may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic, where atactic polymers are preferred-Stereoblock polymers are also included.</p>

<p>Examples of aromatic homopolymers and copolymers derived from vinyl aronatic monomers including styrene are a-rnethylstyrerie. all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl an- thracene. and mixtures thereof. Hornopolyrners and copolymers may have any stereo-structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferre& Stereoblock polymers are also included.</p>

<p>Examples for copolymers including aforementioned vinyl aromatic monomers and comono- mers selected from ethylene, propylene, dienes, nitr'des, acids, maleic anhydrides, male-irnides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof are for example styrene/butadiene, styrene/acrylonitille, styrenefethylene (interpolymers), sty- rene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacry-late, styrene/maleic anhydride, styrenelacrylonitrilelmethyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene po-lyrner or an ethylene/propylenefdiene terpolynier; and bLock copolymers of styrene such as styrene/butadiene/styre ne, styrenefisop rend styre n a, styrene/ethylene/butylenelstyrene or S styrene/ethylen&propylene/styrer e.</p>

<p>Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned above especially including polycycloh exylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).</p>

<p>Homopolymers and copolyrners may have any stereostructure including syndiotaclic, isotac-tic, hemi-isotactic or atactic; where atactic polymers are preferred Stereoblock polymers are atso incEuded.</p>

<p>Examples for graft copolymers of vinyl aromatic monomers are styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene acrylon itnle copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonktrile and methyl methacrylate on polybutadiene; styrene and maleic an- hydride on polybutacliene; styrene, acrylonitrile and maleic an hydride or rrialeiniide on poly- butadiene; styrene and rnalelrrnde on polybutadiene; styrene and alkyl acrylates or meth- acrylates on polybutadiene; styrene and acry1ontrfte on ethylenelpropylen&diene terpoly-mars; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl rnethacryJates, styrene and acrylonitrile on acrylate/butacliene copolymers, as welL as mixtures thereof with the oopoly-mers listed under 6), for example the copolytTier mbctures known as ASS, MBS, ASA or AES polymers.</p>

<p>Examples for halogen-containing polymers are polychloroprene, chlorinated rubbers, chlori-nated and brominated copolymer of isobutylene-isoprene (balobutyl rubber), chlorinated or sulfochiorinated polyeThylene, copolymers of ethylene and chlorinated ethylene, epichloro-hydrin homo-and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chlorIde, polyvinyl fluoride, polyvinylidene fluo- ride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyL chlori-de/vinyl acetate or vinylldene chloride/vinyl acetate copolymers.</p>

<p>Examples for polymers derived froni a,p3-unsaturated acids and derivatives thereof are polyacryla les and polyrnethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.</p>

<p>Examples for copolymera of the monomers mentioned above with each other or with other unsaturated monomers are acryloni trilel buta diene copolyrners, 8crylOfl itrile/alkyl acryla te copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolyrners or acry-Ion itrilel alkyl methacrylate/butadiene terpolymers.</p>

<p>Examples for polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof are for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral. polyal}yl phthalate or polyallyl melanline; as well as their copolymers with olefins mentioned in above Examples for homopolymers and copolyrners of cyclic ethers are polyalkylene glycols.</p>

<p>polyethylene oxide, polypropylene oxide or copolyrners thereof with bisglycidyl ethers.</p>

<p>Examples for polyacetals are polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comononler; polyacetals modffied with thermoplastic polyurethenes, acrylates or MBS.</p>

<p>Examples for polyamlries and copolyamides derived from diamines and dicarboxylic acids andlorfrom aminocarboxylic adds or the corresponding lactams are polyamide 4, polyamlcle 6, polyamide 6l6 6/10, 6/9, 6/12, 4/6, 12112, polyamide 11, polyamide 12, aromatic poly- amides starting from m-xylene diamine and adipic acid; polyamides prepared from hexame-thylenediamine arid isophthalic or/and terephthalic acid and with or without an elastomer as modifier, tar example poly-2A, 4,-trimethylhexamethylene terephthalarnide or poly-rn-pheny-lene isophthalamide and also block copolyrners of the aforementioned polyamides with polyolefins, olefin copolymers, ionorners or chemicaky bonded or grafted elastomers; or with polysthers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyarnides or copolyamides modified with EPOM or ASS; and polyamides condensed during processing (RIM polyamide systems).</p>

<p>Examples tor polyesters derived from dicarboxylic acids and diols and/or from hydroxycar-boxylic acids or the corresponding lactones are polyethylene terephthalale, polybutylene terephtha late, pc]y-1 4-d imethylolcydohexane terephtha late, polyalkylene naphthalate (PAN) and po)yhydmoxybenzoates, as well as Mock copolyether esters cienved from hydroxyl-termi-S nated polyethers; and also polyesters n'iodilied with polycarbonates or MBS.</p>

<p>Examples for crosslinked polymers derived frorri aldehydes on the one hand and phenols.</p>

<p>ureas and melamines on the other hand are phenol/fornieldahyde resins, urea/formaldehyde resins and mela mine/formaldehyde resins.</p>

<p>Examples for natural polymers are cellulose, rubber, gelatin and chemically moditied homolo-gous derivatives thereof, for example cellulose acetatea, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their deri-vatives.</p>

<p>Example for blends oF the aforementioned polymers (polyblends) are PPIEPDM, Poly-arnid&EPDM or ABS, PVC/EVA, PVC/ABS, PVC/RIBS, PC/ABS, PBTP/ABS. PC/ASA, PCIPBI, PVC/CPE, PVC/acrylates, POM/themi oplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPOII-flPS, PPO/PA 66 and copolyrriers, PNHDPE, PNPPI PA/P P0, PBT/P'C/ABS or PBT/PETIPC.</p>

<p>Preferably both the polymer backbone (A and B) and residue of an organic dye (V1 and Y2) have a functional group slected from the electophillc group selected from halide, tosylate, mesylate, methoxy, acid chloride, sulfonyl chloride, epoxides, anhydride; or a nucleophilic group selected from amine, hydroxyl and ttiiol.</p>

<p>Preferably the molecular weight of the polymeric dye is from 400 to 5000.</p>

<p> Anian1 denotes, for example, an organic or inorganic anion, such as halide, preferably ac chloride and fluoride, sulfate, hydrogen sulfate, phosphate, boron tetrafluoride, carbonate, bicarbonate, oxalate or C1-C8a1$cyl sulfate, especially methyl sulfate or ethyl-sulfate: anion also denotes lactate, fomrnate, acetate, propionate or a complex anion, such as the zinc chloride double salt Most preferably are polymeric dyes of formula (2) and (3) I</p>

<p>HN</p>

<p>wherein Y1 is a residue of an organic dye selected from azo, anthrachinone, azomethine, hydrazo-methina, merocyanine. methine and styryl dyes; and iii, n and p are a number from 0 to 1000; wherein in formula (2) the sum of m and n = 3 and wherein in formula (3) the sum of rr and n and p = 3.</p>

<p>Preferred are also polymeric dyes of formula r -i I [Ft] R (5) Rr OtSi-O_-f'-Si-Oj_SH-R3; or R, L JmLft' J P1 [t 13 (6) Yr-XrS O-I-Si-ofsi--X2-Y2; wherein R3 L R3 JR3 ft is C1-Calkyl; and 1, y,, iii and n are defined as in formula (1).</p>

<p>Further preferred are also dyes of formula L;1 (7) Yj-X1-f-( , wherein I OyX-Y, 1.</p>

<p>ft is C-C5alkyI, and x1, x2, V1, Y2and nare defined as in formula (1) The dyes of formula (Ia), (ib) or (Ic) according to the invention are suitable for dyeing or-ganic materials, such as keratin-oontaining fibers, wool, leather, silk, cellulose or polyamides,</p>

<p>-ID-</p>

<p>cotton or nylon, and preferably human heir. 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 Gernerally, hair dyeing agents on a synthetic base may be classiefied into three groupr -temporary dyeing agents -semFpermanent dyeing agents, and -permanent dyeing agents.</p>

<p>The multiplicity of shades of the dyes can be increased by combination with other dyes.</p>

<p>Therefore the dyes of formula (Ia), (lb)and (ic) of the present invention may be combined wIth dyes of the same or other classes of dyes, especially with direct dyes, oxidation dyes; dye precursor combinatIons of a coupler compound as well as a diazotized compound, or a capped diazotized compound; and/or cationic reactive dyes.</p>

<p>Direct dyes are of natural origin or may be prepared synthetically. They are uncharged.</p>

<p>catlonic or anionic, such as acid dyes The dyes of formula (la), (ib) and (ic) may be used in combination with at least one single direct dye different from the dyes of formula (Ia), (lb)and (ic).</p>

<p>Direct dyes do not require any addition of an oxidizing agent to develop their dyeing effect.</p>

<p>Accordingly the dyeing results are less permanent than those obtained with permanent dyeing composItions. Direct dyes are therefore preferably used for semipermanent hair dyeings.</p>

<p>Examples of direct dyes are described in "Dermatology" edited by Ch Culnan, H Maibach, Verlag Marcel Dekker Inc., New York, BasIs, 1986, Vol. 7', Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, and in "Europäisches Inventar der Kosnietilcrohstoffe", 19961 published by The European Commission, obtainable in diskette form from the Bundesver-band der deutsohen Industrie-und Handelsunternerimnen für Arzneirrittel, Reformnwaren und Karperpflegemittel eN., Mannheim. -11 -</p>

<p>More preferred direct dyes which are useful for the combination with at least one single dye ci formula (la), {lb) and (ic), especially for semI pemhlanent dyeing, are: 2-arnino-3-nitrophenol, 2-amino-4-hydroxyethylarnino-anisole sulfate, 2-amino-6-chloro-4-nitropFienoi, 2-cbloro-5-nitro-N-hydroxyethylene-p-phe nylendiarn me, 2-hydroxyethyl-picrarnic acid, 2, 6-diamino-3-((pyridine-3y1)-azo)pyridine, 2-nitro-5-glyceryi-methylaniL 3-methyl- amino-4-nitro-phenoxyetha nol, 4-amino-2-nitrodiphenyleneamine-2'-carboxilic acid, 6-nitro- 1,2,3,4, -tetratiydroquinoxal., 4.-N-ethyl-I,4-bis(2'-hydroxyethylarnino-2-nitroberizene hydrochloride1 1-met hyl-3-nitro-4-(2'-hyd roxyethyl)-arninobenzene, 3-nitro-p-hydroxyethyl- aminop henol, 4-amino-3-nitropheriol, 4-hydroxypropylamine-3-nitrophenoi, hydroxyanthryt-aminopropylmethyl morphrmnc rnethosu Ifate, 4-nitrophenyl -aminoethylurea, 6-niLroiNoluid ne, Acid Blue 62, Acid Blue 9, ACid Red 35, Acid Red 87 (Ecsin). Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 161 Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3. Disperse Red 17, Disperse Violet I, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2.</p>

<p>HC Blue 7, NC Blue 8. HG Blue 12, HcOrange 11 HCOrange 2, HCRed 1, NC Red 10-11, HG Red 13, NC Red ô6, HC Red 3. HG Red BN, HG Red 7, HC Violet 1 NC Violet 2, NC Yellow 2, NC YellowS, NC YellowS, f-IC Yellow 6, NC Yellow?, HG Yellow 9, HC Yellow 12, HG Red B, hydroxyethyl-2-nitro-p-tol uidine, N,N-Bis-(2-Hydrcxyethyl)-2-nitro-p-phenylendiamine, NC Violet 88, Picramic Acid. Solvent Green 7.</p>

<p>Furthermore, the dyes of formula (la), (ib) and (ic) may be conibined with at least one cationic azo dye, for example the compounds disclosed in GB-A-2 319 776 as well as the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein, and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in WO 01166646, especially example 4, or with cationic dyes as described in WO 02/31056, especially example 6. the compound of formula 106; or the cationic dye of formula (3) as described in EP-A-71 4,954, or wIth a yeNow cationc dye of formula (DDI) R1-I)--, wherein</p>

<p>-</p>

<p>-12 -R1 and R2 are each independently of the other a C1-C3alkyI; or an unsubstituted or R3 is hydrogen; C1-C,alkyL C1-Calkoxy; cyanide; or halide; preferably hydrogen; and X is an anion; and preferably a compound of formula (DD1), wherein R, is methyl: P2 is benryl; R is hydrogen; and X is an anion; or wherein R1 is benzyl: R2 is benzyl: R3 is hydrogen; and X is an anion; or wherein R is benzyt; R2 is methyl; P3 is hydrogen; and X is an anion.</p>

<p>Furthemiore, cationlc nltroaniline and anthraquinone dyes are useful for a combination with a dye of formula (la), (ib) and (Ic) (orexample the dyes as described in the following patent specifications: US-S 298 029, especially in ccl 2, I. 33 to col 5, I. 38; US-S 360 930, especially in col 2, I. 38 to ccl 5, I. 49; US-S 169 403, especially in col 2, I. 30 to ccl 5, I. 38; US-S 256 823, especially in cal 4, I. 23to col 5, I. 15; US-S 135 543, especially in cot 4,1. 24to ccl 5, L 16; EP-A-818 193, especialyon p. 2, I. 40 to p. 3, 1.26; US-S 486 629, especially in col 2, I. 34 to col 5, I. 29; and P-A-15B 547, especially on p. 7, 1. 48 to p. 8, I. 19.</p>

<p>The dyes of formula (Is), (ib) and (lc) may aPso be combined with acid dyes, for example the dyes which are known froni the international names (Color index), or trade names.</p>

<p>Preferred acId dyes which are useful for the combination with a dye of formula (la), (ib) and (ic) are described in US Patent 624.8,314. They include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201. Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214. Red Color No. 3, Red Color No. 104, Red Color No. 105(1). Red Color No. 106, Green Color No.21 Green Color No. 3. Orange Color No. 207, Yellow Color No. 20211), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yeflow Color No. 203, Blue Color No. 201, Green Color No. 201. Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231. Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402. Black Color No. 401 and Purple Color No, 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.</p>

<p>These acid dyes may be used eIther as single conponent or in any combination thereof Hair dye compositions comprising an acid dye are known. They are for example described in Dermatology", edited by Cli. Cuinan, H. Maibach, Verlag Marcel Dekker Inc, New York, Basle, 1985. Vol 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially onp.253and254, Hair dye compositions which comprise an acid dye have a phi of 2-6, preferably 2-5, more preferably 2.5-4.0.</p>

<p>The dyes of formula (la), (ib) and (ic) according to the present invention may also readily be used in combination with acid dyes and/or adjuvants. for example -acid dyes and an alkylene carbonate, as described in US patent 6248314, especially in</p>

<p>examples I and 2;</p>

<p>-acid hair dye compositions comprising various kinds of organic solvents rep resented by benzyl alcohol as a penetrant solvent have good penetrability into hair, as described in Japanese Patent Application Laid-Open Nos. 210023/1 986 and 101841/1995; -acid hair dye compositions with a water-soluble polymer or the like to prevent the drooping of the hair dye composition, as described for example in Japanese Patent Application Laid-Open Nos. 87450/1998, 25 5540/1 9ffT and 245345/1996; -acid hair dye compositions with a water-soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application Laid-Open No. 53970/1998 and Japanese Patent Invention No 2391 111 913 The dyes of formula (la), (lb) and (ic) may also be combined with uncharged dyes, for example selected from the group of the nitroanilines, nitrophenylenediarnines, nitroaminop henols, anthraquinones, indophenols, phenazines, phenothiaz ines, bispyrazolons, bispyrazol aza derivatives and methines.</p>

<p>Furthermore, the dyes of formula (Ia), (ib) and (Ic) may also be used in combination with oxidation dye systems.</p>

<p>OddaUon dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer and coupler compounds.</p>

<p>Suitable oxidation dyes are described for example in -DE 19 959 419, especially in ccl 2, I. 6 to col 3, I. 11; -MDerrnatologj', edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986. VS 7 Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264 -267 (oxidation dyes); Preferred developer compounds are for example primary aromatic amiries, which are substituted in the pare-or oriFic-position with a substituted or unsubstituted hydroxy-or amino residue, or diarninopyridine derivatives heterocyclic hydrazones, 4-aminopyrazol derivatives1 2,4,5,6-tetraarriinopyrimidine derivatives, or unsaturated aldehydes as described in DE 19 717 224, especially on p. 2. I. 50 to I.66 and on p. 3 I. 8 to 1. 12, or cationic developer compounds as described in WO 00143367, especially on p., 21. 27 to p. 8, I. 24, in particular on p.9,1. 22to p.11,1.6 Furthermore, developer compounds in their physiological compatible acid addition salt form, such as hydrochloride or sultate can be used. Developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a bass, such as alkari metal-phenolates.</p>

<p>Preferred developer compounds are disclosed in DE 19959479, p. 2, 1. 8-29.</p>

<p>More preferred developer compounds are p-phenyleridiamine, p-toluylendiamine, p-, m-o- aminopheflol, , N-bis-(2-hydroxyethyl)-p-phenylenediarnine sulfate, 2-arriino-4-hydroxy-ethylarninoanisole sulfate, hydroxyethyl-34-.niathylenedloxyanll., I -(2'-hydroxyethyl)-2,5diaminobenzene, 2,6 -dimethoxy-3,5-di amino-pyridine, hydroxypropyl-bis-(N-hydroxyethyl-p- phenylenerbarnine) hyd rocfiloride, hydroxyethyl-p-phenylenediamine sulfate, 4-amino-3-me-thylphenol, 4-rnethylani inophenol sulfate, 2-aminomethyl-4-aminophenol. 4 5-diamino1 -(2-hydroxyethyl)-1 H-pyrazol, 4-amino-m-cresol, 6-amino-rn-cresol, 5-amino-6-chloro-cresol, 2.4,5,6-tetraaminopyrimidine. 2-hydroxy-4,5,6-triaminopyrimidine or 4-hydroxy-2,5,6triarninopyrirnidine sulfate.</p>

<p>Preferred coupler compounds are m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and most preferably the coupler compounds disclosed in DE 19959479, p.1,1. 33 to p. 31. 11 The dyes of formula (la), (ib) and (ic) may also be used together with unsaturated aldehydes as disclosed in DE 19 717 224(p. 2, I. 50 to I. 66 and on p. 3 I. 8 to I. 12) which may be used as direct dyes or, a'ternatively together with oxidation dye precursors Further preferred for a combination with a dye of formula (la), (1 b) and (ic) are the following oxidation dye precursors -the developer/-coupler corn binatio n 24, 5 6-tetraarninopyrirnidine and 2-methyiresorcin e for assessing of red shades; -p-toluenedlamine and 4-amino-2-hydroxytoluene for assessing of blue-violet shades: -p-toluenediarnine and 2-ariiino-4-hydroxyethyarninoar.iso4e for assessing of blue shades; -p4ol ueneclia mine and 2,4-diarnino-phenoxyethyriol for assessing of blue shades; -methyl-4.-aminophenol and 4-amino-2-hydroxytleoluene for assessing of orange shades; -p-toiuenediamine and resorcOie for assessing of brown-green shades; -p-toluenediamine and 1-naphthor for assessing of blue-violet shades, or -p-toluenediarnine and 2-methyiresorcine for assessing of brown-gold shades.</p>

<p>Furthermore autooxidizable compounds may be used in combination with the dyes of formula (la), (1 b) and (ic).</p>

<p>Autooxidizable compounds are aromatic compounds with niore than two substituents in the aomatic 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.</p>

<p>Autooxidizable compounds are for exampre berizene, indol, or ndoI, especially 5,6-dihydroxyindol or 5,6-dihydroxyindol derivatives as described in WO 99/20234, especially on p. 26, I. 10 to p. 28, I. 15, or in WO 00128957 on p. 2, third paragraph.</p>

<p>Preferred autooxidizable benzene derivatives are I,2.4-trihydroxybenzene, I -meLhyl-24,5- trihydroxybenzene, 2, 4-diarrnio-6-niethytphenol, 2-ami no-4-rnethylaninophenol, 2,5-dia -mino-4-niethyl-phenol, 2,6-diamino-4-diethy1aminopl'nol 2,6-diamino-1, 4-ctihydroxy-berizene, and the salts of these compounds, which are accessible with acid.</p>

<p>Preferred autooxidizable Indol derivatives are 5,6-dihydroxyindol, 2-rnetbyl-5,6-di hydroxy- indol, 3-methyl-5, 6-dihydroxyindole, 1 -methyl-5,6-dihyd roxyndol, 2,3-dimethyl-5,6-d ihydroxy- indol, 5-methoxy-6-diliydroxyindoi, 5-acetoxy-6-hydroixyindol, 56 -diacetoxyindol, acid of 5,8-dihydroxyindol-2-carbonacid, and the salts at these compounds, which are accessible with acad.</p>

<p>The dyes of formula (la), (Ib) and (Ic) may also be used in combination with naturally occurring dyes, such as henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rharnnus frangula bark, sage, campeche wood, madder root, catechu, cadre and alkanet root. Such dyeings are described, for example, in EP-A-404 888, especially on p 3,! 55 to p. 4, I. 9.</p>

<p>Furthemiore, the dyes of formula (ia), (ib) and (Ic) may also be used in combination with capped diazotised compounds.</p>

<p>Suitable diazotised compounds are for example the compounds of formulae (1) -(4) in WO 20041019897 (bridging gages 1 and 2) and the corresponding watersoluble coupling components (l)-(lV) as disclosed in the same reference on p. 3 to 5.</p>

<p>Further preferred dyes or dye combinations which are useful for the combInation with a dye of fomiula (la), (ib) and (Ic) according to the present invention are described in (DC-Oil WO 95101772, wherein mixtures of at least two cationic dyes are disclosed, especially p. 2, I. 7 to p. 4, I. I, preferably p. 4. I. 35 to p. 8. I 21: formulations p. 11, last -p.28,L19; (DC-02). US 6,643,256, wherein cationLc dyes are disclosed, especially the compounds of formulae (1), (2), (3) and (4) (col. 1, I. 27-col. 3. I. 20, and preferably the compounds as prepared in the examples ito 4 (ccl. 10, 1.42 to coP. 13. I. 37; formulations ccl. 13, I. 38 to coL 15, I. 8; jQQ): EP 970 685, wherein direct dyes are described especially p. 2, 1. 44 to p. 9, I. 56 and preferably p. 9, I. 58 to p. 48, I 12; processes for dyeing of keratin-containing fibers especially p. 50, I. 15 to 43; formulations p. 50, I. 46 to p. 51, I. 40; (QC-04): DE-A-19 713 698, wherein direct dyes are described, especially p 2, L 61 to p. 3, I. 43; formulations p. 5, I. 26 to 60; -17 - (DC:05): US 6,368,360, wherein directd dyes (ccl. 4,). ito col. 6, I. 31) and oxidizing agents (cal. 6, I. 37 -39) are disclosed; formulations cal. 7, L 47 to col. 9, I. 4; (DC-06): EP 1166 752, wherein caUonic dyes (p. 3, I. 22-p. 4, I. 15) and anionic UV-absorbers (p. 4 I. 27 -30) are disclosed; forrnuations p. 7, I. 50-p. 9, l 56; (DC-Ofl. EP 998,908, wherein oxidation dysings comprising a cationic direct dye and pyra-zolo-(1,5-a]-pyrimidines (p. 2, I. 48 -p. 4, I. 1) are disclosed; dyeing formulations p 47, 1. 25top. 50,1.29; (DC-OS) : FR-2188432, wlieren combinations of catlonic dyes with Arianors are disclosed, especially p. 53, [Ito p. 63, I. 23, more especially p. 51 to 52, most especially Basic Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic Yellow 57, and/or at least one Basic Blue 99; or combInations of erianoren and/or oxidative dyes, especially p. 2, I. 16 to p a, l 16; dyeing formulations on p. 53, I. 1 to p. 63, I. 23: (QC-Oik DE-A-i 9 713 898, wherein the combinations of direct dyes and permanent-wave fixing comprising an oxidation agent, an oxidation dye and a direct dye are dIsclosed; espedally p. 4, I. 65 to p. 5, I. 59; (DC-i 0); EP 850 638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, 1. 27 to p. 7, I. 48 and preferably p. 7, I. 20 top. 9, I. 26; dyeing torrnulations p. 2, I. 3-12 and I. 30 to P. 14, and p 28, I. 35 -p. 30, I. 20; preferably p. 30, [25-p. 32. L 30; (DC-li). US 6,190,421 wherein extemporaneous mixtures ole composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, of a compo-sition (B), in powder form, containing one or more direct dyes (cd. S I. 40-col. 7, I 14), optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agents are disclosed; formulations ccl 8, I. 60 -col 9, I. 56; (DC-i 21 US 6,228,129, wherein a ready4o-use compositIon comprising at least one oxidation base, at least one cationic direct dye and at least one enzyme of the 2-electron oxidoreductase type in the presence of at least one donor for the said eriryme are disclosed; especially coL 8. I. 17-cal. 13, I. 65; dyeing formulations in col. 2, I. 16 to aol.</p>

<p>25, I. 55 a murti-compartrnent dyeing device is described in col. 26, I. 13 -24, (DC-iS)' WO 99/20235, wherein compositions of at least one cationic dye and at least one nitrated benzene dye with cationic direct dyes and nitro benzene direct dyes are described; on p. 2. I. Ito p. 7,1. 9, and p. 39, I. Ito p. 40 I. 11, preferably p. 8, I. 12 to p 251.6; p. 26, L flop. 30,. 15; p. 1, L 25 top. 8,15, p.30,117 top. 34125, p. 8,1.12 to p. 25 I. 6, p. 35, 1. 21 to 27, especially on p. 36. I. Ito p. 3?; (DC-14): WO 99120234, wherein compositions comprising at least one direct cationic dye and at least one autooxidisable dye, especialPy benzene, indol and indol. derivatives are described, preferably direct dyes on p. 2, 119 to p 26, L 4, and autooxichsable dyes as dislosed especially on p. 26, I. 10 to p. 28, 1. 151 dyeing fomiulations especally on p. 34, I. 5 to p. 35, Ii 18; (DC-iS): EP 850 636. wherein oxidation dyeing compositions comprising at least one direct dye and at Feast one rrieta-arninophenol derivative as coupler component and at least one developer compound and an oxidizing agent ai'e disclosed, especially p. 5, I. 41 to p. 7 L 52, dyeing formulations p. 19, I. 50 p. 22, I. 12; LDC-.i EP-A-850 637, wherein oxidation dyeing compositions comprising at least one oxidation base selected from para-phenylenedlamines and bi s(ph enyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler selected from meta-diphenols, and the acid-addition salts thereof, at least one cationic direct dye, and at least one oxidizing agent are thsclosed, especially p. 6, 1 50 to p. 8, I. 44 are discloseded; dyeing formulations p. 21, L 30 -p. 22, 1 57; (DC-ill: WO g9/48856, wherein oxidation dyeing compositions comprising cationic couplers are disclosed, especiaHy p. 9, I. 16 -p. 13, I. 8, and p. 11, I. 20-p. ô2, I. 13; dyeing formulations p. 36, 1 7 -p. 39, I. 24; (DC-18): DE 197 172 24, wherein dyeing agents comprising unsaturated aldehydes and coupler compounds and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy compounds, andfor at least one CH-active compound are disclosed p 3. I. 42 -p. 5 1. 25; dyeing formulations p. 5, I 25 -p. 9, I. 61.</p>

<p>In the dye combinations disclosed in the references (DC-01 -DC-i8) above, the dyes ni formula (is), (ib) and (Ic) according to the present inventIon may be added to the dye combinatLons or dyeing formulations or one or more of the dye components may be replaced with at least one dye of formula(la), (1 b) and (Ic).</p>

<p>The present invention also releates to formulations, which are used for the dyeing of organic materials, preferably keratin-containing fibers, and most preferably human hair, comprising at least one dye of formula (la), (lb)and (ic).</p>

<p>-19 -Preferably the dyes offormula (14 (ib) and (Ic) are incorporated into the composition for treating organic material, preferably for dyeing in amounts of 0.001 -5% by weight (hereinafter indicated merely by "%), particularly 0.005 -4%, more particularly 0.2 -3%r based on the total weight of the composition.</p>

<p>The formulations may be applied on the keratiri-containing fiber, preferably the human hair in different technical forms, Technical forms of formulations are (or example a soFutiori, especially a thickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo, powder, gel, or emulsion.</p>

<p>Customary the dyeIng compositions are applied to the keratin-containing fiber in an amount of 50 to 100 g.</p>

<p>Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or kits' or any of the rriulti-cornpartrnent packaging systems with compartments as described for example in US 6,190,421, ccl 2, I. 15 to 31.</p>

<p>The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably From S to 10.</p>

<p>The dyeing compositions of the present invention are applied on the hair in a temperature range of 25 to 200, preferably 18 to 80, and most preferably from 20 to 40 C.</p>

<p>One preferred embodiment of the present invention relates to the formulation of dyes, wherein the dyes of formula (la), (1 b) and (ic) are in powder form.</p>

<p>Powder formulations are preferably used if stability and/or solubility problems as for example described in DE 197 13698, p 2, 1. 26 to 54 and p. 3, I. 51 top. 4, I. 25, and p. 4, 1.41 to p 5 I. 59.</p>

<p>Suitable cosmetic hair-care formulations are hair-treatment preparations, e.g. tiar-washing preparations n the form of shampoos and conditioners, hair-care preparations, eg pre- -20-treatment preparations or leave-on products such as sprays, creams, gels1 lotions, n'iousses 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 per- manent waves (hot wave, mild wave, cold wave), hair-strghtening 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 orcarnornile.</p>

<p>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, 01W, O1W/O, W/OiW or PIT emulsions and all kinds of rnicroemulsions, creams, sprays1 emulsions, gels, powders and also surfactant-containing foaming solutions, eg. shampoos or other preparations, that are suitable for use on keratin-containing fibers.</p>

<p>Such forms of use are described in detail In Research Disclosure 42448 (August 1999) It necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in US-3 369 970, especially call, I. 70 to ccl 3, I. 55. The dyeing compositions according to the invention are also excellently suitable for the dyeing method described in DE-A-3 529 870 using a dyeing comb or a dyeing brush.</p>

<p>The constituents of the aqueous camer are present in Lhe dyeing compositions of the present invention in the customary amounts; for example enulsitiers may be present in the dyeing compositions in concentrations from 0.5 to 30 % by weight and thickeners in concentrations of from 0.1 to 25 % by weight of the total dyeing composition.</p>

<p>Further carriers for dyeing compositions are for example described in "Dermatology", edited by Ch. Culnan, H. Maibach Verlag Marcel Dekker lnc, New York, BasIs, 1986, Vol. 7, Oh.</p>

<p>Zviak, The Science of Hair Care. chapter 7, p. 248-250, especially on p. 243, I. 1 to p. 244, I. 12.</p>

<p>If the dyes of formula (1 a), (Ib) and (ic) are used together with oxidation dyes and/or the addition salts Thereof with an acid, they may be stored separately or together. Preferably the oxidation dyes and the direct dyes which are not stable to reduction are stored separately.</p>

<p>-21 -The dyes of formula (la), (1 b) and (1 C) may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.</p>

<p>When the dyes are stored separately, the reactive components are intimately mixed with one another directly before use. In the case of dry storage, a defined amount of hot (from 50 to 80't) water is usually added and a homogeneous mixture prepared before use.</p>

<p>The dyeing compositions according to the invention may comprise any active ingredients, additives or adjuvants known for such preparations, like surfactants, solvents, bases, acids, ID perfumes, polymeric adjuvants, thickeners and light stabilisers.</p>

<p>The following adjuavents are preferably used in the hair dyeing compositions of the present invention: -non-ionic polymers, for example vinylpyrrolidone/vinyl acrytate copolyrriers. polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetate copoPymers and polysiPoxanes; -cationic polymers, such as quaternised cellulose ethers, polysiloxanes having quaternary groups, dimethyldia llylammoniurn chloride polymers, copolyrriers of dimethyldi allyl-arnrnoniurn chloride and acrylic acid, as available commercially under the name Merquat 280 and the use thereof in hair dyeing as described, for example, in DE-A-4 421 031. especially p. 2, I. 20 to 49, or EP-A-953 334, especIally p. 27, lIT to p 30,1 11; -acrylarnideldimethyldiallylamnionium chloride copolymers, diethyl-sulfate-quaternised di- methylaminoethyl niethacrylateMnylpyrrolidone copolyniers. vinylpyrrolidone/imidazol I -nium methoobloride copolymers; -quaternised polyvinyl alcohol: -zwltterionic and amphoteric polymers, such as acrylanido-propyltrimethylanimonium chloride/a crylate cc p0 lyrners and octyla crylani ide/rn ethyl rnethacrylate/tert-butyl-aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers; -anionic polymers, such as for exaniple, polyacryhc acids, crosslinked polyacrylic acids, vinyl acetatelcrotonic acid copolymers, vinylpyrroildone/vinyl acrylate copolymers, vinyl acetate/butyl nialeate/isobornyl acrylate copolymers, methyl vinyl etherlmaleic anhydride copoymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers; -thickeners, such as agar, guar gum, alginates, xartthan gum. gum arabic, karayn gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl celFulose and carboxymethyl cellulose, starch fractions and derivatives.</p>

<p>-22 - such amylose, amylopectin and dextrins, clays, e.g bentoriite or hilly synthetic hydro-colloids such as, for example, polyvinyl alcohol; -structuring agents, such as glucose and malec acid; -hair-conditioning compounds, such as phospholipids, br example soya lecithin, egg lecithin1 cephalins, sihcone oils, and conditioning compounds, such as those described in DE-A-19 729 080, especIally p. 2, 1. 20 to 49, EP-A-834 303, especially p. 2, I. 18-p. 3, 1.2, or EP-A-312 343, especially p.2,1-59-p. 3, Lii; -protein hydralysates, especially elastin, collagen, keratiri, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quaternised protein hydrolysa tes; -perfume oils, dimethyl isosorbitol arid cyclodexLrins, -solubilisers. such as ethanol, isopropanol, ethylene glycol, propylene glycol, gPycerol and dlethylene glycol.</p>

<p>-anti-dandruff actke ingredients, such as plroctones, olamines and zinc Omadine, -substances for adjusting the pH value; -panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins; -cholesterol; -light stabilisers and UV absorbers as listed in Table below: Table i WV absorbers which cray be use in the dyeing corrioosltions ci the oresent invention NcL Cherrücal Name CAS No. 1 (t/-)-1,7,7-trimethyl-34(4-rnethylphenyl)methyleneJbicyclO-36861-47-9 -[2.2.llheptan-2-one ____ ____ ____ 2 1,77-trin'iethyl-3-(phenylmethylene}blcycloE2.2.1]heptan -2-one 15087-248 3 (2-HydroxymethoxyphenylX4-rnethylphenyl)methaflofle 1641-17-4 4 2,4-di hydroxybenrophe none 131-56-6 2,2',4,4'-tetrahydroxybenzophenone -131-555 S 2-Hydroxy-4-methoxy benzophenone; .. --- 7 2,2 -dihyd roxy-4,4r_dimeoxybenzophenone -131-54-4 S 2,2'-Dihydroxy-4-rnet.hoxybenzophenone 131-53-3 9 1 -[4-( 1,1 -dimathylethyl)p hen yl]-3-(4-rnethoxyp he nyl)propa ne-I,3-70356-09-1 diane 3,3,5-Trimethyicyclohexyl-2-hydroxy benzoate -118-56-9 11 isopentyl p-rnethoxycinnamate. 711 7-1 0-2 12 Menthy1-amlnobenzoate 134-09-8 13 Meny! salicylate -. 89-46-3 14 2-Ethy[riexyl 2-cyano,3,3-diphenyracrylate 8197-30-4 2-ethylhexyl 4-(dirnethylamlno)benzoate 21245-02-3 16 2-ethylhexyl 4-rnethoxycinnamate. 5466-77-3 -23 -Table 1: Liv absc rbers which may be use in the dyeingonipositions of the present invention Chemical Name CASNO. -- 17 2-ethylhexy! salicylate 110' 16 Benzoic acid, 4, 4', 4"-(l1 3, 5-triazire-2, 4,5-triyltriirnino)tiis-,tris(2-881 22-990 ethyihexyl jester; 2,4, 6-lila nilino-(p-ca rbc-2'-eth ylhexyl-1 -oxO-1,3,5-trlazine _______________ 19 Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 1 13010-52-9 2-Propenarnide, N-[4-I( 4,7,7-trimethyl-3-oxobicyclo2.2. 1)hept-2-147897-12-9 -ylidene)rnethyllphenyllmethyl]-, hornopolymer _____________ 21 Trlethanolarnine saricylate 2174-16-5 22 2,2'-Methylene-bis-{6-( 2W be nzotriazol-2-y l)-4-( 1,1131 3-tetramethyl-103597-45-1 -butyQ-phenoll ______________ 23 2,4-b is{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4 187393-00-6 -methoxyphenyl)-(1,3,5)-triazine (Tinosorb 5) -- 24 Benzoic add, 4,4'-I(6-[(4-j[( 1,1 -dimethylethyl)aminojcarbonyll-154702-15-5 phenyija mine] 1,3,5-triazne-2,4-diyl]diimino)bis-, bis(2 -ethylki exyl)-ester ______________ Phenol, 2-(2H-benzotriazo l-2-yl)-4-melhyl-6-[2-methyl-3-[1,33, 3-155633-54-8 -tetran ethy-t(tri rnethylsi lyl)oxy]disdoxanylpropy11-_____________ 26 Dimethicodiethylbezalmaloriate. 207514-74-1 V Benzoic acid, 2-(4-(diethylamirio)-2-hydroxybenzoyl]-. hexyl ester 302 776-68-7 28 1,3,5-Triazine, 24 6-tiis(4-mcthoxyphenyfl-7753-12-0 29 1,3,S-Triazlne, 2,4 6-trlsj4-j(2-ethylhexyl)oxyjphenyl]-208114-14-1 2-Propenoic acid, 3-( 1 N-imidazol-4-yI)-104-96-3 31 Benzolc acid, 2-hroxy-, __ 94134-93-7 32 1,2,3-Propanetriol, I -(4-aniinobenzoate) -136-44-7 33 Benzeneacetic acid, 3,4-dimethoxy-a-oxo-4732-70-1 - 34 2-Propenoic acid, 2-cyano-3,3-diphenyl-. eIhy --5232-99-5 Anthralinic acid, p-menth-3-yl ester 134-09-8 -.</p>

<p>36 1,3, 5-lriazine-2,4,6-triarTIine, N, N'-bis(4-(5-( 1,1 -dimethylpropyl)-2-288254-16-0 benzoxazolyljphenyll-N"-(2-ethylhexyl)-or Uvasorb K2A 37 2-Hydroxy-4-rTlethoxy benzophenone-5-sulfoni!ci _.... --4065-45-6 38 Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts 56039-58-8 -.</p>

<p>39 Methyl N, N,N-trimethyl-4-I(4,7,7-trimethyl-3-oxobicycki[2,2,1 Ihept-52793-97-2 -2-ylidene)methyIniliniun1 sulphate; _____________ 4-aniinobenzoic acid.. 150-1 3-0 41 2-phenyl-1 H-benzfmldazole-5-sulphonic acid 27503-81-7 - 42 3, 3'-(1, 4-phenylenediTiethylene)bis7, 7-dimethyl-2-oxo-90457-82-2 -bicyclo[221]heptane-1-methanesultonic acid] ____________ 43 1 l-1-Senzimidazole-4,6-disultonic acid, 2,2'-( 1,4-phenylene)bis-, 180898-37-7 disodium salt _____________ 44 Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-( 1-92484-48-5 methyipropyl)-, monosodium salt _______________________ _____________ 1 -Dodecanaminiurn, N-[3-[4-(dimethylamino)benzoyIan'inOJ-156879-41-3 -prcpyj]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) ____________ 46 1 -Propananiniurn, N,N,N-trimethyl-3-[( 1 -oxo-3-phenyl-2-propenyl)-1771 90-g8-6 -amino]-, cFdoride ----______ -24-Table 1 UVabsorbers which may be use in the deino c mpositions of [he present invention ______________ !4ChernicalNsrne CASNO.</p>

<p>4/ ll-1-Berizimidazole-4,6-disulfonic acid, 2,2'-(14-phenylene)bis-170864-82-1 48 1-P ropanaminium, 3_[3-[3-(2H-benzotriazol-2-yl)-5-( 1.1 -dim ethyL-340964-15-0 ethyl)-4hyd roxyphenyl-I -oxopropyl]aminoj-N,N-diethyl-N-methyl -, -meth_ysultate (salt) ____________________ _____________ 49 2 2'-bis( 1, 4-phenylene)-1 H-benzimldazole-4,6-rtisulphonic acid vim-349580-12-7, rio sodium salt or Disodkim phenyl ciibenziniidazole tetrasulfonate orNeoheliopanAP ____ The use of UV absorbers can effectIvely protect natural and dyed hair from the damaging rays of the sun and increase the wash fastness of dyed hair.</p>

<p>Furthermore, the following tJV absorbers or combinations may be used in the dyeing compositions according to the invention: -cationic benzotriazole UV absorbers as for example described in WO 01/36396 especiaflyon p. 1, 1. 20 to p 2, I. 24. arid preferred on p. 3 to 5, and on p. 26 to 37; -cationic benzotriazole UV in combination with antioxidants as described in WO 01136396. especially on p. 11, I. 14 top. 18; -U'] absorbers In combination with antioxidanis as described in US Patent 5 922 310, especially in col 2, I. 1 to 3; -U'] absorbers in combination with anticxidents as described in US Patent 4756493.</p>

<p>especially in col 1, 42 to col 2, I. 7, and preferred in ccii 3, 43 to col 5 I. 20; -combination of UV absorbers as described in US Patent 5 830 441, especially in ccii 4, I. 53 to 56; -combination of UV absorbers as described in WO 01/36396, especially on p. 11, I. 9 to 13; or - triazine derivatives as described in WO 952244T, especially on p, L 23 to p. 2, 1. 4, andpreferredonp.2,l.11 top.3,l. l5andmostpreferredonil6tol and l2to 16 Suitable cosmetic preparations may usually contain (105 to 40 % by weight, preferably from 0.1 to 20 % by weight, based on the total weight cit the composition1 of one or more UV absorbers; -consistency regulators, such as sugar esters, polyol esters or polyol alkyl ethers; fats and waxes, such as spermaceti, beeswax, montan wax, paraffins. fatty alcohols and fatty acid esters: -fatty alkanolarnides; -polyethylene glycols and polypropylene glycols having a molecular weight of from 150 to 000, for example such as those described in EP-A-801 942, sspecaOy p. 3, 1. 44 to -complexing agents, such as LOTA, NTA and phosphonic acids, -swelling and penetration substances, such as polyols and polyol ethers, as listed extensively, for example, in EP-A-962 219, especiafly p. 27, I. 18 to 38, for example glycerol, propylene glycol, propylene glycoi monoethyl ether, butyl glycol, benzyl alcohol.</p>

<p>carbonates, hydrogen carbonates, guanidines, urea and also primary, secondary and tertiary phosphates, irnldazoles, tannins, pyrrole; -opacitiers, such as latex; -pearlising agents, such as ethylene glycol mono-and di-stearate; -propellants, such as propane-butane mixtures, N20, dimethyl ether, CO2 and air; * antioxidants: -sugar-containing polymers, as described in EP-A-970 687, especially p. 28,1. l7top.</p>

<p>29,1.23; * quaternary ammoniurn salts, as described in WO 00110517, especially p. 44, L 16 to p. 46, I. 23.</p>

<p>-Bacteria inhibiting agents, like preservatives that have a specific action against gram- positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil, A natural deodorising agent of interest is the terpene alcohol famesol (3,711-tnniethyl-26,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol n'onolaurate has also proved to be a bacterlostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % by weight1 based on the solids content of the preparations: The dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are rwitterionic or ampholytic, or more preferably anionic, non-ionic and/or cationic surlactants. -26 -</p>

<p>Suitable anionic surfactants in the dyeing compositions according to the present invention include all anionic surfac&-active substances that are suitable for use on the human body.</p>

<p>Such substances are characterised by an anionic group That imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately from 10 to 22 carbon atoms. In addition. glycol or polyglycol ether groups, ester, ether arid amide groups and also hydroxy groups may be present in the molecule. The following are examples of suitable anionic surfactants, each in the form of sodium, potassium or ammoniurn salts or mono-, di-or tri-alkanolammoniurn salts having 2 or 3 carbon atoms in the alkanol group: -linear fatty adds having 10 to 22 carbon atoms (soaps), -ether carboxylic acids of formula R-O-(CH2-CHrO)x-CH2-COOH, in which R is a l. ar alkyl group having 10 to 22 carbon atoms and x = 0 or from I to 16.</p>

<p>-acyl sarcosides having 10 to 18 carbon atoms rn the acyl group, -acyltaurides having 10 to 18 carbon atoms in the acyl group, -acyl isothionates having 10 to 18 carbon atoms in the acyl group, -sulfosuccinic mono-and di-alkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, -linear alkane suffonates having 12 to 18 carbon atoms, -linear a-olefin sulfonates having l2to 18 carbon atoms, -a-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, -alkyl sulfates and alkyl polyglycol ether sulfates of fomiula R'-O(CHrCHrO)..-SOH. in which R' is a preferably tar alkyl group having 10 to 18 carbon atoms and x' =0 or from ito 12, -mixtures of surface-active hydroxysulfonates according to DE-A-3 725 030, especially p.3,1.431055, -sulfated hydroxyalkylpolyethylene andfor hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially p. 4, I. 42 to 62.</p>

<p>-sulfor'iates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3 926 344, especially p. 2, I. 36 to 54, -esters of tartaric acid and citric acid with alcohols which are addition products of approximately from 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having from B to 22 carbon atoms, or -anionic surfactants, as described in WO ooiiosi 6, especially p. 45, I. 11 to p. 48, I 3.</p>

<p>Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxyhc 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-C22carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid Surface-active compounds that carry at least one quaternary arnnioniurn group and at least one -000 or -SOj group in the molecule are terminated zwitterionic surfactants. Preference is given the so-called betaines, such as the N-alkylNN-dimetbylanirrionium glyclnates, for example cocoalkyldirrethyla mmonium glycin ate, N-acylaminopropyl-N, N-cfimethylammonium glycinates, for example coccacylaminopropyldimethylamrTionium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazol. having from 8 to 18 carbon atoms in the alkyl or acyl group and also coooscylarninoethylhydroxysthylcarboxyrTlethyl glyclnate. A preferred zwitterionic surfactant is the faLty acid amide derivative known by the CTFA name cocoami-dopropyl betaine.</p>

<p>Ampholytic suriactants are surface-active compounds that, in addition to a C5-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 capabre of forming internal salts. Examples of suitable arnphol ytic surlactants include N-alkylglycines, N-alkytpropionic acids, N-alkylaminobutyric acids, N-alkyliniinodipropionic acids, N-hydroxyethyl-N-alkylaniidopropylglycines N-alkyltaunnes. N-alkylsarcosines, 2-alkylaminoprop ionic acids and alkylaminoacetic each having approxImately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference Is given are N-cocoalkylaminopropionate1 cocoacylaminoethylammnopropionate and C12-C 18acylsaroosne Suitable non-ionic suriactants are described In WO 00/10519, especially p. 45, I. 11 to p. 50, I, 12 Non-Ionic surtactants contain as hydrophic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such so compounds are, for example -addition products of 2 to 30 mol of ethylene oxide and/or 0 to S mol of propylene oxide with l,ar fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms and with alkyiphenots having 8 to 15 carbon atoms in the alkyl çroup, -28 - -C12-C22 fatty acid mono-and di-esters of addition products of 1 to 30 rnol of ethylene oxide with glycerol, -C-Calkyl-mono-and -oligo-glycosides and ethoxylated analogues thereof, -addition products of 5 to 60 niol of ethylene oxide with castor oil and hydrogenated castor oil, -addition prod ucts of ethylene oxide with sorbitan fatty acid esters, -addition products of ethylene oxide with fatty acid alkanolarnides.</p>

<p>The surfactants which are addition products of ethylene andior propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a "normalTM homologue distribution or products having a restricted tiomologue distrIbution, "Normal" homologue distribution are mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts.</p>

<p>The use of products having restricted hornologue distribution may be preferred.</p>

<p>Examples of cationic surfactants that can be used in The dyeing compositions according to the Invention are especially quaternary ammonium compounds. Preference is given to am monium halides, such as alkyltrimethylarnmonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylainmonium chlorides, for example cetyltrlmethylammonlum chloride, stearyltrirTlethylammoniurri chloride, distearyldimethy-larnmoniurn chic ride, lauryldimethylammoniurn chloride, lauryldimethylbenrylanimonium chloride and tricetyl-methylarnmoniurn chloride. Further cationic surfactants that can be used in accordance with the invention are quaternised protein hydrolysates.</p>

<p>Also suitable are cationic silicone oils, such as, for example, the commercIally available pro-ducts Q2-1224 (manufacturer: Dow Corning; a stabilised trimethylsilylarnodiniethicone), Dow Corning 929 emulsion (comprising a hydroxylamino-rT'iodified silicone, which is also referred to as amodimethicone), $M-2059 (manufacturer: General Electric), SLM55067 (manu-facturer; Wacker) and also AbiP-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt: -29-dlquaternary polydimethylsiloxanes, qua terniurii-80), or silicones, as described in WO 00/12057, especially p. 45, I. 9 to p. 55, I. 2.</p>

<p>Alkylamidoamines, especially fatty acid amidoamines, such as the slearylamidopropyldi-methylamine obtainable under the name Tego Amid@18 are also preffered as surlactants in the present dyeing compositions. They are distinguished not only by a good conditioning action but also especially by their good biodegradability.</p>

<p>An example of a quaternary sugar derivative that can be used as cationlc suits ctant is the commercial product Glucquat1OO, according to CIFA nomenclature a "lauryl methyl gluceth-1 0 hydroxypropyl dimonium chloride'.</p>

<p>The alkyl-group-containing compounds used as surlactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.</p>

<p>A further embodiment of the present invention relates to the dyeing ol keratin-containing fibers.</p>

<p>The processes comprises (a) treahng the keratin-containing fiber with at least one dye of Formula (is), (ib) and (Ic) and (b) leaving the fiber to stand and then rinsing the fiber The dyes of formula (Ia). (ib) and (ic) are suitable for all-over dyeing of the haLr, 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.</p>

<p>The dyes of formula (la), (lb)and (ic) are applied on the hairfor 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.</p>

<p>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 10 be obtained.</p>

<p>Further preferred is a process for dyeing keratin-containing fibers which comprises treating the keratin-containing fiber with at least one dye of formula (1 a), (Ib) and (ic)1 a base and an oxidizing agent A preferred embDdirnent for dyeing keratin-containing fibers, in particular human ha+r, w1th a dye of formula(la), (lb)and (Ic) and an oxidizing agent, comprises a,) treating the keratin-containing fiber with the ocidizing agent, which optionally contains at leastone dye of forrnula(la), (lb)and (ic), b1) treating the keratin-containing tibe with an oxidizing agent free composrtion, which optionally contains at least one dye of formula (Ia). (ib) and (Ic): or alternatively a4 treating the keratin-containing fiber with an oxidizing agent free composition, which optionally contains at least one dye of formula (Ia), (ib) and (Ic), b2) treating the keratin-containing fiber with an oxidizing agent, which optionally contains least one dye of formula (la), (1 b) and (ic), with the proviso that at least in one of the process steps a1), a2), b1) orb2) a dye of tomiula (la), (lb)and (lc)is present.</p>

<p>In general, the oxidizing agent containing composition Is left on the fiber for 0 to 45 minutes, in particular for 15 to 30 rriinutes at 15 to 45t.</p>

<p>The oxidizing agent free composition usually comprises customary adjuvants and additives.</p>

<p>Preferred are those, which are described in German Patent Application, in ccl 3, 1. 17 to I. 41.</p>

<p>In general, the dye ci formula (Ia), (1 b) and (ic) and the oxidizing agent free composition are left on the fiber for 5 to 45 minutes, in particular for 10 to 25 minutes at 15 to SODC, One preferred embodiment of the process is to wash the hair after dyeing with a shampoo ani/or a weak acId, such as citric acid or tartrate acId.</p>

<p>The dyes of formula (Is), (lb) and (lc)which are stable to reduction can be stored together with the oxidizing agent free compositions and may be applied as a single coniposition.</p>

<p>Advantageously the compositions comprising a dye of formula (la), (ib) and (lc) which are not stable to reduction are prepared with the oxidizing agent free composition just before the dyeing process.</p>

<p>In a further embodiment, the dye of formula (is), (1 b) and (Ic) and the oxidizing agent free composition may be applied simultaneously or in succession.</p>

<p>Customary, the oxidizing agent containing composition is evenly applied in a sufficient amount related to the amount of hair4 usually in amounts of 30 to 200 g.</p>

<p>Oxidizing agents are for example persulfate or dilute hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkal. earth metal peroxides, organic per-oxides1 such as urea peroxides, melarnine peroxides, or alkalirnetalbromat fixations are also applicable if a shading powder on the basis of semi-permanent, direct hair dyes is used.</p>

<p>Further preferred oxidizing agents are -oxidizing agents to achieve lightened coloration, as described in WO 97/20545, especially p. 9, I. S to 9, -oxidizing agents in the form of permanent-wave fixing solution, as described in E-A-19 71 a 698, especiaffy p. 4, I. 52 to 55, and I. 60 and 61 or EP-A-1062940, especially p. 6, I. 41 to 47 (and in the equivalent WO 99140895), Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration from about 2 to 30 %, more prsferably about 3 to 20% by, and most preferably from 6 to 12% by weight the corresponding composition.</p>

<p>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 3 %, based on the total dyeing composition.</p>

<p>In general, the dyeing with an oxidatlve agent is carried out in the presence of a base1 for example ammonia, alkali metal carbonates earth metal (potassium or lithium) carbonates, alkanol amines, such as mono-, di-or triethanolamirie, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula R p N-P-N, wherein R is a propylene residue, which may be substituted with OH or C1-C4aikyl.</p>

<p>R, R4, R5 and R are Independently or dependently from each other hydrogen, C1-C4alkyl or hydroxy-(C-C4alkyl.</p>

<p>The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in padka4ar about 2 to 5 One preferred method of applying formulations-comprising the dyes of formula (la}, (Ib) and (lc) on the keratin-containing fiber1 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.</p>

<p>The first compartment contains for exarnle at least one dye of formula (la), (ib) and (Ic) and optionally further direct dyes and a basifying agent. and in the second compartment an oxidizing agent; or in the first compartment at least one dye of formula (la), (ib) and (ic) and optionally further direct dyes, in the second compartment a basifiying agent and in the third compartment an oxidizing agent.</p>

<p>Preferably, a ready-to-use composition is prepared according to a first preferred embodiment by a prooess which comprises a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenedlamines and bis(phenyl)- alkylenethamines, and the acid-addition salts thereof, at least one coupler, especially selec-ted from meta-phenylenediamines and the acid-addition salts thereof, and at least one dye ci formula (la), (ib) and (Ic), on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing (A) and (B) together immediately before applying this mixture to The keratin-containing fibers.</p>

<p>According to a second preferred embodiment for the preparaUon of the ready-to-use dye composition, the process includes a prerirninary step which involves separately storing, on -33 -the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenedianiines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from rneta-phenylenediamines and the acid-addition salts S thereof; on the other hand, a composition (A') comprising, in a medium which is suitable tor dyeing, at least one dye of formula (la), (1 b) and (lc), and finally, a composition (B) containing, In a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use immediately before eppfying this mixture to the keratin-containing fibers.</p>

<p>The composition (A') used according to this second embodiment may optionally be In powder form, the cationic dye(s) oF formula (1 a), (1 b) and (1 c) (themselves) constituting, in this case, all of the composition (A') or optionally being dispersed in an organic and/or inorganic pulverulent excipient.</p>

<p>When present in the composition A', the organic excipient may be of synthetic or natural origin and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or unmodified starches, as well as natural poducts such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.).</p>

<p>When present in the composition (A'), the inorganic excipient may contain metal oxides such as titanium oxides, aluminIum oxides, kaolin, talc, silicates, mica and silicas.</p>

<p>A very suitable excupient in the dyeing compositions according to the invention is sawdust.</p>

<p>The powdered composition (A') may also contain binders or coating products in an amount which preferably does not exceed approximately 3% by weight retative to the total weight of composition (A'). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant origin.</p>

<p>The composition (A') may optionally contain other adiuvants, ri powdered rorm, in particular surlactants of any kind, hair conditioners such as, for example, cationic polymers, etc. -.34-Generally the hair is rinsed after treatment with the dyeing solution anwor permanent-wave solution.</p>

<p>A further preferred embodiment of the present InventIon relates to a method of dyeing hair with oxidative dyes, which comprises a, mixing at least one dye of formula (la), (ib) and (Ic) and optionally at least one coupler compound and at least one developer compound, and an oxidizing agent, which optionally contains at least one further dye, and ft contacting the keratin-containing fibers with the mixture as prepared in step a.</p>

<p>For adjusting the p H-value organic or inorganic acids, as for example described in DE 199 59 479, ccl 3, L 48 to I. 53 are suitable.</p>

<p>Furthermore, the present invention relates to a process of dyeing of keratin-containig fibers of the dyes of formula (la), (1b)and(Ic)withautoOxideble compounds and optionally further dyes.</p>

<p>The process corn prlses a. mixing at least one autooxidable compound and at least one developer compound and at least one dye of formula (la), (ib) and (ic) arid optionally further dyes, and b. treating the keratin-containing fiber with the mixture prepared in step a.</p>

<p>Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the dyes of formula (Ia), (1 b) and (1 a) and capped diazotised compounds, which comprises1 a. treating the keratin-containing fibers under a!kaline conditions with et least one capped diazotised compound and a coupler compound, and optionally a developer compound ad optionafly an oxidizing agent, and optionally in the presence of a further dye, and cptionaUy with at least one dye of formula (la) (lb)and (ic), and b adjusting the pH in the range of 6 to 2 by treatment with an acid, optionally in the presence of a further dye, and optionally at least one dye of formula (Ia), (ib) and (ic), with the proviso that at least in one step a or b. at least one dye of formula (Ia), (1 b) and (Ic) is present.</p>

<p>The capped diazotised compound and coupler compound and optionally the oxidizing agent and developer compound can be applIed in any desired order successively or simultaneously.</p>

<p>Preferably, the capped diazotised compound and The coupler compound are applied simultaneously, in a single composition.</p>

<p>"Alkaline conditions" denotes a phi in the range from 8 to 10, preferably 9-10, especially 9.5- 101 which are thieved by the addition or bases, for example sodium carbonate, ammonia or sodium hydroxide The bases may be added to the hair, to the dye precursors, the capped diazotised compound and/or The water-soluble coupling component, or to the dyeing compositions comprising the dye precursors.</p>

<p>Acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.</p>

<p>The ratio of the amount of alkal. dyeing composition applied in the first stage to that of acid dyeing composition applied in the second stage Is preferably about from 1:3 to 3:1, especially about 1.1.</p>

<p>The alkaline dyeing compositions of step a. and the acid dyeing compositions of step b. are left on the fiber for 5 to 60 minutes at 15 to 45t, In particular for 5 to 45 minutes at 20 to 30 C.</p>

<p>Furthermore, the present invention relates to $ process for dyeing keratin-containig fibers with the dyes or formula (la), (1 b) and (ic) and at least one acid dye.</p>

<p>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 dyed.</p>

<p>Preparation Examples</p>

<p>Part A: Poivethylenirnine based The exaaipies Al to A28 are prepared by reacting one of the polyethyleneimines PEI 1 to PEI 5 with one of the dyes Dye 1 to Dye 5. The reaction mixtures are worked up by one of the workup procedures 1 to 5 The reaclion conditions and workup prooedures for each example are given in table 1. The analytical data forthe products are given in table 2.</p>

<p>Polyethyleneiniines used Wi examples Al to A28: PEI 1 with an average molecular number weight (Mn) of 423 g/rnol PEI 2 with an average molecular number weight of 600 gFmol PEI 3 with an average molecular number weight of 1200 g/nioi PEI 4 with an average molecular number weight of 1800 g/mol PEI 5 with an average molecular number weight of 10000 glmol Dyes use in examples Al to A28: -.</p>

<p>Dyel -Cl -/\ / Dye2: -. c ---</p>

<p>I</p>

<p>Dye3: -----ci -/ t -37 -Dye4: -9 \Q_J,N Cl Uye: -a pio Ci Dye / \ I</p>

<p>-</p>

<p>Workup Procedure 1: After cooling the reaction mixture is evaporated to dryness.</p>

<p>The powder is taken in successively in acetone and dichloromethane, filtered off, washed with the same solvent and dried. FinaLly the product is dissolved In ethanol and dried again.</p>

<p>Workup Procedure 2.</p>

<p>The reaction mixture is cooled to room teniperature and the solvent is evaporated to dryness-The obtained oil is dissolved in methanol and the solution is dropped into acetonitrile. The precipitate is filtered off and dried under vacuum.</p>

<p>Workup Procedure 3: The maclion mixture is cooled to room temperature, the product is filtered off and dried in vacuum.</p>

<p>Workup Procedure 4: The reaction mixture is cooled to room temperature and 1 eq. of hydrochForic acid (relative to the amount of dye) Is added. The precipitated product is filtered off and dried in vacuum.</p>

<p>Workup Procedure 5; The reaction nixture is cooFed to room temperature and the solvent is evaporated to dryness.</p>

<p>The residue is dissolved in ethanol and filtered The solvent of the filtrate is a9ain evaporated and the remaining product is stirred in isopropanol and dried.</p>

<p>Table 1: Reaction conditions for the examples Al -A28 Mn (PEI) is the average molecular number weight of the polyethyleneirnine. The dye equivalents are given relative to the number of PEI nitrogen atoms.</p>

<p>Table 1</p>

<p>Exanjpj MnPE1) EaDv Solvent rLtl re Worku y Proiuct Procedure Al 423 Dye 1 0,5 isoprop 55-60 23h 1 104 red A2 423 Dyel I isoprop. 60 22h 2 17 red water AS 422 Dyel 1 60 50h 2 15 red (pH7-9) A4 423 Dyel I MeCH 60 24h 2 13 red AS 423 Dye 2 0,5 isoprop. RT 24h 71 red A6 423 Dye2 I oprop RT 24h 3 73 red AT 423 bye 1 0.5 isopro --60 -24h 4 65 red A8 42à Dye 1 0.25 isopro 60 24h 4 91 red A9 -423 DyeI 0l 3soprop. 60 24h 4 88 red ____________________ -. water AlO 423 Dye 1 05 40-60 24h 5 58,2 red (pH 11.5) All 423 Dye3 031 AeON i 55 24h 1 130 violet Al 2 423 -Dye 3] 0.5 AeON 55 24ti 1 122 violet A13 600 Dyel' I MeOl-1 60 225h 2 red A14 600 Dye2! 1 isoprop. 40 22h 3 51 red MS 600 Dye 1 0.5 isoprop 60 20li 4 --23 red AI6 -1200 Dye i: 025 -iiprb. 55-60 24h 1 105 red All 1200 Dyel 1 MeOH 60 24 2 23 red A19 1200 Dye2 1 isoprop. 40 22h red A19 1800 Dyel -C38 Liji_prap. 1 -red A20 1800 Dye 1 1 MeOH 60 24 2 26 red P21 1800 -Dye2 I jisoro. 40 2211 -3 i red A22 10000 Dye 2 1 isoprop 40 -22lt 3 -36 red P23 423 Dye41 0,5 E1OH 78 193b 2 58 orange -39 - iiSe I -Example Mn(PEfl Qw EQ Dye olvent T "Ci Tsme Workt& Product Procedure --Color A24 600 Dye 5 b',5 BuOb 60-100 2511 4 28 yellow A25 600 DyeS 01 RuOH 100 C 21h 192 88 yellow A28 600 byeS 025 1 BuO 100 C 21h 088 61 -A27 423 DyeS 015 B.iOH -. 100 C 22h 0,21 12 yellow -A28 423 Dye 6 0,1 j CHCI3 40'C Oh -0 07 63,U yellow Tab = Analytical data for examples Al -A28. The ration n(Dye)/n(Npci) is the ratio of poly-mer bound dye molecules to the total number of nitrogen atoms in the polymer Exsmple Mn (GPCRI) (w3ter I H nmr (D20), Qnrn) n(Dve)/n(N1 Al -485nm (m, 2H)j,5(m. 21-I), 6,9 (m, 2H), 2,64.5 ______ ____ ____ (m,1ftDMSO-d6 --j A2 2937 490nni 62-8.1 (lx, 611), 26-.41 (br, 13H) -0,63 -AS -1980 4B7nrn V{brrn,2H), 7,3{brm,2H), 78(brrn,2H) 016 A4 3506 4QSnm 2-8,1 (br, 611), 2,2-4I0 (br, 1311) 0,63 7 7 (rn, 214), 7,3(m, 211), 68 (m, Il-I). 6.6 (m, AS 3145 49mm 1H),2.6-4.1(br,14H) ---____________ 7.5 (m, 21-1), 7.1 (m, 211), 6.5 (m, 211). 2 5-3 7 0,61 A6 3567 493nm (br, 13H1 -_______ A7 2491 466 nm 7.8 (p1, 2H), 7 3 (rn 211), 6.7 (ni, 211), 2.6-4.1 _________ _____ (br,13.</p>

<p>7.8 (m, 211). 7 3(rn, 211), 6.8 (rn, 2H). 2 8-&9 A8 -485nm ______ -iL?'!!1) -_____ _________ 7.7 (rn, 211), 7.1 (ml 2H), 6.6 (m, 211), 2 5-3.9 -488nm -____________ ______ br, 4911) _______ 7.9 (br, 211), 7 3 (br, 211)68 (Lw, 211), 4Q1 2.6 0,09 AlO -494nm</p>

<p>______ _____ ______________ -</p>

<p>All --S2Onm -I --- 7.8(rn, 1H), 7.5-7.7(m, 3H). 7 l5(rn, IH), A12 -527nm 6,85(rn, 111), 41(rn, 611). 26-31(br, 8H), 3.3(s, - __________ ____ ______ 31-1) _______________ EAI 3 3605 488 nrn 6.5-7,5 (br, 411), 6,1 (m, 2H), 1.9-3M (br,1 311) 0,55 A14 4819 494 rim (ir. 211), 7.3 (rn, 2H), 6.7 (in, 21-I), 2.6-4.0 _____ ____ ____ (br,14H) ____________ 0,51 485 7.5 (in, 211), 7.1 (m, 211). 6.5 (m, 211), 2.5-3 9 -.</p>

<p>A15 6240 _________ ___________ (water) 14H) -. 0,48 7,9 (m, 2H), 7 5 (m, 21-1), 68 (rn, 2H), 4.0 (m, 611), 23-3.5 (bc, 1711) in MeOH44 0. 23 A16 - _______ _____---73(rn, 2H), 7.1 (m.211),64 (m, 2H), 2A-3i All 5341 488nm __________ --(br,17H) -- 7.6 (ni, 2H), 7 2 (in, 211), 6.6 (m, 214), 2.6-4.0 0,4 A19 - ________ ___________ (br, 16H) A19 -4670 J 7.0-6.1 (br, 4H), 65 (m, 214). 2A-3 9 (br, PH) 0,35 -A20 5548 I 486nrn 7.0-8.1 (br, 4H), 6.5 (ni, 2H), 2.4-39 (tir. 19H) -0.32 A21 7284] 490nm 7.6(m.2H), 72(rn, 211), 6.6 (rn 2H),2.5-4.0 0.36</p>

<p>-</p>

<p>!xmp1e Mn (GFc.31) 1 (waLer) IH nmr (020). 5 (ppm) n(Dye)/n(NpI ____--______ -(br,17H) --A22 11814 488nm 78(m,2H)72(m,2H).65(m.2H).2.440 042 ___________ -_______ (br3 1 6H) -- 8.3 (m, 2H), 7 5(m, 6H), 6.7 (m, 2H), 4.0 (m, -A23 32ö9 452 nrn ________________ _____ 3H, 2.4-38 (br, 22H) ___________ A24 -419nm 8.5-6.9(br, 1Ol-t),2.S-46(br22H) ----0,27 A25 -421 nm 8.5-70(br, 1OH),4.5-2(br, 52H) -. 0.1 _A28 _________ 420 rim 8.5-1.O(br, IQH). &8-23(br26H) 0,2 A27 -423 nm 8.2 -7.1 (br m, 8H), 6.? (br fli, 2H). 4.0 -32 (br 0 28 __________________ rn, 20 H) A28 -419 rim 8.4-69(br, IOH),4,4(tar, 2H), 35(s, 3H), 3.3 0,08 I ___________ -(br, 2H), 2.8 -2 3 (br, 53H), 2.1 (br, 2H) ______ _____________ Part B: Polysiloxane baae $amDle A-2t + (1</p>

<p>N N</p>

<p>N</p>

<p>F-I I</p>

<p>4.75g of aminopropyflerminated polydirnethylsiloxarie ABCR (0,005 mol) are suspended in 1 Sri isopropanol and 2.67g of 2-(4-Methoxy-pheflylazo)-1,3-dimethyl-3-irrlidazol-1 -lurn (am dye A) are added. The reaction mixture is heated to 5&C for 24h. After cooling the reaction mixture is dried, taken in 6Ornl chiorofomi and washed 3 x with 40m1 water/acetic a;id.</p>

<p>The organic phase isdnied again giving6g ota red powder (Yield 81%).</p>

<p>NMR in CD2CI2 in ppm: 7.1. br, 21-I; 73 br, 2H; 6.8, br 21-1; 62, br, 1H; 3.9, s. Sd: 3.25, s, 2H; 17, hr, 2H; 0.6, br, 21-1; 0, Lw, 62H XmBxPfl MeOH = 518 rim Exarnole A-3D:</p>

<p>____</p>

<p>-f-±o J[ JO-fr Toluene _?i+0 U Ptcat.</p>

<p>HN</p>

<p>To a solution of 7.5 ml of methylhydrosiloxane-dimethylsiloxane copolymer [68037-592] (Gelest F-IMS 301; MWI900-2000, 25-30 mol% S1H, d O.9S; 30 mmol eq.) in 35 ml of toluene 2.25 ml of allylamine (30 rimol) and 200pPof platinium (0)-I,3-divinyl-1,1,3,3-tetramethyldisiloxane complexe in xylerie [68476-92-2]. The reaction mixture is agitated for 3 days at 55CC and then evaporated to dryness to give 8.85 g polymer.</p>

<p>MNR in DCM in ppm: 2.5 (t, 21-1), 1.6 (br. 2H ); 1 4 (br, 2H); (}4 (t, 2H)</p>

<p>Example A-SI: oQ N1</p>

<p>_o+ro_frfi_o ti_ FrOH.60t -i-o±o-4-o} rN 942 mg of polysiloxane A-3D are taken in 15 ml isopropanol and reacted with 1.66 g of2-(4-Methoxy-phenylazo)-1,3-dimethyl-3-irnidezol-1-iurfl (azo dye A)for 16 Ii at 60t. After evaporation of the fsoproparinl under vacuum, the reaction mixture redisolved in 40 ml DCM (2 mm in ultrasonic bath) and 40 ml water (2 mm in ultrasonic bath). The emulsion 0CM! water is left overnight The 0CM and water phases are separated, leaving a viscous phase which is again treated with DCM and water (same procedure as above). The viscous phase is then taken in 10 ml methanol and dried under vacuum (imbar) to give 598 mg of a red solid NMR: 1 H in MeOh 7M(ni, 2H}, 7,4(ni, 2H). 61(m, 2H), 3.9(m, 6H), 3.2 (rn, MeON + 2H).</p>

<p>1.65(rn, 21-4), 0(m, 30H) F' C: Polyethprimine based</p>

<p>V</p>

<p>IPrOH or H2N+LOL * 75t.24h Xp-0Me, o-F V = Ci, MS03 -pora: A-32 orttio:A-33 -1'</p>

<p>Example #32;</p>

<p>Reaction of poly( propyleneglyool}bis(2-amifloprOPYlether) with 2-(4-Methoxy-phenylezO)-13-dimethyl-3H-imidazOl-1 -iuni chloride: 2g (0.0044 eq moWN) of poly(propyleneglycol)bis(2-amiflopropylether) (from Aldrich CAS (9045-10-01 MW 456) are reacted with 266g (O1Olmol) of 2.<4-rnethoxy-phenyLazo)-1 3-dimettiyl-3H-btidaZal-1-iUm chloride in 14 ml Isopropanol from 55 to 80 C for 21h. After cooling, the reaction mixture is evaporated to dryness. solubiliseci in lOOmI dichloron'iethane and washed 3x with 25m1 water and soda to give after evaporation at the organic phase 3,lSg of the expected red polymer (yield 63%).</p>

<p>NMRin DM50 in ppm: 7.4, br, 11-I; 715, s, IH; 6.6,br, U-I; 3.75, S1 3H; 3.2-31, br, IOH; 1.1, br, 9H X4PLEX in MeOH = 503 mm -43-</p>

<p>Example #33:</p>

<p>Reaction of pa ly( propylenglycol)bis(2 -amiriopropylether), with 2-(2-Fluoro-phenylazo)-1 13 dimethyl-3l-l-imidazo-1-lvm sulfonate: 1 g (0.0044 eq.rnol/N) of poiy(propylenglycol)bis(2-aminopropylether) (from Aldrich CAS [9046-10-0] MW 456) are reacted with 1.92 g (O0O44 rnol) of 2-(2-fluoro-phenylazo)-13-dimethyl-SH-imidazol-1-Iurn surfonate in 6 ml acetonitrile at 75 C for 24ft After coohng, the reaction mixture is evaporated to dryness, solubilised in lOml dichiororriethene and washed 3x with 25m1 water to give after evaporation of the organic phase 1.56g of the expectS violet polymer (yield 67%).</p>

<p>NMR in CHCI in ppm: 9.3, br 1H; 8, br, 2H, 7.65, d, 1H, 7.4, t, 1H, 6.7, br, 1H, 4.1, s, 6H; 3 1-38, br, 231-I; 1.3. br, 51-I; 0 9-1.1, br, IBH ?vrruw in MeOH = 531 mm</p>

<p>Example A-34; MaN</p>

<p>+ -o--Q-\_ WC4h ci CI p Reaction of Trirnethloylpropanetris[poly(propyleriglycol)amin terrninatedj ether with 2-(4-Methoxy-phenylazo)-1 13-dirnethyl-3H-imidazol-1 -iuni chloride: 1 g (0.00631 moIf N) of trirnettiloylpropanetrlspoly(propylenglycol)amin terminated] ether from Aldrich GAS [39423-51-3] are reacted with 1.68g (0,00631mo1) of 2-(4-mettloxy-phenylazD)- 1,3-dimethyl-3H-imidazol-1 -ium chloride in lml isopropariol at 80C for 24k After cooling the reaction mixture is evaporated to dryness. solubilised in 7bnil dichloro-methane and washed 3x with 25m1 water to give after evaporation of the organic phase 2.23g of the expected red polymer (yield 90%).</p>

<p>-44 - NMR in CD2CI2 in ppm: 7.6, br, 3H; 6.8, br, 2H, 6.5, br, 2H; 6.3, 8, 2H; 2.6-3.9, br, 25H; 0.6- 1.4,br, 14H in MeCH = 518 rim Exam le A-35 A suspension of 0,Sg copolyglycidylmeLacrylate-butylacrylate (1.72mrnol epoxy eq) in 1 ml acetonitrile and 4m1 isopropanol is heated to 65 C until dispersion of the polymer.</p>

<p>0,559 of 2-(N.N -4-(methyl-(2-methyla ml no-ethyl)-amino]-phenyl no)-1,3-diniethyl-3H-pn'iidazol-l-ium chloride (1.72rrimol) are then added at 40CC and the reaction mixture is heated again at 60 C for 40h.</p>

<p>After cooling the reaction mixture is evaporated to dryness, taken in brine and the polymer is extra cled in dichloromethane.</p>

<p>White salts are filtered off and the organic layer is evaporated and dissolved in methano! The rest of solid is filtered off and the solution evaporated to give ig of a dark red powder.</p>

<p>NMR in MeOD in ppm' 7,9; br, 2H; 7,5, s, 2H; 6.95, br, 2H; 4, br, 121-1; 3,5-3-9, br, 3H; 311 3,3, hr, 6H(+MeOD); 2,7, br2H; 25, br, 2H: 2,4, br, 41-i; 16. br, 3H; 0-7-1.5, br,121-1</p>

<p>Example A-36:</p>

<p>CI + N.-</p>

<p>-</p>

<p>CI N -;N Fl</p>

<p>K</p>

<p>1.06g copolyacrylic acid-butylacylate (19.5% solution n dioxan (1.6mmol eq. COOK)) are diluted in SmF aoetonitrilt O.5g N-ethyl-N-(3-dirnethylamiopropyt)carbodiirT'iid (3.2rnrnol) are added and the reaction mixture is cooled to 5 Ck After 45mm O.52g 2-(N, N-4-Lmeth yl-(2-rnethylaminc -ethyl)-aminol-phenylazo)-1, 3-dimethyl-3l-{-imidazol-1-iuni chloride (1.6rnmol) and cL4Sg pyrldine (4.Snirnol) are added and the reaction rrtixture is then agitated at room temperature for 18h. -45 -</p>

<p>After evaporation of the solvents the powder is washed with ethylacetate and dried to give 0.74g of a dark red powder.</p>

<p>NMR In MeOD in ppm: 1191 br, 2H; 7,5, br, 21-I; 6,9, br, 2H; 3191 br, 81-I: 3,6, br. 4H; 25-3,4.</p>

<p>br, 23H; 0,7-20, br, 16H B. Aoollcaton Examples: For the application examples the following hair types have been used: -I blonde hair tress (VIRGIN White Hair), -1 middle blonde hair tress (UNA-Europ. nature hair, Color middle blonde), -I bleached hair tress (UNA-Europ nature hair, Color white bleached).</p>

<p>Coloring Solution: 01 % wiw of one of the dyes described in examples Al to A28 were dissolved in a Plantaren solution (10 % wlw Plantacare 200UP (ID: 185971.5) in water, pH adjusted to 9.5 with 50% citric acid solution or monoethanolamine solution). For some examples different solvents or solvent rriixtures have been used, which are given in Table 3.</p>

<p>The hair tresses are dyed according to the following procedure: The coloring solution was applied directly to the dry hair, incubated for 20 mm. at room temperature, and then rinsed off under tap water (water temperature: 37 C +/-1 C; flow rate of waLer: 5-6 l/minj. Then it is pressed out with a paper towel and dried over night at room temperature on a glass plate.</p>

<p>To determine the wash fastness two sets of hair tresses are dyed under the same conditions.</p>

<p>One set of the dyed tresses is washed with a commercial shampoo (GOLDWELL delinition Color & Highlights, color-conditioner shanpoo) using approx. 0.5g shampoo for each tress under tap water (water temperature: 3,7 C tI_ I D(. flow rate 5-6 Flmin). 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 is repeated 10 times.</p>

<p>Then the color loss of the set of washed tresses relative to the set of unwashed tresses is evaluated using the Grey Scale according to: Industrial Organic Pigments by Herbst&Hunger, 2nd ed., p. 61, Nr 10; DIN 54001-6-1982. ,Herstellung und Bewertung der Anderung der Farbe, ISO 105-A02-lgga.</p>

<p>Table 3: Results for Application Examples 81 -B31 Hair --Examole Qy Solvent jj Color Intensity Brilliance fastness Bi -Al Water (pH 6$) blond red good good 3 _________ -middle red good good 3 I _________ ________ ________________ blond _______ ________ ______________ bleached red good good 3-4 Plantaren IWater 32 Al blond red good good *1 ____ ______ _______ _______________ middle red good good I 3 _______ ____________ blond ______ ________ _________________ ______________ bleached red good good 3-4_ -A2 Coloring Solution blond red good good 4-5</p>

<p>_____________ ________________ __________________________________ _________________ _______________ __________________ -I</p>

<p>middle red good good 45 ______________ blond ______ ________ ________ _______ --bleached red -good good 4 PlantarenIMBOH blond red good good 4 B4 AZ _______ 3'l ______ _______ ________ ________ _________ ______ _________--middle red good good 4 blond ________ ________ _______ --bleached red good -good -4</p>

<p>-____</p>

<p>43 Coloring Solution blond red good good 4-5 middle red good good 4 blond _______ ________ _________ ________ _____________ bleached -red good good 3-4 red- 86 44 Coloring Solution blond brown good good 4 middle red-good good 4 blond brown ________ -.</p>

<p>bleached ______________ brown good good 3-4 87 AS ColorIng Solution blond red I good good 4 middle --red good good 4 ________ blond _______ ________ _________ _________ _______ -bleached red -good 1 good 68 46 Coloring Solution blond red good good 4 _____ _______ ______________ --______ _______.1 -_______ middle red good I good 4-S _________________ blond _______ _________ _______ ______----bleached -red good -good 4 -4-,------.---Table 3: Results for Apphcatiwj Exarnoles 81 -831 _________ ______ --Hair --_______ Example Dy Solvent Color Intensity Brilliance Plantaren Solution 09 A7 blond red good good 4-5 ___________ ________ (pH 515) -________ _______ ________ -________ middle red good good 4-5 _______________ blond _____ ________ ________ _______________ teched red good good 4 BlO AS Coloring Solution blond ed good good 4-5 middle red good good 4 blond _______ ________ _________ ________</p>

<p>_--_ --_</p>

<p>bleached red good good _3-4 -.... --Bi 1 A9 Coloring Solution blond red good good 4 middle -red I good r good 4-5 _____--blond ___________ _________ _____ ---bleached red good I good 3-4 B12 AlO Coloring Solution blend red good good 4-5 I I middle ________________ ______________ blond -red [ good good 3-4 _______________________ bleached red good good 4 813 All Water (ph 6P9) blond violet good good 3 I middle violet good good 3-4 I blond _______ ________ _________ ________</p>

<p>I ---________________________ ______________________</p>

<p>I _____________ bleached violet good good 3 914 All ColorIng Solution blond violet good good 3-4 mIddle violet good good 3 ______ blond _______ ________ ________ _____ ---bleached violet good good 3 - Plantaren mater -B15 A12 blond violet good good 3 1:1 _________ _______ _____________________ middle violet good good 3 blond _______ ___________ _________ -bleached _vLolet good good - 3-4 red- * B16 Al 3 Coloring Solution blond brown good good 4-5 middle red- * blond brown good good 45 red-bleached brown good good 4 HB17 -A14 Coloring Solution blond good good 3-4 brown _______ ---________ --middle red-' blond brown -good I good 4 --I -______ bleactiedred-IgoodjgOOd 3-4 Table 3: Results for Application Examples Bi -B31 fElL Wask Example py Solvent Color Irnerisity Brilliance fastness -_____ _____ brown __________ BIB Al 5 Coloring Solution blond red good good i 4 mddle _______________ blond red good good 4-5 ________ -bleached red -good good 819 A16 Water (pH 8,3) bleached copper good good L 2-3.</p>

<p>copper good good 3-4 _______ --____________ bleached copper good good, 4 red-B20 A17 Coloring Solution blond good good 3-4 _____ ________ brown ________ __________________ middle red- _______ _____ blond brown good good L H---bleached brown good good 3-4 * B21 A19 Coloring SolutIon blond bn good good 3</p>

<p>___________ _______________ -</p>

<p>__________ --middle red-good good 4 5 blond Jbrown _______ ___________________ I bleached brown good I good 1 4 -A19 Water/Methanol4:1 blond red good good 3 P2-middle I _______________ blond red good good 3 _______-. --____ bleached _red good good 3 B23 A20] Coloring SoP red-ution blond good good 4 brown _________ * middle red-I _______________ blond brown good goOd 4-5 bleached brown good good 3-4 B24 A21 Colorrng Solution blond good good -_2-3 middle red- _______________ blond brown good 4 -. --_____ bleached good good 4 - 825 A22 Coloring Solution blond red-good good 3 brown __________</p>

<p>_______________ ______________ ---_______________ --________________ ----</p>

<p>middle red- ________________ blond brown good good 4 * ________ eached brown good -good -4 1 826 * A23 Coloring Solution blond orange good good S</p>

<p>_____________ ----____ ______ _____ ______ I ______ -49-</p>

<p>Table 3: Results for Application ExarnpiesBl-B31 I Wh -Exam* Qy Solvent] Qp!cr InLensity d!!e fastness _______________ re orange good good 5 -bleached 1 orange good I good 4-5 B27 A24 Coloring Solution blond yellow good good 4 Yellow -good good 4-S -______________ bleached yellow good good 4 B28 A25 Coloring Solution blond yellow good good 3-4 yellow good good 4 _________ -. -bleached yellow good good a R29 A26 Colonng Solution blond yellow good good 4 _______ _______________I yellow good good 4-5 -__ -hedyeRowgoOdgood3J B30 A27 Coloring Solution blond yellow moderate moderate 4-5 I middle ---I - _______________ blond yellow moderate moderate 45 ---. bleached yellow moderate moderate 3-4 B31 A28 Coloring Solution blond yellow good good 4 -middle blond yellow good good 45 _________________ --bTii yellow good good 3-4</p>

<p>Example B32</p>

<p>0.1% of compound at formula A-29 is dissolved in a 10% solution of a non-ionic surfactant (Plantacare 200UPr Henkel) adjusted to pH 9.5 using citric acId or monoetrianolarnine. This red dyeing solution is applied on the dry hair (two blond, two middle blond and two damaged hair strands) and allowed to stand for 20mm at room temperature. Then, the strands are rinsed under tap water and dried I 2h.</p>

<p>PartBB: Results: Hair Type Color Intensity Brllance] WsshingFastness -Blond red -good good L 1-2 Middle blond red -good good 2-3 Damaged red good good 3 -50-çple 033: 0 1% at compound of formula A- 31 is dissolved in a 10% solution of a non-ionFc surfactant (Plantacare 200UP, Henkel) adjusted to pH 9.5 using citric acid or monoethanolamine. This red dyeing solution is applied on the dry hair (two blond, two middle blond and two damaged hair strands) and allowed to stand for 20niin at room temperature. Then, [he strands are rinsed under tap water and dried I 2h.</p>

<p>Part 88: Results: Hair Type Color Intensity Brillance Washing Fastness Blond red moderate moderate 3 Middle blond red -good good 3-4 Dama9ed red good -goad 3</p>

<p>Examples B34 B36;</p>

<p>0.1% of compound of formula A32-, A-33 and A-34 respectively are dissolved in a 10% solution of a non-ionic surfactant (Plantacare 200UP Henkel) adjusted to pH 9.5 using citric acid or monoethanolemine. This red or violet dyeing solution is applied on the dry hair (two bland, two middle bland and two damaged hair strands) and allowed to stand for 20mm at room temperature. Then, the strands are rinsed under tap water and dried 12h.</p>

<p>Results: _________ ___________ __________ ___________ _________ __________ Compound Polymer Hair Type Color Intensity Briflance Washing of formula ________ ____________ _________ __________ ________ Fastness A-32 -linear Blond red goad good -. 3 ___________ _________ Mid blond red good good 4-5 ___________ _________ bleached red good good 4 A-33 linear Blond violet *_jood good 4 ___________ -. Middle b!ond violet good good 3-5 bleached violet good good 4 -. A-34 branched Blond red_ _good good 4 _____ ________ Middle bland red good good 4 __________ ________ bleached red good -good 4</p>

<p>Examples 860 -070:</p>

<p>0.1% of compound of formula A-35 and A-36 respectively are dissolved in a 10% solution of a non-ionic surfactant (Plentacare 2001lP, Henkel) adjusted to pH 9.5 using citric acid or manoethanolanine.</p>

<p>-51 -This red or violet dyeing solution is applied on the dry hair (two blond, two middle blond and two damaged hair strands) and aHowed to stand for 20mm at room temperature.</p>

<p>Then the strands are rinsed under tap water and dried 1 2h.</p>

<p>opound Hair Tv Color lritensiy Brillance Washing ol formula ____ A-35 Blond red good good 3 __________ Middle blond red good good --3 -__________ bleached red --good good 3 A-36 Blond red _agpd good 3 --Middle blond red good good 3-4 __________ bleached_ red ____________ good 3 Mixtures of polymeric dyes: A dye ernulsion pH 105</p>

<p>INGREDIENT -</p>

<p>Mndure of dyes as described in table 4, 5 and 6 -x Cetearyl Alcohol --i oo Ceteareth-20 --. 4 5Q fysorbate 60 -2.30 Glyceryl Stearate SE 200 SorbitanStearste _____________________ 075 Oleth-5 __________________________________________ 1.25 Capryhclcapric Triglyceride __________________________________ -0.50 Disodium EDIA ______________ Q.05_ Monoethanclamine 99% Ammoniuni Hydroxide 29% ___________________________ 6.60 -Dihydroxypropyl PEG-S Linolsammoniurri Chloride -______ 0.50 Hydrolyzed Soy Protein 20% 0 50 -Fragranoe Drom 847 735 -Day at the Reach ___________________ -050 Deionized Water 70 C ad ioo.ao is mixed with 1 5 weight of 9% hydrogen peroxide solution and the mixture is Immediately applied to a tress of brown hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried. The color of the dyed tresses is given in Table 4 -52 -table 4. Mixtures of two polymeric dyes Camp. _____ _____ Formulation No.: __________ fona _______ A24 yellow 0, 05 0,3 A27 yellow 0,05 _____ 005 _____ _____ 0,1 _____ -A23 orange 0,05 ____ ____ ____ 0105 ____ 0.1 0,5 A7 red _____ 0,05 O, _____ 0,05 0,05 ____ _____ All violet _____ _____ _____ 0.05 _____ 0,05 ____ 0,5 ba ye content X 0 1 01 0.4 0.1 0.1 0.1 0.2 1.0 Colorresulton B R B C B bleachedhair --, ____ ____ ____ -.</p>

<p> C = copper, C) = orange. B = brown, R = red labIa 5: Mixtures of three polymeric dyes.</p>

<p>Como. I --Formulation No: formula pl 645 646 547 848 549 A27 yellow 0,1 0,07 -. _9_ A23 orange 01 0,02 0 4 007 0,03 -Al red ____ ____ 03 DM1 0,03 All violet 0,1 0,1 i 0.1 0,03 ____ TotaldyecontentX 02 019 0. 6 0,11 0,09 Color resulton I bleached iiair " S B B B B S black, Bbrown TabPe.5: Mixtures of polymeric and direct dyes.</p>

<p>Qomo. --Formulation No.: formula ______ ___ 655 556 7 A27__ _jDow -01 0.5 0.3 0.4 ____ ---A7 red 0.2 -____ ____ ____ 0.2 01 ____ All violet ___ ___ ____ ____ ___ ____.1.02 Direct Dye ____ ____ -BacYellow57 -. _ 0.2 _____ BasicReci 76. 0j 01 ____ F-CRedNo-3 _______ o L. 01 -. -HCRedBN I 0.1 ___ ___ ___ 01 0.1 Basiç_rownl6 01**__ -05 ________ ____ BasicBrownl7 0.1 ____ ____ 05 ________ ____ Basic Blue? -. . ____ 0.01 ____ Basic Blue 99 01 [ _____ _____ 1.0 _____ Total dye contentX 0.5 L 02 -OS OA 241 I 05 0.3 0.3 -53 - _____ Formulation No.: --formula Color ________ B 0 010 B R oj R</p>

<p>______________________ _____________________________________</p>

<p>1)0 orange, B = brown, R= red</p>

<p>Example B58:</p>

<p>A dye emulsion (pH=a,8), containing 1 % of the dye AIS and:; pH= 9.8 Cetyistearylalcohol ---_____________________________ -. 11.00 -.</p>

<p>Oleth-b ---. 5.0 Oleic acid ___________ 2.5 Stearic acid monoethanolamide 2.5 --Coco fatty acid monoethanolamide --25 Sodium laurylsulphate 1.7 1,2-Propanecliol --. 1.0 Amrrioniumchloride -----0.5 EDTA, Tetrasodiumsalt --0.2 Perfume _______________________________________ 0.4 Cornproteinhydroiysate. -. ___________________________ 0.2 Silica 0.1 is mixed with the same weight of 6 % hydrogen peroxide solution and the mixture is immediately applied to a tress of brown hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried. The tress has been dyed red.</p>

<p>Examole 559: A dye emulsion, containing 0.1 %of the dye A16 and 3.5 % Cetearyl alcohol 1.0 % Ceteareth 30 0.5% Glycol Distearate 3.0 % Stearamide DEA 1.0 % Sodium Oleoamphohydroxypropyl Sultonate 0.5 % Polyquarternium-6 and water ad 100% is applied for 30 minutes, at room temperature to bleached human hair, and rinsed. The result is a red dyeing with good fastnesses. -54-,</p>

<p>ExamDlQ86 A dye erriutsion containing Cetearyl Alcohol -: _______________ 12.000 Ceteareth-25 5.000 GlyceryiStearateSE - 2.500 Glycol Distearate _____ _____________________________ 0.500 !ysothate 60 -0.500 Oleth-lO 2.000 Cetearyl Octanoate 0.750 Deionized Water lOt ______________ Disodium EPTA_... -0.050 ---. ___ _____________________ _0.900 Monoethanolarnine 99% --1.000 Hydrolyzed Wheat Protein 20% --ipqo_ -Monoethanolamine 99% __________________________ -0,900 Fragrance 0mm 854 148 LInden Blossom 0.500 pH-Value. 9.90-1O.40 --_________ is apped for 30 minutes, at room temperature, to middle blond human hair, and rinsed. The result is a red dyeing with good fastnesses.</p>

<p>Example 861:</p>

<p>60m1 of part A. SOcnl of part B and 3 ml of part C are mixed in a mixing bow] or applicator bottle and the mixture is immediately applied to a tress of brown hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried. The tress has been dyed in an intensive red, Shade: Pure Red -INGREDIENT w/w% iiit A Deionized Water RI --20.00 ____________ Sodium Sullite 0.60 ___________ Disodium EDTA 0.05 ____________ Cocamidopropyi Betaine 30% --400 ___________ Propylene Glycol _______ ___ - ____________ Morroethanolamine 99% 1.00 -. ToIuene-25-Oiamine Sulfate 0.25 _____________ p-Amninophenol ---0.50 -. 4-Aniino-2-Hydroxytoluene 0.70 _____________ 2-Mejy-5-Hydroxyethylaminopheno I 0.50 _____________ 2-Amirto-4-Hydroxyethyl AA Sulfate 0.10 -_________ Erythorbic Acid 0.40 --Deionized Water RI _________ 4355 -Hydroxyethylcellulose -Natrosol 250 I-HR CC -0-75 -55-.</p>

<p>Shade: Pure Red INGREDIENT --wlw% -_______ bikwiized Water RT -10.00 -Isopropyl AIcoh -. -800 -______ Oleth-lO 1.00 ___________ OleicAcid 1.10 __________ LectarnldeMEA --1.00 _____________ Fragrance Drorn 837 375 Tropical Fever 0.50 -- ____________ Diflydroxypropyl PEG-S Linolearnmonium Chloride --0.50 _______ Hydrolyzed Soy Protein -.._____ 0.50 -_____________ Monoethanolamine 99% -2.50 _____________ Total. .... ______190.00 Part B:. -Deionized Water RT --. 60.50 DeveloDer 6% Disodium Phosphate _.. 0:15 ____________ Salcare SCBO ___________________________ 5.00 _______ Glycerin 99% --.-..</p>

<p>_____________ Sodium Lauretti Sulfate 27% t00 ____________!tldronic Acid 603.. 0.35 -______ Hydrogen Peroxide 50% _____________ --12.00 __________ Tota 100.00 Part C -INGREDIENT w/w %, _________ Deionized Water RI ___________________ 97.18 --Compound MB _____ 1.00 -Total: -________________________________ 100.00</p>

<p>Example 862:</p>

<p>Adye emulsion (pH 10.5), containing 1 % of the dye AIS:; pH 10.5 INGREDIENT w/w % Cetearyl Alcohol 12.00 Cetearelh-20 ____ 4.50 Polysorbate 60 ___________________________ 2,30 GlyceryistearateSE -. .-.--------2.00 Sorbitan Stearate. -0.75 -Oieth-5 ____________________ 1.25 Caprylic/Capric Trig iyceride -0.50 Deionized Water 70"Q _____ 66.65 DisodiurriEDTA ----. 0.05_ Monoethanolarnine 99% --0,90 Ammonium Hydroxide 29% ---6.60 Dihydroxyopyi PEG-5 Linolearnmonium Chloride 0.5Q_ Hydrolyzed Soy Protein 20% ___________ 0.50 Fragrance Drom 847 735 -Day at the Beach -0.50 Total: ________________________ __________________. 100.00_ -56 -is mixed with 1.5 weight of 9% hydrogen peroxide solution and the mixture is immediately applied to a tress of brawn hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried. The tress has been dyed in an intensive red.</p>

<p>Example B63;</p>

<p>A dye emulsion containing 1 %ofthedyeAl6and INGREDIENT wtw% Deionized Water RT -6468 AcryiateslClO-30 AIkyAcrylate Crosspolymer 0,55 Sodium Hydroxide 25% -_________________. - DMDM Hydantoin. 2kP. -Sodium Cocoamphoacetate32% 15.00 Ococarnidopropyl Betaine 30% ____________ 3.00 Decyl Glucoside 3.00 Polyguaternlum-7 --0 50 PEG-iS Copolyamine, 0.50 PEG-75 Lanolin ________________________________________ 0.50 - Deionized Water RT ---__________________________ 1(100 -Dodium EDTA ____ 0.05 BasicOrange3l __________________________________ 0.Q8_ BaS Yellow 87 --0.01 Basic Red 51 0.01 PEG-40 Hydrogenated Castor Oil 0 9i Fragrance Drom 837 375 rropical Fever ___________________ 0 45 Citric Acid 25% Solution: 0.20 Total: -100.00 is applied for 3orriin, at room temperature, to blond human hair, and rinsed.</p>

<p>The result is a very attractive vibrant red dyeing with good fastnesses.</p>

<p>Example 664:</p>

<p>A tress of blond hair is shampooed with a shampoo, containing 0.1 %of the dyeAi6and _________ Disodiurri PEG-S Laurylcitrate Sulfosuccinate, Sodium Laureth Sulfate 8.25% Sodium Cocoamphoacetate 20. 9% Methoxy PEG/PPG-7l3Arriinopropyl Dimethicone --0.5% ydroxypropyi Guar hydroxypropyltrirnonium Chloride 03% PEG-200 Hydrogenated Glyceryl Palmate; PEG-i Glyceryl Cocoate ---2.5% PEG-i 50 Distearate __________________________ 0.5% CitricAcid(30%) _______________ 2.2% Perfume; Preservatives _________________________________ --Water -. ---1-P4100% After 5 minutes the tress is rinsed and dried. The tress has been dyed red,</p>

<p>Example B65:</p>

<p>A conditioner containing 0.1 % of the dye A16 and Cetyl Alcojjq__ 3.00% Cetera reth-25 0 50% Distearyldirnonium Ctoride 1.00% Quaterriium-80 0 50% Cifric Acid Ad pH=5 Perfumes; Preservatives. -g.s.</p>

<p>Water --Ad 100% is applied to a tress of shamoooed bland hair. After 1 5mm the tress is rinsed and dried.</p>

<p>The tress has been dyed red.</p>

<p>Exa mole 866: A conditioner containing 0.1 % of the dye A16 and Cetyl Alcohol 3.00% Cetera reth-20 0.5 0% Hydroxypropyl Guar, Hydroxypropyltrimoniurn chLoride 1.00% Ouaterniuni-80 0.50% CitricAcid _______________________-AdpH=5 Octocrylene -. 0.1 But)1 Methoxybibenzoylmethane --0.1 - Pert unie Preservatives --Water --Ad 100% is eppbed to a tress of shampooed blond hair. After 15mm the tress is rinsed and dried.</p>

<p>The tress has been dyed red.</p>

<p>Example B66:</p>

<p>A conditioner containing 0.1 % of the dye A16 and Cetaryl Alcohol, Sodium Ceteart Sulfate ___.</p>

<p>Ceterareth-25 0.50% Distearyldimoniurn Chloride _________________________ _1.00% Ciuaterniurn-80 -____ Citric Acid Ad pH=5 Camphor BenzalkoniumMethosulfate __________ 0.1 Ethyl Sahcylate 0.1 -58 -Perfumes; Preservatives 111J1 Water --is applied to a tress of shampooed blond hair. After 1 5mm the tress is iinsed and drie The tress has been dyed red.</p>

<p>Example B67:</p>

<p>A conditioner containing 0.1 % of the dye A16 and Cetyl Alcohol ___________________________________________ 3.00% -Ceterareth-25 --_______________________________ 0.50% Disteardimonium Chloride -.-____ 1.00% Quatemlum-80 -. 050% -Citric Acid ___________________________ Ad pH5 Dirnethicorie --0.9 Phen1trrnethicone. Silicone Ouaternium-1 5, Laureth-4 (Polysil 1 840} 2.5_ Polysilicone-15 -0.8 Perfumes; Preservatives q.s.</p>

<p>Water --Ad 100% is applied to a tress of shampooed blond hair. After I bniin the tress is rinsed and dried.</p>

<p>The tress has been dyed red.</p>

<p>Example B68;</p>

<p>A dye emulsion, containing 0.1 %ofthedyeAl6and 3.5 % Cetearyl elcohol 1.0% Ceteareth 80 0.5 % Glycol Distearate 3.0 % Sleararriide DEA 1.0 % Sodium Oleoamphohydroxypropyl Sulfonate 0.5 % Polyquarternium-6 0.2 % DisodiurTi distyrylbiphenyl disulfonate and watered 100% is applied for 30 minutes, at room temperature to bleached human hair, and rinsed. The result is a red dyeing with good fastnesses -59-</p>

Claims (1)

1. <p>Claims 1. Polymeric dye of formula r t2tt) -bAn.</p>

   <p>* LB m H L (Y12) r 2r* 12 bAn (ib) t A -fo rA 1;or L ml I aAn1 I aAn1 I Xi (Y1) ]</p>

   <p>L</p>

   <p>(Y1')__Xi-{-A lii b_EA1_x_(y:) A and B, independently froni each other represent a polymer backbone, X1 and X2 independently from each other are a linkage group selected from -C,-C,alkylene-; CrCi 2alkenylene-; -C5-C10cycloalkylene-; C5-C10arylene; -C5-C10arylene-(C1 -C10a1ky-lene)-; -C(O)-; -(CH2CHrO)i.5-; -C(O)O-; -OCO-; -N(R1)-; -CON(R1)-; -(R1)NC(O)-; -0-: -8-; -8(0)-; -S(O)2-; -S(0)2-N(R1R2); or the direct bond; R1 and N2 Independently from each other are hydrogen; or unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic. interrupted or uninterrupted C1-C14alkyl; C2-C1 4alkenyl; C6-C,0aryf; C6-C10aryl-C1 -Cioalkyl; or C5-C10alkyl(C5-Cinaryl); V1 and V2 Independently from each other are a residue of an organic dye; or hydrogen; wherein at least one oft1 and V2 is a residue of an organic dye, An., An2 and An3, independently from each other are an anion, a and b independentty from each other are a number from 1 to 3; m is a number from 0 to 1000; n isanumberfrom0toi000;and p IS a number from ito 1000; wherein the sum of m + n t p = a.</p>

   <p>2. Dye according to claim 1, wherein V1 end V2 independently from each other are selected from the group of anthraqulnone, acn-dine, azo, azamethtne, hydrazomethine, triphenylmethane, benzodifuranone, coumarine, diketopyrrolopyrrol, dioxazine, diphenyl methane, formazane, indigoid indopheriol, nap h-tha pride, napht hoquinone, nitroaryl, rnerocyanine, methine oxa zine, perinone, perylene, pyrenequinone, phtalocyanine, phen azine, quinone imine, q uinacridone, q uinop htalor'ie, styryl, stilbene, xanthene. thiazJne and thioxanthene dyes.</p>

   <p>3. Dye according to claim 1 or 2, wherein V1 and V2 independently from each other are selected from anthraquinone, azo, azomethine, hydrazomethine, merocyanlne, rnethine and styryl dyes.</p>

   <p>4. Dye according to any of claims 1 to 3, wherein VI and V2 have the sanie meaning.</p>

   <p>5. Dye according to any of claims 1 to 4, wherein A and B, independently from each other are selected from polyethylenimlne, polypropylene- irnine, polyvinylarnine; polyvinylimine; polysiloxane; polystyrene, polyvinylimidazol, poly- vinylpyridine, poIyDADMAC, p0 lyvinylalcohol, polyacrylate, polymethacryPate; poly-urethanes derived from hydroxyl-temiinated polyethers, polyesters or polybutadienes on the one hand and aliphabc or aromatic polyisocyanatea on the other, as well as pre-cursors thereof; polyam ides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acIds or tt'ie corresponding lactams; polysaccharide, starch, cellulose, lignin; and copolymers and blends of the mentioned polymers.</p>

   <p>6. Dye according to any of clams 1 to 5, wherein both the polymer backbone (A and B) and residue of an organic dye (V1 and Y2) have a functional group slected from the electophilic group selected from halide. tosylate, mesylate, methoxy, acid chloride, sulfonyl chloride, epoxides, anhydride; or a nucleophilic group selectS from amine, hydroxyl and thiol.</p>

   <p>7. Dye according to any of claims I to 6, wherein the molecular weight of the polymenc dye is from 400 to 5000.</p>

   <p>& Dye according to any of clairris 1 to 7, whIch corresponds to formula (2) wherein vi Vt is a residue of an organic dye selected from an, azometfitne, hydrazornethine, rnerocyanine, methine and styryl dyes: and m and n are a number from 0 to 1000; wherein the sum of mn and n' 3.</p>

   <p>9. Dye according to any of claims I to 7, which corresponds to formula (3) NIfIi} wherein V1 is a residue oran organic dye selected from no, azorriethine, hydrazomethine, merocyanine, rnethine and styryl dyes; and m, n and pare a number from 0 to 1000; wherein the sum of ni, n and p = 3.</p>

   <p>lO Dye according to any of clams I to 7, which corresponds to formuFa P _i if r 1 (5) RrSr&"-j--Si-O] iOfthR &ein R L L% R3 R4 is C,-Ca1kyI; and X1, X2, V,, V2, m and nare defined as in clairri (1).</p>

   <p>11. Dye according to any of clams 1 to 7, which corresponds to formula R3 [R3]R (6) YrXrSi_OhSHOfSIX2V2 wherein S3 L R3]nft R3 is Cl-G,alkyl; and -62 -X1. X2, V1. Y2 and n are defined as in claim (1).</p>

   <p>12. Dye according to any of clams ito 7 which corresponds to formul 1R I (7) YrX1 wherein -r Jn R, is C1-C5aIkyl; and X1, X2, V, V2 and n are defined as in claim 1.</p>

   <p>13. A composition compnsung at least one dye of fomiula (is). (lb)or{lc)as defined in claim t 14. A composition according to claim 13 comprisIng n addition at least one single further di-met dye and/or an oxidative agent.</p>

   <p>15. A composition according to claim 13 or 14 in form of a shampoo, a conditioner, a gel or an emulsion.</p>

   <p>16. A method of dyeing organic materiai, which comprises treating the organic material with at least one dye otformula (Ia), (It,) or (Ic) according to claim 1, oracomposition according to any of claims lSto 15.</p>

   <p>17. A method according to claims 16, which comprises treating the organic materIal with at least one dye of formula (Ia), (ib) or (IC) as defined in claim 1 and an oxidative agent and.</p>

   <p>optionally, a further dtrect dye.</p>

   <p>1& A method according to claim 16 or 17, which comprises treating the organic material with at least one compound of formula(la), (lb)or(lc)as defined in claim land at least one single oxidative dye. or treating the the organic material with a dye of formula (la). (lb) or (ic) as defined in claim 1 and at Least one single oxidative dye and sri oxidative agent.</p>

   <p>19. A method according to any of claims 16 to 18 whereIn the organic material is selected from keratin-oontaining fibers, -63 -A method according to claim 10 wherein the keratin-containing fiber rs human hair</p>