WO2011051087A1 - Tinting agent - Google Patents

Abstract

The invention relates to an agent for changing the color of keratinic fibers, comprising at least one dye and/or one dye precursor and 1,3-butanediole in a cosmetically acceptable carrier.

Description

 "Tint"

The present invention relates to agents for the color change of keratin-containing fibers, in particular human hair, containing 1, 3-butanediol, and a method for dyeing keratin-containing fibers, in particular human hair.

 Preparations for tinting and coloring hair are an important type of cosmetic. They may be used to slightly or more intensely nuance the natural hair color according to the desires of the corresponding person, to achieve a completely different hair color, or to mask unwanted color tones, such as gray tones. Conventional hair dyes are formulated either on the basis of oxidation dyes or on the basis of substantive dyes, depending on the desired color or durability of the dyeing. Often, combinations of oxidation dyes and direct dyes are used to achieve special nuances.

 Colorants based on oxidation dyes result in brilliant and lasting color shades. However, they require the use of strong oxidizing agents such as hydrogen peroxide solutions. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or atmospheric oxygen with each other or under coupling with one or more coupler components, the actual dyes.

Colorants based on direct dyes do not require an oxidizing agent and can be formulated at pH values in the region of the neutral point; but give less permanent colorations. The absorption capacity of the dye molecules on the hair as well as the gloss of the colored hairs can not fully satisfy in many cases either.

 Recently, so-called combination preparations have been developed to reduce the burden of the usual multi-stage process, especially in direct application by consumers. In addition to the customary components for tinting and / or dyeing the hair, these preparations additionally contain active ingredients which were formerly reserved for hair aftertreatment agents. The consumer thus saves an application step; At the same time, packaging costs are reduced because one product is less needed. Another field of application for such combination preparations is the color refreshment of previously oxidatively dyed fibers.

It has surprisingly been found that the use of 1,3-butanediol in color-changing agents, preferably in combination with a polymer of the diallyldimethylammonium chloride type, can increase the gloss of the fibers Wet combability of the fibers can be improved and the durability of the color change achieved can be increased.

 A first subject of the present invention are therefore agents for the color change of keratinic fibers containing in a cosmetically acceptable carrier at least one dye and / or a dye precursor and 1, 3-butanediol.

 Keratin fibers are wool, furs, feathers and especially human hair to understand. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers, such as regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

 The term "color change of keratin fibers" used according to the invention encompasses any form of color change of the fibers, including in particular the color changes encompassed by the terms tinting, bleaching, oxidative dyeing, semipermanent dyeing, permanent dyeing and temporary dyeing, in which a dye and / or a dye precursor is used.

 The inventive compositions contain the 1, 3-butanediol preferably in an amount of 0.01 to 10 wt .-%, in particular in an amount of 0, 1 to 5 wt .-%, most preferably in an amount of 0.5 to 2 wt .-%, each based on the ready-to-use agent.

Within the scope of the work on which this invention is based, it has surprisingly been possible to show that the stated effects according to the invention can be further increased if the agents furthermore contain at least one nourishing polymer.

 Among the nourishing polymers, the homopolymers and / or copolymers of diallyldimethylammonium chloride have been found to be most preferred.

 Thus, it may be particularly preferred according to the invention if the agents according to the invention contain a homopolymer of diallyldimethylammonium chloride.

 Also preferred according to the invention, however, are agents which, in addition to the 1,3-butylene glycol, contain a copolymer of diallyldimethylammonium chloride and a nonionic and / or anionic comonomer.

Preferred comonomers according to the invention are acrylic acid, methacrylic acid, acrylamide, and methacrylamide. Accordingly, agents containing a copolymer of diallyldimethylammonium chloride with acrylamide and / or acrylic acid and / or methacrylamide and / or methacrylic acid are also preferred. Such polymers are sold commercially, for example under the trade name Merquat ^® by the company Ondeo Nalco. These are for example:

Merquat ^® 100 poly (dimethyldiallylammonium chloride) (ca. 40% solids; INCI

Name: Polyquaternium-6) (Ondeo Nalco)

Merquat ^® 280 dimethyldiallylammonium acrylic acid copolymer (about 35 active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco) Merquat 281 dimethyldiallylammonium chloride acrylic acid copolymer (about 39-43% solids in water, INCI name: Polyquaternium-22) (Ondeo-Nalco)

Merquat ^® 295 dimethyldiallylammonium acrylic acid copolymer (about 35-40% solids in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)

Merquat ^® 550 dimethyldiallylammonium chloride acrylamide copolymer (about 8.1-9.1%

 Active substance in water; INCI name: Polyquaternium-7) (Ondeo-Nalco)

Merquat ^® Plus 3330 dimethyldiallylammonium chloride acrylic acid acrylamide terpolymer (about 9.5%

 Solid in water; INCI name: Polyquaternium-39) (Ondeo-Nalco) The agents according to the invention preferably contain the diallyldimethylammonium chloride polymer in an amount of from 0.01 to 10% by weight, in particular in an amount of from 0.1 to 5% by weight, especially preferably in an amount of 0.5 to 2 wt .-%, each based on the ready-to-use agent.

 In the context of the work on which this invention is based, it has additionally been found that the increase in gloss, the improvement in wet combability and the prolongation of the durability of the color changes are particularly great if the compositions according to the invention also contain at least one thickening polymer which has no diallyldimethylammonium chloride units ,

 In this case, preference is given to polymers which increase the viscosity of aqueous phases in cosmetic preparations. In aqueous phases, their viscosity-increasing function is due to their solubility in water or their hydrophilic nature.

 According to the invention, the following polymers have proved to be preferred:

Acrylamide Copolymer, Acrylamide / Sodium Acrylate Copolymer, Acrylamide / Sodium Acryloyl Dimethyl Taurate Copolymer, Acrylates / Acetoacetoxyethyl Methacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, Acrylates / C 10-30 Alkyl Acrylate Crosspolymer, Acrylates / Ceteth-20 Itaconate Copolymer, Acrylates / Ceteth -20 Methacrylate Copolymer, Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates / Vinyl Isodecanoate Crosspolymer, Acrylic Acid / Acrylonitrogen Copolymer, Alcaligenes Polysaccharides, Ammonium Acrylates / Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Ammonium Acryloyl Dimethyl Taurate / Vinyl Formamide Copolymer, Ammonium Acryloyl Dimethyl Taurate / VP Copolymer, Ammonium Polyacryloyl Dimethyl Taurate , Ascorbyl methylsilano l Pectinate, Butoxy Chitosan, Calcium Potassium Carbomer, Calcium Starch Octenyl Succinate, C20-40 Alkyl Stearate, Carbomer, Cholesterol / HDI / Pullulan Copolymer, Cholesteryl Hexyl Dicarbamate Pullulan, Diglycol / CHDM / Isophthalates / SIP Copolymer, Dimethicone Crosspolymer-2, Dimethicone Propyl PG-Betaine, DMAPA Acrylates / Acrylic Acid / Acrylonitrogen Copolymer, Ethylene / Sodium Acrylate Copolymer, Hydroxyethyl Acrylate / Sodium Acryloyl Dimethyl Taurate Copolymer, Hydroxypropyl Ethylenediamine Carbomer, Isobutylene / Sodium Maleate Copolymer, Methoxy PEG-22 / Dodecyl Glycol Copolymer, Octadecenes / MA Copolymer, PEG-800, PEG Crosspolymer, PEG-150 / Decyl Alcohol / SMDI Copolymer, PEG-175 Diisostearate, PEG-190 Distearate , PEG-15 glyceryl tristearate, PEG-140 glyceryl tristearate, PEG-240 / HDI copolymer bis-decyltetradeceth-20 ether, PEG-100 / IPDI copolymer, PEG-180 / Laureth-50 / TMMG copolymer, PEG-10 / lauryl dimethicone Crosspolymer, PEG-15 / lauryl dimethicone crosspolymer, PEG-2M, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-25M, PEG-45M, PEG-65M, PEG-90M, PEG-1 15M, PEG-160M, PEG-120 Methyl Glucose Trioleate, PEG-180 / Octoxynol-40 / TMMG Copolymer, PEG-150 Pentaerythrityl Tetrastearate, PEG-4 Rapeseedamide, PEG-150 / Stearyl Alcohol / SMDI Copolymer, Polyacrylates-3, Polyacrylic Acid, Polycyclopentadienes, Polyether-1, Polyethylenes / Isopropyl Maleate / MA Copolyol, Polymethacrylic Acid, Polyquaternium-52, Polyvinyl Alcohol, Potassium Aluminum Polyacrylate, Potassium Carbom PPG-14 Laureth-60 Isophoryl Dicarbamate, PPG-14 Palmeth-60 Hexyl Dicarbamate, PVP / Decene Copolymer, PVP Montmorillonite, Ricinoleic Acid / Adipic Acid / AEEA Copolymer, Sodium Acrylate / Acryloyl Dimethyl Taurate Copolymer, Sodium Acrylate / Acrolein Copolymer, Sodium Acrylate / Acrylonitrogen Copolymer, Sodium Acrylate Copolymer, Sodium Acrylate / Vinyl Isodecanoate Crosspolymer, Sodium Acrylate / Vinyl Alcohol Copolymer, Sodium Carbomer, Sodium Isooctylene / MA Copolymer, Sodium Polyacrylate, Sodium Polyacrylate Starch, Sodium Polyacryloyl Dimethyl Taurate, Sodium Polymethacrylate, Sodium Polystyrene Sulfonate, Sodium Styrene / Acrylate Copolymer, Sodium Tauride Acrylate / Acrylic Acid / Acrylonitrogen Copolymer, Starch / Acrylate / Acrylamide Copolymer, Steareth-60 Cetyl Ether, Steareth-100 / PEG-136 / HDI Copolymer, Synthetic Fluorophlogopite, TEA Carbomer, Tromethamine Acrylates / Acrylonitrogen Copolymer, Tromethamine Magnesium Aluminum Silicates.

Particularly preferred according to the invention are the thickening polymers of the polyacrylic acid type, in particular the polymers known under the INCI names Calcium Potassium Carbomer, Carbomer, Potassium Carbomer and Sodium Carbomer.

The thickening polymers are preferably present in the compositions according to the invention in amounts of from 0.0001 to 4% by weight, in particular from 0.01 to 2% by weight, very particularly preferably in amounts of from 0.1 to 1% by weight, in each case based on the ready-to-use agent.

The compositions according to the invention contain, as in a first embodiment as a color-modifying component, at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually organic compounds such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes. Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and Disulfonic acid) (Cl 47.005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4- ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (Cl 13.015, Acid Yellow 9 ), 5-Hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (Cl 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [( 4-phenylamino) phenyl] azobenzenesulfonic acid, sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45, 350; Acid Yellow 73, D & C Yellow No 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (Cl 10,385; Acid Orange 3), 4 - [(2,4-dihydroxy phenyl) azo] -benzenesulfonic acid sodium salt (Cl 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (Cl 15.510; Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-) dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (Cl 20, 170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (Cl 14.710, Acid Red 4), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (Cl 14,720; Acid Red No.14), 6-hydroxy-5 - [(4- sulfonaphth-1-yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (Cl 16,255, Ponceau 4R, Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2 7, 7-naphthalenedisulfonic acid trisodium salt (Cl 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33 ), 5- (acetylamino) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (Cl 18.065, Acid Red 35), 2- (3-hydroxy-2, 4,5,7-tetraiodo-dibenzopyran-6-on-9-yl) -benzoic acid disodium salt (Cl 45,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (Cl 45, 100; Acid Red 52), 8- [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27,290; Acid Red 73), 2 ', 4', 5 ', 7' Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' - [9H] xanthene] -3-one disodium salt (Cl 45.380; Acid Red 87), 2 ', 4', 5 ', 7'-tetrabromo-4,5,6J-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one disodium salt (CI 45,410; Acid Red 92 ), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -3-one-disodium salt (Cl 45425; Acid Red 95), 2- Hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (Cl 15,685, Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1-phenyl- 4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) - azo] -2-naphthalenecarboxylic acid calcium salt (Cl 15,850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt ( Cl 14,700; Food Red No. 1; Ponceau SX; FD & C Red No. 4), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (Cl 61, 570; Acid Green 25), bis [4- (dimethylamino) phenyl] - ( 3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50), bis [4- (diethylamino) -phenyl] (2,4- disulphophenyl) carbenium inner salt, sodium salt (2: 1) (Cl 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4- disulfophenyl) -carbenium inner salt, calcium salt (2: 1) (Cl 42,051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohex

ethylbenzene methanaminium hydroxide, inner salt, sodium salt (CI 42.080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62,055, Acid Blue 25), 1-amino-4- (cyclohexylamino) -9, 10-anthraquinone-2-sulfonic acid sodium salt (Cl 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro- 3-oxo-1H-indole-5-sulfonic acid disodium salt (Cl 73.015; Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl- 4-sulfophenyl) amino] xanthylium inner salt, sodium salt (CI 45.190, Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (Cl 60.730 D & C Violet No. 2, Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] sulfone (Cl 10.410, Acid Brown 13), 5-amino 4-hydroxy-6 - [(4-nitrophenyl) azo] -3- (phenylazo) -2,7-naphthalene disulphonic acid disodium salt (C.I. 20.470; Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalenesulfonic acid chromium complex (3: 2) (Cl 15.71 1; Acid Black 52 ), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7-naphthalenedisulfonic acid, tetrasodium salt (Cl 28,440; Food Black No. 1), 3 ', 3 ", 5', 5" - tetrabromophenolsulfonephthalein (bromophenol blue), 3,4,5,6,3 ', 3 ", 5', 5" octabromophenolsulfone phthalein (tetrabromophenol blue) ,

 Preferred anionic substantive dyes are those having the international designations or trade names tetrabromophenol blue, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7 , Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (Cl 51, 175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino)]. naphthyl] carbenium chloride (Cl 42,595, Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8 ), 3,7-di (dimethylamino) phenothiazine-5-ium chloride (Cl 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (Cl 44.045; Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11, 154; Basic Blue 41), 8-amino 2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (Cl 56.059, Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42.535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42.520, Basic Violet 2), tri [ 4- (dimethylamino) -phenyl] car Benium chloride (Cl 42,555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (Cl 45,170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (Cl 42.510 Basic Violet 14), 1, 3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (Cl 21, 010; Basic Brown 4), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12.250, Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [( 4-amino-3-nitrophenyl) azo] - 7- (trimethylammonio) -2-naphthol chloride (Cl 12,251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzenaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (Cl 50.240, Basic Red 2), 1, 4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1 , 2,4-triazolium chloride (Cl 11, 055, Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene chloride (CI 12,245, Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (Cl 41, 000; Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3- trimethyl-3H-indole-1-chloride (Cl 48.055; Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) -phenyl) azo] -pyrazol-5-one chloride (Cl 12,719, Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) phenylmethanol (CI 42,000; Basic Green 4), 1- (2-morpholinium-propylamino) -4-hydroxy-9,10-anthraquinone-methylsu lfat, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

 Preferred cationic substantive dyes are included

 (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

 (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

 (C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 1 1 are called.

 Preferred cationic substantive dyes of group (c) are, in particular, the compounds disclosed in the priority document with the designations (DZ1) to (DZ9). The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Suitable blue nitro dyes are in particular: 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2- nitrobenzene (HC Blue 10), 4- [di (2-hydroxyethyl) amino] -1 - [(2- methoxyethyl) amino] -2-nitrobenzene (HC Blue 1 1), 4- [ethyl (2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12) , 2 - ((4-Amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene ( HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl ) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

 Suitable red nitro dyes are in particular: 1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and salts thereof, 1, 4- Diamino-2-nitrobenzene (Cl 76.070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13 ), 1-amino-4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino 4- (methylamino) -2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [( 2-hydroxyethyl) amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2- nitrobenzene (HC Orange 2), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -

2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1, 4- [di ( 2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 1 1), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4- Amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol ( HC Red BN), 2,5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2 -nitropyridin,

3-Amino-6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-Amino-6- (methylamino) -2-nitropyridine, 6 - (ethylamino) -3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H- 1,4-benzoxazine (HC Red 14). In particular, suitable yellow nitro dyes are: 1,2-diamino-4-nitrobenzene (Cl 76.020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2- [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4- [(2,3- Dihydroxypropyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1- methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4- bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 1: 1), 1 - [(2'-ureidoethyl) amino ] -4-nitrobenzene, 1-amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1- ch lor-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4- [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2-hydroxyethyl) amino] -3- nitro-benzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] -1-nitrobenzene.

 Suitable quinone dyes are in particular: 1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (Cl 61, 545, Disperse Blue 23), 1- [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (Cl 61, 505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9 , 10-anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (Cl 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7-beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (Cl 75,470, Natural Red 4), 1 - [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8 ), 1, 4-diamino-2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 1 1, Solvent Violet No. 26), 1, 4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61, 100 , Disperse Violet 1), 1-amino-4- (methylamino) -9, 10-anthraquinone (C.I. 61, 105, Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-Chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1, 4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (Cl 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro- 5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

 Suitable neutral azo dyes are in particular: 1 - [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (Cl 11, 210, Disperse Red 17), 1- [Di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3 Methylbenzene (HC Yellow 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (Cl 1 1855 Disperse Yellow 3), 4 - [(4-nitrophenyl) azo] aniline (Cl 1 1, 005, Disperse Orange 3).

Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 1, HC Red 13, HC Red BN, HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) - aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino 5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro 1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2- Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

 It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

 Furthermore, as direct dyes also naturally occurring dyes may be used, as for example in henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

 Very particular preferred substantive dyes according to the invention are Basic Brown 16, Basic Yellow 57, Basic Blue 99, HC Blue 2, 4-amino-3-nitrophenol, HC Yellow 13, HC Blue No. 12, 1-Amino-5-chloro-4 (2,3-dihydroxypropylamino) -2-nitrobenzene (Red Y), Acid Violet 43, 4 - [(2-hydroxyethyl) amino] -3-nitrophenol (Red B54). hydroxyethyl-2-nitro-toluidine.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

 In a second embodiment of the present invention, the agent may contain at least one dye precursor.

 Under dye precursors according to the invention both oxidation dye precursors and precursors of natural analog hair dyes understood, each under the action of an oxidizing agent (optionally oxygen from the air) form the actual dyeing the hair dyes.

 For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

These further coloring substances are described below:

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts.

Particularly preferred p-phenylenediamines are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine and N- Phenyl-p-phenylenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine and their physiologically acceptable salts.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

 Preferred binuclear developer components are in particular: N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol and bis (2-hydroxyethyl) Hydroxy-5-aminophenyl) -methane and their physiologically acceptable salts.

 Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts.

Preferred p-aminophenols are in particular p-aminophenol, N-methyl-p-aminophenol, and 4-amino-3-methyl-phenol and their physiologically tolerated salts.

 Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-5-methylphenol and its physiologically acceptable salts.

Furthermore, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazolo-pyrimidine derivatives and their physiologically acceptable salts.

 Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine and their physiologically tolerated salts.

 A preferred pyrazole derivative is 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiologically acceptable salts.

 Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.

 Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. These groups are conjugated by a double bond system. When the cyclic compound is a six-membered ring, said groups are preferably in ortho position or meta position to each other.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5- and 2,7-dihydroxynaphthalene, 1-acetoxy-2-methoxynaphthalene, resorcinol, 4-chloro-resorcinol and 2-amino-3-hydroxypyridine and their physiologically tolerated salts. According to preferred coupler components are

 (A) m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- (2'-hydroxyethyl ) - amino-2-methylphenol and 2,4-dichloro-3-aminophenol,

 (B) o-aminophenol and its derivatives, for example 2-amino-5-ethylphenol,

 (C) m-Diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2' - hydroxyethylamino) benzene, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol,

 (D) o-diaminobenzene and its derivatives,

 (E) di- or trihydroxybenzene derivatives such as, for example, 2-methylresorcinol and 1,2,4-trihydroxybenzene,

 (F) pyridine derivatives such as 3-amino-2-methylamino-6-methoxypyridine, 2,6-diaminopyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-amino-3-hydroxypyridine and 3,5-diamino 2,6-dimethoxy,

 (G) naphthalene derivatives such as 1-naphthol and 2-methyl-1-naphthol,

 (H) morpholine derivatives such as 6-hydroxybenzomorpholine,

 (I) quinoxaline derivatives,

 (J) pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

 (K) indole derivatives such as 6-hydroxyindole,

 (L) pyrimidine derivatives or

 (M) Methylenedioxybenzene derivatives such as 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene

and their physiologically acceptable salts.

 Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5- and 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-methylresorcinol and 2, 6-Dihydroxy-3,4-dimethylpyridine and their physiologically acceptable salts.

 The inventive compositions contain both the developer components and the coupler components preferably in an amount of 0.005 to 20 wt .-%, preferably 0, 1 to 5 wt .-%, each based on their total weight. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proved to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 : 2, may be included.

In a further embodiment of the present invention, the agents according to the invention comprise at least one precursor of a naturally-analogous dye. As precursors of natural analogue Dyes are preferably those indoles and indolines used which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring.

 Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline and 2,3-dioxoindoline (isatin) and their physiologically acceptable salts.

 A particularly preferred derivative of indole is 5,6-dihydroxyindole and its physiologically acceptable salts.

The agents according to the invention preferably contain the indole or indoline derivatives in an amount of 0.05-10% by weight, preferably 0.2-5% by weight, in each case based on their total weight. The agents of the second embodiment of the invention contain with particular preference additionally hydrogen peroxide. Here, agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are particularly preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ 0 ₂ ) included.

The hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ 0 ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used.

Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6 to 12 percent solutions in water are used.

 Furthermore, it has proved to be advantageous if the color-modifying nonionic surfactants according to the invention contain.

 Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, explicit reference is made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company m.b.H. Stuttgart, 1974, pages 466-474, as well as the original works cited therein.

Particularly preferred non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity refers to this Rather, it refers to the fact that the chosen substances should preferably be free from solvents, stabilizers and other impurities.

Preferred nonionic surfactants are

- Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, especially 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ^® Dehypon LT 054, a _Ci-2 -i8 Fettalkoholol + 4.5 ethylene oxide-butyl ether.

 - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.

- alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides.

 Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.

Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxy- stearate (commercial product: Dehymuls ^® PGPH (Henkel)).

 Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).

 - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

 Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.

Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous. Furthermore, the color-modifying agents according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants may be very particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C 12 H 25 - (C ₂ H ₄ O) 6 -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C 8 -C 22 Carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

 These anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before. Suitable nonionic surfactants are in particular C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

 Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and

Tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained. As a further constituent, the compositions according to the invention may contain at least one ammonium compound from the group of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably from 1 to 5,% by weight, based on the total composition of the composition ,

 Furthermore, the dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and

Additives, such as

 nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,

 cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinylalcohol,

 zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,

 anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers, and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers .

 Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

 Structurants such as maleic acid and lactic acid,

 hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

 Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,

 Perfume oils, dimethylisosorbide and cyclodextrins,

 Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

 fiber-structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,

 quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers like silicones, Dyes for staining the agent,

 Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

 Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines, substances for adjusting the pH, for example customary acids, in particular edible acids and bases,

 Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

 Plant extracts such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.

 Cholesterol,

 Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

 Fats and waxes such as spermaceti, beeswax, montan wax and paraffins, fatty alcohols and

fatty acid ester,

 fatty acid,

 Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

 Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

 Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

 pigments

 Stabilizing agent for hydrogen peroxide and other oxidizing agents,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, C0 ₂ and air,

 antioxidants

contain.

 With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schräder, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

 The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents.

The compositions according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solvents. solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide a powdered or tablet-shaped formulation, which is preferred for dyeing and / or brightening agents. For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

Preferred agents according to the invention are characterized in that they additionally comprise a nonaqueous solvent, particularly preferred compositions according to the invention the solvent in a concentration of 0, 1-30 weight percent, preferably in a concentration of 1 - 20 weight percent, most preferably in a concentration of 2 - 10 weight percent, each based on the agent included.

 In further preferred agents according to the invention, the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and mixtures thereof.

 The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent.

Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. The presence of oxidation dye precursors is therefore not a mandatory requirement for the use of oxidizing agents in the compositions of the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.

 However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are according to the invention suitable, which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as the laccases, or in situ produce small amounts of hydrogen peroxide and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

 Pyranose oxidase and e.g. D-glucose or galactose,

 Glucose oxidase and D-glucose,

 Glycerol oxidase and glycerin,

 Pyruvate oxidase and pyruvic acid or its salts,

 Alcohol oxidase and alcohol (MeOH, EtOH),

 Lactate oxidase and lactic acid and their salts,

 Tyrosinase oxidase and tyrosine,

 Uricase and uric acid or their salts,

 Choline oxidase and choline,

 Amino acid oxidase and amino acids.

When using oxidizing agents, the actual colorant is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of the formula (Ia) and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, e.g. a dyeing shampoo was used.

 In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxide is sulfate solutions may be preferred as the oxidizing agent.

For the application of the compositions of the invention on the hair dyeing and / or brightening agents are mixed immediately before application with a hydrogen peroxide solution. The Concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are used. The proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is chosen in particular when no too pronounced Blondierwirkung is desired.

 Particularly preferred compositions according to the invention comprise one or more substances from the group nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS), ethylenediamine diglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-Ν, Ν'-disuccinic acid (GADS). , Ethylenediamine-N-N'-diglutaric acid (EDDG), 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), ethylenediaminetetraacetic acid (EDTA), ethylenedicysteic acid

(EDC), diaminoalkyldi (sulfosuccinic acid) (DDS), ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA), N-2-hydroxyethyl-N, N-diacetic acid, glyceryliminodiacetic acid, N-2-hydroxypropylsulfonic acid, lminodiacetic acid, Aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid, 8-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid, dipicolinic acid, 1-hydroxyethane 1, 1-diphosphonate (HEDP) and their salts and / or derivatives.

 Preferred agents according to the invention are formulated with little or no water. Particularly preferred agents according to the invention are characterized in that they contain less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water, preferred agents being anhydrous. The water content of the agents can be determined, for example, by means of titration according to Karl Fischer.

 A second object of the present invention is a process for the color change of keratin fibers, in particular human hair, in which

 if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 is applied to the fiber, optionally adding a further agent M3 to the means M2 before use,

 this agent M2 is rinsed from the fiber after 5-30 minutes

 and, after the treatment, if appropriate, an aftertreatment agent M4 is applied to the fiber and rinsed off after a contact time of a few minutes, at least one of the agents M1, M2 or M3 being an agent according to the invention.

Accordingly, the agents according to the invention can be formulated as single-component agents (color-modifying agent M2), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used is produced in such systems by the consumer directly before use by mixing the components. According to the invention, it is particularly preferred if the agent is formulated as a one-component agent which acts on the hair without pre- or post-treatment. In this case, the agent according to the invention can be applied to both wet and dry hair.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

B e i s p e e l e

 1 coloration examples:

 1.1 Preparation of Dyeing Creams

 The following coloring creams were produced:

 1.2 List of raw materials used

Dehydor LS 2 C ₁₂ -i4 fatty alcohol with approx. 2 EO units (INCI name: Laureth-2) (Cognis Pulcra)

Dehyton ^® PK 45 N, N-dimethyl-N- (cocamidopropyl) ammoniumaceto betaine (ca. 44%

 Solid; INCI name: Agua (Water), Cocamidopropyl Betaine) (Cognis)

 Emulgade "" 1000 Nl INCI name: Cetearyl alcohol, Ceteareth-20) (Cognis)

Lorol (techn.) ^® Ci2-i8 fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Merguat ^® 100 poly (dimethyldiallylammonium chloride) (ca. 40% solids; INCI name: polyquaternium-6) (Ondeo Nalco)

Texapon ^® NSO lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis) 1.3 Coloring and determination of wet combability

 1.3.1 Pretreatment of the strands

 The strands (Kerling Euronaturhaar, blond, 12cm long) were treated with a watery

Texapon ^® NSO solution (3 wt .-% active matter content, pH 6-7) thorough cleaning. Subsequently, the combing forces were determined before the product application as a reference value.

 1.3.2 Coloring

 The recipes were applied in a ratio of 4g cream: 1g hair on the strands. After a contact time of 20 minutes at 32 ° C, the hair was rinsed with 32 ° C warm tap water for 2 minutes (flow 0.51 water per minute). Aftertreatment was not carried out.

 1.3.3 Measurement of combing forces

 To determine the combing force, the tresses were combed with fine-toothed hard rubber combs from Hercules Sägemann (Hamburg, Germany).

 Each strand was combed three times before the actual measurement was started. Thereafter, 10 combing operations were performed during which the tress was rotated slowly. The mean value of the combing force was determined. Each tress was measured before and after the application of the hair treatment agent to be examined. Table 1 shows the change in the combing force and the work done.

12 hair strands per product were used.

 1.3.4 Calculation and statistics

 The series of measurements were evaluated using the following tests included in the STATISTICA 8.0 software (StatSoft Inc., USA):

 Shapiro-Wilk's W-Test (normal distribution)

 Outlier Test (Grubbs)

 Paired two sample student t test

 Kruskal-Wallis test (one-way analysis of variance by ranks, non-parametric method) The following measured values were obtained:

After tinting with an agent according to the invention (formulation B), the fibers have improved wet combability, which manifests itself in the fact that less work has to be expended for combing the strands. In addition, it could be shown by these experiments that the addition of Polyquaternium-6, the wet combability of the tress even further improved (corresponding to a significantly reduced required combing work).

Claims

Patent claims 1. agent for color change keratinischer fibers, containing in a cosmetically acceptable carrier at least one dye and / or a dye precursor, characterized in that it contains 1, 3-butanediol.  2. Composition according to claim 1, characterized in that it further contains at least one nourishing polymer.  3. Composition according to one of claims 1 or 2, characterized in that it contains as a nourishing polymer is a homopolymer and / or a copolymer of diallyldimethylammonium chloride.  4. Composition according to claim 4, characterized in that it contains the homopolymer of Diallyldimethylammoniumchlorids.  5. Composition according to claim 4, characterized in that it contains a copolymer of diallyldimethylammonium chloride with acrylamide and / or acrylic acid and / or methacrylamide and / or methacrylic acid.  6. Composition according to one of claims 1 to 5, characterized in that it further contains at least one thickening polymer which has no diallyldimethylammonium chloride units.  7. Composition according to claim 6, characterized in that it contains a thickening polymer of the polyacrylic acid type.  8. Composition according to one of claims 1 to 7, characterized in that it contains at least one substantive dye selected from the nitierten benzene derivatives, the cationic substantive dyes and the anionic substantive dyes.  9. A process for the color change of keratin fibers, in particular human hair, characterized in that  if desired, a pretreatment agent M1 is applied to the fiber, then  a means M2 is applied to the fiber, optionally adding a further agent M3 to the agent M2 before use, rinsing this agent M2 off the fiber after a period of 5-30 minutes, and after treatment optionally a post-treatment agent M4 the fiber is applied and rinsed off again after a reaction time of a few minutes,  wherein at least one of the means M1, M2 or M3 is an agent according to any one of claims 1 to 8.