WO2008151940A1

WO2008151940A1 - Method for filling hair color changing agents

Info

Publication number: WO2008151940A1
Application number: PCT/EP2008/056590
Authority: WO
Inventors: Wolfgang Wolff; Mustafa Akram; Holger Wildt
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-06-13
Filing date: 2008-05-29
Publication date: 2008-12-18
Also published as: DE102007027862A1; JP2010529156A; JP5612466B2

Abstract

The object of the present application is a method for filling hair color changing products into packaging, wherein, in a first step, the hair color changing preparation is filled into the packaging; in a second step, a preparation is applied to the surface of the hair color changing preparation, the preparation containing at least one reducing agent; and in a third step, the packaging is closed. Using this method, it is now possible to reduce or completely avoid discoloration of the hair color changing agents during storage, which often leads to product complaints.

Description

"Method of filling hair color-changing agents"

The present application relates to a method for filling hair color-changing products in packaging, wherein on the already filled preparation, a preparation containing a reducing agent is sprayed, and the use of such reducing agent-containing solutions to prevent changes in hair color-changing agents during storage.

Human hair is treated today in many ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

For temporary dyeings usually dyeing or tinting agents are used which contain as coloring component so-called substantive dyes. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyes are usually sensitive to shampooing, so that sometimes an undesirable shift in shade or even a visible "discoloration" occurs.

For permanent, intensive dyeings 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 stains are characterized by excellent, long lasting staining results. For naturally acting dyeings, a mixture of a larger number of oxidation dye precursors must usually be used; In many cases, direct dyes are still used for shading.

Finally, recently, a novel dyeing process has received much attention. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. In, In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.

In the two last-mentioned processes for achieving permanent dyeings, dye precursors are respectively applied to the hair, from which the actual dyes develop by oxidation. Since the dye precursors used are therefore highly sensitive to oxidation, there are regularly problems with the filling and storage of these components.

Thus, such agents are filled for example in airtight packaging, which are partially rinsed after filling with a protective gas to remove the residual oxygen. Likewise, an attempt is made to minimize the gas space by a maximum filling of the tube (beyond the nominal volume). Nevertheless, discoloration of the hair-color-changing preparation has repeatedly been observed in the past, which is an indication of an at least partial oxidation of the dye precursors and regularly lead to complaints by hairdressers and end users.

There was therefore still a need to improve the filling process with the aim of avoiding the partial oxidation of the dye precursors in the package.

It has now surprisingly been found that this undesirable oxidation reaction can be largely avoided if a preparation containing at least one reducing agent is applied to the already filled hair color-modifying agents.

A first subject of the present application is therefore a method for filling hair color-changing products in packaging, in which the hair color-changing preparation is filled into the package in a first step, in a second step, a preparation is applied to the surface of the hair color-changing preparation, the at least one Contains reducing agent, and in a third step, the packaging is closed.

An essential step of this process is the application of the preparation containing at least one reducing agent. The preparations according to the invention preferably contain the at least one reducing agent in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For this purpose, such carriers are for example solutions, creams, emulsions, gels or surfactant-containing foaming solutions.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a C ₁ -C ₄ -alkoxy, in particular ethanol or isopropanol. The preparations applied according to the invention may additionally contain other organic solvents, such as, for example, methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

Furthermore, it may be preferred according to the invention if the area of the packaging located above the surface of the hair-color-changing preparation is rinsed with a gaseous preparation which has a reducing action or if it is introduced into the packaging space which is not filled with filling material. In the context of this embodiment, the carrier may be both a gas or a mixture of different gases.

An essential component of the preparation applied in the second step of the process according to the invention is the at least one reducing agent.

Although in principle there is no restriction as regards the choice of reducing agent, sulfur-containing reducing agents and hydrides have proven to be particularly suitable in the work on which this application is based.

In the context of a first preferred embodiment of the present invention, therefore, a sulfur-containing compound is used as the reducing agent. As such, in particular sulfides, sulfites, dithionites, thiosulfates and thioglycolic acid and their salts in question. These compounds are preferably used in the form of their alkali metal, ammonium and / or alkaline earth metal salts. Particularly preferred are the sodium, ammonium and potassium salts, the sodium salts of these compounds are very particularly preferred according to the invention.

According to the invention, according to this embodiment, sodium sulfide, sodium sulfite, sodium dithionite, sodium thiosulfate, thioglycolic acid and ammonium thioglycolate are particularly preferable.

In the context of a second preferred embodiment of the present invention, therefore, a hydride is used as the reducing agent. The hydrides used are in particular lithium aluminum hydride and sodium borohydride. Particularly preferred reducing agents according to the invention are ammonium thioglycolate, sodium dithionite, ascorbic acid and sodium sulfite. Ammoniunnthioglykolat and sodium dithionite are very particularly preferred according to the invention.

The reducing agents are preferably contained in the preparation applied in the second step of the process according to the invention in amounts of from 1 to 10% by weight, in particular from 2 to 5% by weight.

Furthermore, it has proved to be advantageous according to the invention when the preparation applied in the second step of the process according to the invention is adjusted to a specific pH with the aid of alkalizing agents, acidifying agents and optionally pH-buffering substances. In this way, the good stability of the preparation before the actual application to the hair color-changing agent can be further increased.

The preparation preferably has a pH of from 1 to 7, in particular from 2 to 6, very particularly preferably from 2 to 4.

To adjust the pH, preference is given to using alkalizing agents, for example alkali metal or alkaline earth metal hydroxides, ammonia or organic amines. The organic amines are preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1 , 3-propanediol, 2-amino-2-methylbutanol and triethanolamine. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred within the scope of this group. Also, the use of amino acids and / or oligopeptides such as ω-aminocaproic acid as the alkalizing agent is preferred in the context of the present invention.

Furthermore, such amino acids and oligopeptides are preferably used, whose 2.5 wt .-% solutions in water have a pH of 9 and greater. Such an amino acid is arginine which is preferably used.

To adjust the pH, preferably at least one organic or inorganic acid is used as the acidifying agent. Hydrochloric acid, sulfuric acid and phosphoric acid are to be mentioned in particular as preferred inorganic acids. As organic acids, acetic acid, glycolic acid, citric acid, tartaric acid, lactic acid and malic acid are preferable. Malic acid is a particularly preferred acid used.

Examples of buffer systems which are preferred according to the invention are the tris / HCl buffer (about pH 6.5), the diammonium hydrogenphosphate / potassium carbonate buffer, the sodium phosphate buffer (suitable up to about pH 8.5), the citric acid / sodium citrate buffer, the glycine. Sörensen NaOH buffer (pH 8.6-10.4), the Sörensen glycine-HCl buffer (pH 1, 2-3.4), the triethanolamine / HCl buffer (pH 6.8-8.8 ), of the Triethanolamine / CO ₂ buffer (pH 7-12), the ammonium carbonate / ammonia buffer (pH 8-10.5) and a HEPES buffer (4- (2-hydroxyethyl) piperazine-1-ethanesulfonic acid); for example, commercially available from Sigma; pH range approximately from 6.8 to 8.2). Buffer systems with a molarity of 50 to 15 μm have proven particularly suitable. In the case of the HEPES buffer, a molarity of 10 mM is particularly preferred.

Furthermore, in the work on which this invention is based, it has been found that the wetting of the surface of the hair color-modifying agent is in some cases not yet sufficiently satisfactory, so that product stains due to oxidation can still occur at certain points.

This could be avoided in the context of a first preferred embodiment of the present invention, when the composition applied in the second step of the method according to the invention is set relatively thin during application to the hair color-changing component, but then the viscosity of the applied preparation increases on contact with the hair color-changing agent ,

Therefore, the composition applied in the second step of the process according to the invention preferably contains at least one thickener.

In a first preferred embodiment, the thickener is an anionic synthetic polymer. Preferred anionic groups are the carboxylate and sulfonate groups.

Examples of anionic monomers from which the polymeric anionic thickeners may consist are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trade drawing Carbopol ^® commercially. Also preferred is the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially.

Within this first embodiment, it may further be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, styrene, itaconic acid mono- and diesters, vinylpyrrolidone, vinyl ethers and vinyl esters. Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas.

However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; Suitable alkoxylated fatty alcohols are in particular steareth-20, beheneth-25 or ceteth-20. Such copolymers are sold by Rohm & Haas under the trade names Aculyn ^® 22 ^® Aculyn 88, Aculyn ^® 28 as well as by the company National Starch under the trade names Structure ^® Structure 2001 ^® 3,001th

Further preferred are copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters and styrene, as sold under the INCI-declaration Styrene / Acrylates copolymers. A preferred commercial product of this type is, for example Acusol ^® OP 301 from Rohm & Haas.

Also preferred are copolymers of acrylic acid, methacrylic acid or d- to C ₆ alkyl esters and vinyl neodecanoate, such as Acrylates / Vinyl Neodecanoate Crosspolymer marketed by the company Rohm & Haas, for example, under the trade name Aculyn ^® 38 and the INCI declaration.

Preferred anionic copolymers are also acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be present in crosslinked form, with crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide. Such a polymer is contained in the commercial products Sepigel ^® 305 and Simulgel® ^® 600 from SEPPIC. The use of these compounds, which in addition to the polymer component a hydrocarbon mixture (C ₁₃ -Ci ₄ -lsoparaffin or Isohexadecan) and a non-ionic emulsifier (Laureth-7 or polysorbate-80), has proven to be particularly advantageous in the context of the teaching of the invention.

Polymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are preferred thickeners. A 1, 9-decadiene cross-linked methyl vinyl ether-maleic acid copolymer sold under the name Stabileze® ^® QM. In a second embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group via a CI_ ₄ - are attached to a hydrocarbon group made up of acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable.

Homopolymers of the general formula (I),

R ¹ - [CH ₂ -C] _n -

COO- (CH ₂ VNR ² R ³ R ^{4 x "} ( ^! )

in which R ¹ = -H or -CH _3, R ^2, R ³ and R ⁴ are independently selected from CI_ ₄ -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n a natural number and X ^'is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (I) and nonionic monomer units, are particularly preferred cationic polymeric gellants. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:

R ¹ is a methyl group

R ² , R ³ and R ⁴ are methyl groups m is 2,

Suitable physiologically acceptable counter ions X ^"include halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preferred are halide ions, particularly chloride.

A particularly suitable homopolymer is, if desired, crosslinked,

Poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallyl polyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, monnitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 50% polymer content, an additional component: Mineral oil (INCI name: Mineral Oil) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, other components: mixture of Diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol Dicaprylate / Dicaprate) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-trideceth-6) commercially available.

Copolymers containing monomer units according to formula (I) as non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid and methacrylic acid alkyl esters CI_ _4-d- ₄ alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide

Methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ^® SC.

In a third preferred embodiment, naturally occurring thickening agents are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gum. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are marketed under the trade name Jaguar ^® C from Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ - to C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gums of free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gum are under the trade names Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar DC 293 and Jaguar ^® ^® HP105 Rhone Poulenc commercially available.

Further suitable natural thickening agents are also already known from the prior art. It is therefore explicitly referred to the work of Robert L. Davidson entitled "Handbook of Water soluble gums and resins", published by Mc Graw Hill Book Company (1980).

Also preferred according to this embodiment are biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, vegetable exudate gums such as gum arabic, ghatti gum, gellan gum, karaya gum, tragacanth gum, carrageenan gum, guar gum, Agar-agar, locust bean gum, tamarind kernel flour, glycogen, pectins, alginates, starch fractions and derivatives such as amylose, amylopectin, furcellaran and dextrins, cellulose derivatives such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses.

Preferred hydroxyalkylcelluloses are, in particular, the hydroxyethylcelluloses sold under the names Cellosize ^® Amerchol and Natrosol ^® Hercules and the hydroxypropylcelluloses, the hydroxypropylmethylcelluloses and the methylethylcelluloses; the hydroxyethylcelluloses as well as the hydroxypropylcelluloses are particularly preferred. Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ^® by Aqualon, Aquasorb ^® and ambergum ^® from Hercules and Cellgon ^® from Montello. Preference is furthermore given to sodium carboxymethylcellulose.

Starch and its derivatives are also preferred. Starch is a storage material of plants, which occurs mainly in tubers and roots, in grain seeds and in fruits and can be obtained from a variety of plants in high yield. The polysaccharide which is insoluble in cold water and forms a colloidal solution in boiling water may be, for example, potatoes, cassava, maranta, maize, cereals, rice, legumes such as peas and beans, bananas or certain types of palms (e.g. the sago palm). Natural, plant-derived starches and / or chemically or physically modified starches can be used according to the invention. Modification can be achieved, for example, by introducing different functional groups on one or more of the hydroxyl groups of the starch.

Typically, they are esters, ethers or amides of starch with optionally substituted Cr to C ₄₀ radicals. Especially advantageous is a etherified with 2-hydroxypropyl corn starch as it is, for example, sold by National Starch under the trade name Amaze ^®.

But also nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidone, can be used as thickeners according to the invention. Preferred nonionic, fully synthetic polymers are for example marketed by BASF under the trade name Luviskol ^®. Such nonionic polymers, in addition to their excellent thickening properties, also allow a significant improvement in the sensory feeling of the resulting preparations.

As inorganic thickeners, phyllosilicates have proven to be particularly suitable in the context of the present invention. In particular, clays, such as bentonite, and synthetic layered silicates, such as the chemical sold by the company Süd under the trademark Optigel ^® magnesium phyllosilicate are preferred.

The thickeners are contained in the preparations preferably in an amount of 10 to 60 wt .-%, in particular from 15 to 40 wt .-%. In the context of this embodiment, the thickening agents have proved to be particularly suitable, which have a thickening effect in an alkaline medium.

These requirements are met in particular to a particularly high degree by thickening polymers which contain as monomers, acrylic acid and / or acrylic acid derivatives and / or methacrylic acid and / or methacrylic acid derivatives and optionally further comonomers.

To avoid repetition, reference is made at this point to the relevant statements above in the text.

Furthermore, these requirements are met to a particularly high degree by the derivatives of cellulose.

With regard to these polymers, reference is explicitly made to the statements already made above.

Other thickening components which are particularly suitable for the purposes of the present invention are ethoxylated and / or propoxylated fatty alcohols and also branched and / or unbranched fatty acids, which may optionally also be ethoxylated and / or propoxylated, and derivatives thereof. These are, for example addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms. As a derivative, ethoxylated and / or propoxylated dimers of fatty acids come into consideration as 60 and the INCI nomenclature PEG-150-distearate marketed by Rohm & Haas, for example, under the trade name Aculyn ^®.

As part of a second preferred embodiment of the present invention was the selective Produktanfärbung be particularly advantageously avoided when applied in the context of the second step of the inventive method the preparation is solid at room temperature and a melting point between 40 and 7O ⁰ C, preferably between 45 and 6O ⁰ C.

In the context of this embodiment, in the second step of the process according to the invention, the preparation containing the at least one reducing agent is sprayed hot.

The preparations used in the context of the present invention furthermore preferably contain at least one fatty substance.

Under fatty bodies according to the invention preferably fatty acids, fatty alcohols, natural and synthetic waxes and emulsifiers understood. The fatty acids used can be linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms. Preference is given to fatty acids having 10 to 22 carbon atoms. Among these could be mentioned, for example, isostearic as the commercial products Emersol ^® 871 and Emersol ^® 875, and isopalmitic acids such as the commercial product Edenor ^® IP 95, and all other products sold under the trade names Edenor ^® (Cognis) fatty acids. Further typical examples of such fatty acids are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic as well as their technical mixtures, which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids. Particularly preferred are usually the fatty acid cuttings obtainable from coconut oil or palm oil; In particular, the use of stearic acid is usually preferred.

The amount used is 0.1 to 15 wt .-%, based on the total agent. In a preferred embodiment, the amount is 0.5-10% by weight, very particularly preferably amounts of 1-5% by weight.

Fatty alcohols which may be used are saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ - C ₃₀ -, preferably C ₀ - C ₂₂ - and particularly preferably C ₂ - C ₂₂ - carbon atoms. Decanols, octanols, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol are, for example, decanol, octanolol, dodecadienol, decadienol , as well as their Guerbet alcohols, this list should have exemplary and non-limiting character. However, the fatty alcohols are derived from preferably natural fatty acids, which can usually be based on recovery from the esters of fatty acids by reduction. Also usable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols. Such substances are, for example, under the names Stenol ^® such as Stenol ^® 1618 or Lanette ^® such as Lanette ^® O or Lorol ^®, for example, Lorol ^® C8, Lorol C14 ^®, Lorol C18 ^®, ^® Lorol C8-18, HD-Ocenol ^®, Crodacol ^® such as Crodacol ^® CS, Novol ^®, Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or acquire Isocarb® ^® 24 for sale. Of course, wool wax alcohols, as are commercially available, for example under the names of Corona ^®, White Swan ^®, Coronet ^® or Fluilan ^® can be used according to the invention. The fatty alcohols are used in amounts of from 0.1 to 20% by weight, based on the total preparation, preferably in amounts of from 0.1 to 10% by weight.

The natural or synthetic waxes used according to the invention are solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, fruit waxes such as apple wax or citrus wax, microwaxes of PE or PP. Such waxes are available, for example, from Kahl & Co., Trittau.

As the last group of fat bodies preferred according to the invention, the emulsifiers may be mentioned at this point. Such emulsifiers are, for example

Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear

Fatty alcohols having 8 to 22 carbon atoms, fatty acids having 12 to 22 carbon atoms and alkylphenols with

8 to 15 C atoms in the alkyl group,

Ci ₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide

Polyols having 3 to 6 carbon atoms, in particular glycerol,

Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters,

Fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, wherein

Oligomerisierungsgrade of 1, 1 to 5, in particular 1, 2 to 2.0, and glucose as

Sugar component are preferred,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example, the commercially available

Product Montanov ^® 68,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 C

atoms,

Sterols. Sterols are understood to mean a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterines) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol.

Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

Phospholipids. Of these, especially the glucose phospholipids, e.g. as lecithins or

Phosphatidylcholines from e.g. Egg yolk or plant seeds (e.g., soybeans) are understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol

Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate

(Dehymuls ^® PGPH commercial product)

Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca,

Mg and Zn salts. The agents according to the invention preferably contain the emulsifiers in amounts of 0.1-25% by weight, in particular 0.5-15% by weight, based on the total agent.

The compositions according to the invention may preferably contain at least one nonionic emulsifier having an HLB value of 8 to 18, according to the methods described in the Römpp-Lexikon Chemie (Hrg. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764, listed definitions. Nonionic emulsifiers having an HLB value of 10 to 15 may be particularly preferred according to the invention.

Among the emulsifier types mentioned, the emulsifiers which do not contain any ethylene oxide and / or propylene oxide in the molecule can be very particularly preferred.

The agents of this embodiment preferably have a pH of from 2 to 11, especially from 2 to 9. With regard to the pH adjusting agent, reference should be made at this point to the above statements.

In a further embodiment of the present invention, the surface of the hair color-changing preparation is covered with a reducing gas. Reducing gases contain H ₂ , CO, SO ₂ and / or hydrocarbons as reducing constituents, the reducing effect of the gas mixtures being dependent on the content of these gases. The hydrocarbons consist in particular of aliphatic compounds. Reducing gases also contain only a small amount or no oxygen. The maximum oxygen content according to the invention is below 5%, preferably below 2%. According to the invention, both reducing gases of natural origin and gases produced by technical processes can be used. Thus, because of its content of gaseous hydrocarbons, natural gas is a reducing gas which is preferred according to the invention; Further preferred according to the invention are reducing gases such as those produced during the gasification and pyrolysis of waste, sewage sludge and organic wastes, for example methane, ammonia and hydrogen sulphide.

Although the gases according to the invention can also be used in principle as a pure substance, according to the invention they are preferably incorporated in a gaseous carrier. As carriers, the reducing gases preferably contain inert gases such as argon and nitrogen. Examples of such gas mixtures are

2% H ₂ in N ₂ and 30% He,

0.12% CO ₂ in Ar,

2.4% H ₂ in Ar,

- 2% CO ₂ in Ar as well

- 10% H ₂ in N ₂ The hair color-changing preparation filled in the first step of the process according to the invention preferably contains at least one dye precursor.

With regard to the usable dye precursors, the present invention is not subject to any restrictions. The colorants according to the invention can be used as dye precursors

• Developer and / or coupler type oxidation dye precursors, and

• contain precursors of naturally occurring dyes, such as indole and indoline derivatives, as well as mixtures of representatives of these groups.

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. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

G ¹ represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -alkoxy - (C 1 -C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a (C ₁ to C ₄ ) -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G ² represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -alkoxy - (C ₁ -C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) - polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, a (C ₁ to C ₄ ) - acetylaminoalkoxy radical, a mesylamino (C ₁ -C ₄ ) -alkoxy radical or a (C ₁ to C ₄ ) - carbamoylaminoalkoxy radical;

G ⁴ represents a hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl radical or, when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group ,

Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p- phenylenediamine, 2,5-dimethyl-p-phenylenediannine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (.beta.-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediannine, N, N-dimethyl-3-methyl-p-phenylenediannine, N, N- (ethyl, β -hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediannine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediannine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H- innidazol-1-yl) propyl] annine, 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salting.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) - p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine , as well as the physiologically acceptable salts of these compounds.

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.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a (C 1 to C ₄ ) -alkyl radical, by a (C 1 to C ₄ ) -hydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which of a or a plurality of nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or (C 1 to C ₈ ) -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a (Ci to _C4) alkyl, a (Ci to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for bridging Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical, with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

The substituents used in formula (E2) are defined according to the invention analogously to the above statements.

Preferred dinuclear developing agents of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino -propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4 '- aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis ( 2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

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. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which: G ¹³ represents a hydrogen atom, a halogen atom, a (Ci to _C4) alkyl, a (Ci to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ polyhydroxyalkyl radical, a (Ci to C ₄₎ alkoxy (C 1 to C ₄ ) -alkyl radical, a (C 1 to C ₄ ) -aminoalkyl radical, a hydroxy (C 1 to C ₄ ) -alkylamino radical, a (C 1 to C ₄ ) -hydroxyalkoxy radical, a (C 1 to C ₄ ) - Hydroxyalkyl (Ci to C ₄ ) -aminoalkylrest or a (di - [(Ci to C ₄ ) -alkyl] amino) - (Ci to C ₄ ) -alkylrest, and

G ¹⁴ represents a hydrogen or halogen atom, a (Ci to _C4) alkyl, a (Ci to C ₄₎ - monohydroxyalkyl radical, a (C ₂ to C ₄₎ polyhydroxyalkyl radical, a (C ₁ to C ₄₎ - alkyl alkoxy (d to _C4), a (C ₁ to C ₄₎ aminoalkyl radical or a (C ₁ to C ₄₎ -Cyanoalkylrest, G ¹⁵ is hydrogen, a (C ₁ to C ₄₎ alkyl radical, (C ₁ to C ₄ ) monohydroxyalkyl, C ₂ to C ₄ polyhydroxyalkyl, phenyl or benzyl, and G ¹⁶ represents hydrogen or halogen.

The substituents used in formula (E3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, A-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, A-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may be selected from heterocyclic

Developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.

Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and

G ^{20 represents} a hydroxy group or a group -NG ²¹ G ²² , in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C 1 to C ₄ ) -alkyl group, a (C 1 to C ₄ )

Monohydroxyalkylgruppe, with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 is} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 is} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (Ci to C ₄ ) -

Alkyl group, a (C ₁ to C ₄ ) -Monohydroxyalkylgruppe, a (C ₂ to C ₄ ) -polyhydroxyalkyl, an optionally substituted aryl group or an optionally substituted aryl (C 1 to

C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{26 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,

G ²⁶ represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -

Monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and

G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -

Alkyl group or a (C ₁ to C ₄ ) -Monohydroxyalkylgruppe, in particular for a

Hydrogen atom or a methyl group. Preferably, in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the 3-position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are, in particular, the compounds which are selected from 4,5-diamino-1-naphthylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 -phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-naphthylpyrazole, 4,5-diamino-3-tert-butyl-1-naphthylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4.5 Diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxynethylpyrazole, 4,5-diamino-3-hydroxynethyl-1-methylpyrazole, 4.5- Diamino-3-hydroxynethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) -annino-1,3-dimethylpyrazole, and their physiologically acceptable salts.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and their tautomeric forms, if a tautomeric equilibrium exists:

in which:

G, G and G, G are independently a hydrogen atom, a (C ₁ to C ₄₎ - alkyl radical, an aryl radical, a (C ₁ to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ - Polyhydroxyalkyl radical is a (C ₁ to C ₄ ) alkoxy (C ₁ -C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) - aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical , a (C ₁ to C ₄ ) -alkylamino- (C ₁ -C ₄ ) -alkyl radical, a di - [(C 1 -C ₄ ) -alkyl] - (C 1 -C ₄ ) -aminoalkyl radical, where the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C ₁ to C ₄ ) monohydroxyalkyl or a di [(C ₁ -C ₄ ) -hydroxyalkyl] - (C ₁ to C ₄ ) aminoalkyl, the X radicals are each independently a hydrogen atom, a (C ₁ to C ₄₎ - alkyl radical, an aryl radical, a (C ₁ to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ - polyhydroxyalkyl radical, a (C ₁ to C ₄₎ aminoalkyl radical, a (C ₁ to C ₄ ) -alkylamino- (C ₁ -C ₄ ) -alkyl radical, a DK (C ₁ to C ₄ ) alkyl] - (C ₁ -C ₄ ) -aminoalkyl radical, where the dialkyl radicals are optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a (C ₁ to C ₄₎ hydroxyalkyl, or DK (C ₁ to C ₄₎ hydroxyalkyl] amino- (C-ι-C ₄₎ - alkyl group, Amino radical, a (C ₁ to C ₄ ) -alkyl or DK (C ₁ to C ₄ ) -hydroxyalkyl] amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 if p + q equals 2, n has the value 0, and the groups NG G and NG G occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (E7) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E7) may be mentioned in particular: pyrazolo [1, 5-a] pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; Pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazolo [1,5-a] pyrimidin-7-ol; 3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazolo [1, 5-a] pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.

Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) - methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2, 5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine , 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6):

Examples of (C 1 to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ ,

-CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C ( CH ₃ J ₃ .

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ ,

-OCH ₂ CH ₂ CH ₃ , -OCH (CHs) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , -OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH,

CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is 1, 2

Dihydroxyethyl.

Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred

Examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -

Monohydroxyalkylamino groups, imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) -monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ ,

-NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ . Examples of (Ci to _C4) are -Trialkylamnnoniunngruppen -N ⁺ (CH ₃₎ _3, -N ⁺ (CH _S) ₂ (CH ₂ Cl I _3),

-N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH,

-NH-CH ₂ CH ₂ CH ₂ OH ₁ -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C 1 to C ₄ ) -alkoxy (C 1 to C ₄ ) -alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ ,

-CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ),

-CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ).

Examples of hydroxy (C 1 to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-

CHCH (OH) CH _3, -0-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C 1 to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ ,

-O-CH ₂ CH ₂ CH ₂ NHC (O) CH ₃₁ -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃₁ -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylanninoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ ,

-O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂₁ -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C 1 to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH (NH ₂ ) CH ₃₁ -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN ₁ -CH ₂ CH ₂ CN ₁ -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C 1 to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH ₁ -

CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH ₁ -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH ₁ -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C 1 to C ₄ ) hydroxyalkyl] amino (C 1 to C ₄ ) alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂₁

-CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂₁ -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂₁ -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ ,

An example of aryl groups is the phenyl group.

Examples of aryl (C 1 to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

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. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes: m-aminophenol and / or its derivatives,

m-diaminobenzene and / or its derivatives,

o-diaminobenzene and / or its derivatives,

o-aminophenol derivatives, such as o-aminophenol,

Naphthalene derivatives having at least one hydroxy group,

Di- or trihydroxybenzene and / or derivatives thereof,

- pyridine derivatives,

- pyrimidine derivatives,

Monohydroxyindole derivatives and / or monoamine indole derivatives,

Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,

Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Morpholine derivatives, for example 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),

in which

- G ¹ and G ² independently represent a hydrogen atom, a (Ci to C ₄₎ - alkyl group, a (C ₃ -C ₆₎ cycloalkyl group, a (C ₂ to C ₄₎ alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, an aryl (d to C ₆ ) alkyl group, an AmInO (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) dialkylamino (C ₁ -C ₆ ) alkyl group or a (C ₁ to C ₆ ) alkoxy (C ₁ -C ₆ ) alkyl group, wherein G ¹ and G ² together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,

G ³ and G ⁴ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) - Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₆ ) alkoxy (C ₂ to C ₆ ) alkoxy group, an aryl group or a heteroaryl group. Particularly preferred m-aminophenol coupler components are selected from at least one compound from the group formed from m-aminophenol, 5-amino-2-naphthylphenol, N-cyclopentyl-3-aminophenol, S-amino-chloro-θ- methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-anninophenol, S-trifluoroacetylamino ^ -chloro-n-ethylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-nethoxy 2-naphthylphenol, 5- (2'-hydroxyethyl) amino-2-naphthylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylannino) benzene, 3-ethylamino-4-naphthylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.

The m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein

- G ⁵ , G ⁶ , G ⁷ and G ⁸ independently of one another represent a hydrogen atom, a (Ci to

C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄₎ alkoxy alkyl (C ₁ to C ₄₎ alkyl group, an aryl (C-ι-C _4), a heteroaryl- (C-ι-C ₄₎ - alkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle

- G ⁹ and G ¹⁰ are independently a hydrogen atom, a halogen atom, a (C ₁ to C ₄₎ alkyl group, an ω- (2,4-diaminophenyl) - (C-ι-C ₄₎ alkyl group, a ω- (2,4-diaminophenyloxy) - (C ₁ -C ₄ ) -alkoxy group, a (C ₁ to C ₄ ) -alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) -alkoxy- (C ₂ to C ₄₎ alkoxy group, an aryl group, a heteroaryl group, a (C ₁ to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ - polyhydroxyalkyl group, a hydroxy (C-ι-C ₄₎ alkoxy.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5- methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dinethylphenyl} annino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino 4- (2-methoxyethoxy) -5-methylphenylannin, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the above-mentioned compounds.

The o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein

- G ¹¹ , G ¹² , G ¹³ and G ¹⁴ independently of one another represent a hydrogen atom, a (Ci to

C ₄₎ alkyl group, a (C ₃ -C ₆₎ cycloalkyl group, a (C ₂ to C ₄₎ alkenyl group, a (Ci to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ -polyhydroxyalkyl group, a (Ci to C ₄₎ alkoxy alkyl (Ci to C _4), aryl (Ci to C ₄₎ alkyl group, a heteroaryl- (Ci to C ₄₎ - alkyl group, a (C ₂ to C ₄₎ Perfluoracylgruppe, or together with the nitrogen atom form a five-membered or six-membered heterocycle

- G ¹⁵ and G ¹⁶ are independently a hydrogen atom, a halogen atom, a carboxyl group, a (Ci to C ₄₎ alkyl group, a (Ci to _C4) alkoxy group, a hydroxy group, a (Ci to C ₄₎ - Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C 1 to C ₄ ) alkoxy group.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),

wherein

G ¹⁷ and G ¹⁸ independently of one another represent a hydroxyl group or a group,

NG G, in which G and G independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group, an aryl group, a (C ₁ to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ -polyhydroxyalkyl group, a (C ₁ to C ₄₎ alkoxy alkyl (C-ι-C _4), aryl (C ι to C ₄ ) alkyl group, a heteroaryl (C-ι to C ₄ ) alkyl group,

G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -alkoxy group.

It is preferred if, according to formula (K4), the radicals G ¹⁷ and G ^{18 are} in the ortho position or in the meta position relative to one another.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.

Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein G ²³ is a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -

Cycloalkyl group, a (C ₂ to C ₄₎ alkenyl group, a (C ₁ to C ₄₎ monohydroxyalkyl, a (C ₂ to C ₄₎ -polyhydroxyalkyl group, an aryl- (C-ι-C ₄₎ alkyl group,

G ²⁴ represents a hydroxy group or a group -NG ²⁶ G ²⁷ , in which G ²⁶ and G ²⁷ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group , a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,

G ^{25 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) alkyl group, with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG ^{23 of} the formula.

Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.

The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein

G ²⁸ is a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -

G represents a hydroxy group or a group -NG G in which G and G independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,

G ^{30 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) alkyl group, with the proviso that G ²⁹ binds in the meta position or ortho position to the structural fragment NG ^{28 of} the formula.

Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-Trihydroxypyrimidine, 2-amino-4-naphthylpyrinnidine, 2-amino-4-hydroxy-6-naphthylpyrinnidine and 4,6-dihydroxy-2-methylpyrinnidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-naphthylphenol, S-amino-1-chloro-θ-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-naphthylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis ( 2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylannino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino ) -1-ethylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} -annino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2- ethoxy-5-methylphenyl) -annino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dinethylphenyl} -annino) -ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-Amino-4- (2-methoxyethoxy) -5-methylphenylannin, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4-trihydroxybenzene , 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6 -methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dinethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2 , 7-Dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of aforementioned compounds.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven 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 , can stand.

In the following, examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6) are listed:

- (- / H ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ .

Examples of (C ₃ to C ₆ ) cycloalkyl groups according to the invention are cyclopropyl, cyclopentyl and cyclohexyl.

Examples of (C 1 to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ ,

-OCH ₂ CH ₂ CH ₃ , -OCH (CHs) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , -OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group. In addition, preferred examples of (Ci to C ₄₎ monohydroxyalkyl group -CH ₂ OH, - CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH _3, -CH ₂ CH ₂ CH ₂ CH ₂ OH are mentioned, wherein the group -CH ₂ CH ₂ OH is preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group.

Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are especially -NH _2, (C ₁ to C ₄₎ -Monoalkylanninogruppen, (C ₁ to C ₄₎ -Dialkylanninogruppen, (C ₁ to C ₄₎ -Trialkylamnnoniunngruppen, (C ₁ to C ₄₎ - Monohydroxyalkylaminogruppen, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ . Examples of (C ₁ to C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , - (- / H ₂ CH ₂ CH ₂ -U-CH ₃ , -CH ₂ CH ₂ -U-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -U-CH ₂ CH ₃ , -CH ₂ CH ₂ -U-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkoxy groups are the groups -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ CH ₂ -O- CH _3, -0-CH ₂ CH ₂ -O-CH ₂ CH _3, -0-CH ₂ CH ₂ CH ₂ -O-CH ₂ CH _3, -O-CH ₂ CH ₂ -O-CH (CH ₃₎ ₂ , -O- CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ .

Examples of hydroxy (C 1 -C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CH ₂ CH (OH ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃₁ -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

An example of aryl groups is the phenyl group, which may also be substituted. Examples of aryl (C 1 to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN1),

) in the independently

R ¹ is hydrogen, a C ¹ -C ₄ -alkyl group or a C 1 -C ₄ -hydroxy-alkyl group,

R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C 1 -C ₄ -alkyl group, and

R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-dihydroxyindoline.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

R ¹ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ is hydrogen, a dC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a

C 1 -C ₄ -alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

Furthermore, the agents may contain 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 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.

Anionic 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 (Cl.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 (CI 13,015 Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (CI 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 (Cl. 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-dihydroxyphenyl) 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 dimethyl-phenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170, Acid Orange 24), A-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (Cl.14,710, Acid Red 4), A- Hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalene-sulfonic acid disodium salt (Cl 14.720; Acid Red No.14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7- naphthalene-disulfonic acid trisodium salt (Cl.16.185; Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (Cl.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-tetraiodedibenzopyran-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-ethylethaneamnonium hydroxide, inner salt, sodium salt (Cl.45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1, 3-disulphonic 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-4,5,6,7-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 44.0 90; Food Green no. 4; Acid Green 50), bis [4- (diethylamino) phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 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) (CI 42,051, Acid Blue 3), N- [4 - [(2, 4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine hydroxide, inner salt, sodium salt (CI 42,080, Acid Blue 7), (2-Sulfophenyl) di [4- (ethyl (4-sulfophenyl) methyl) amino) phenyl] -carbenium dinatrium 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-annino-4- (cyclohexylannino) -9,10-anthraquinone-2-sulfonic acid, sodium salt (CI. 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-sulphone fophenyl) amino] xanthylium inner salt, sodium salt (Cl. 45.190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 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-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro 1-naphthalenesulfonic acid-chromium complex (3: 2) (Cl 15.711; Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo ] naphth-1-yl) azo] -1, 7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440, Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue). Preferred anionic substantive dyes are those under the international designations or trade names 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.

Cationic direct dyes:

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 (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride ( Cl.44,045; Basic 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; 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (Cl 42.520; Basic Violet 2), tri [4- (dimethylamino) -ph enyl] carbenium 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, 1010 Basic Violet 14), 1, 3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 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 (CI 12,251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (Cl 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 (Cl 12,245, Basic Red 76), di [4- (dimethylamino) phenyl] -iminomethane-hyd Rochloride (Cl. 41, 000; Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48,055, Basic Yellow 11), 3-Methyl-1-phenyl-4 - [(3- (trimethyl-ammonio) -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-morpholiniumpropylamino) -4- hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle, has 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 11 are called.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cl ^"

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.

Nonionic substantive 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) -annino] -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) -annino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-din-tin-aminobenzoic 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-phenyl-aminobenzene benzene.

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 its salts, 1, 4-diamino-2-nitrobenzene ( Cl., 76,070), 4-amino-2-nitro-diphenylannin (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) -annino] -2-nitrobenzene (HC Red 3), 4 - [(2 - hydroxyethyl) methylannino] -1- (n-ethylannino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) -annino] -5-methyl-2-nitrobenzene, 1-amino-4- (n-ethylannino) 2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) -annino] -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-dihydroxypr opyl) amino] -2-nitrobenzene (HC Red 1 1), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2- nitrophenyl) -annino] -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) -annino] -2-nitropyridine, 3 -Amino-6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (n-ethylannino) -2-nitropyridine, 3-amino-6- (methylannino) -2-nitropyridine, 6- (Ethylamino) -3 - [(2-hydroxyethyl) -annino] -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1 , 4-benzoxazine (HC Red 14). Suitable yellow nitro dyes are in particular:

1,2-diamino-4-nitrobenzene (CI 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-methylannino-4-nitrobenzene, 2,3- ( Dihydroxypropoxy) -3-methylannino-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 11), 1 - [(2'-ureidoethyl) amino] -4-nitrobenzene, 1-amino-4 - [(2-aminoethyl) -annino] -5-methyl-2-nitrobenzene, A- [(2-hydroxyethyl) amino] -3-nitro-1-ethylbenzene, 1-chloro-4 - [( 2-hydroxyethyl) amino] -3-nitrobenzene (H C 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-nitrobenzamide (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 (CI 61, 505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10- anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (CI 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 (CI 75,470, Natural Red 4 ), 1 - [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) -annino] -9,10-anthraquinone (HC Red 8) 1,1,4-diamino-2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, 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 (Cl. 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- (methylannino) phenyl) innino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} -annino} -5 - [(2-hydroxyethyl) -annino] -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-indole-2-one 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 (CI 1 1855, Disperse Yellow 3), 4 - [(4-nitrophenyl) azo] -aniline (CI 11, 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 HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 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-ethylbenzene, 1-amino-4- (2-hydroxyethyl) -annino-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 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 they do not adversely affect the coloring 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 flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

The agents used according to the invention preferably contain the dye precursors and / or substantive dyes 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 solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a powdered or tablet-shaped formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a CC ₄ -alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents. The hair color-changing preparations applied in the first step of the method according to the invention and the preparation applied in the second step of the method according to the invention can furthermore contain all active ingredients, additives and auxiliaries known for the particular type of preparation. In many cases, these preparations 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, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps )

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acylsarcosides having 10 to 18 C atoms in the acyl group,

Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear α-olefin sulfonates having 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37

23,354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to

DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15

Molecules represent ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

Nonionic surfactants contain as hydrophilic group z. Example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear

Fatty alcohols having 8 to 22 carbon atoms, fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,

glycerin,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particular preference is given to those alkylpolyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ to d ₆ -alkyl groups or essentially of C 1 ₂ - to d ₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ - group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimetic acid thylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group and capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, acylaminoethylaminopropionat the coconut and the C _12-i ₈ acyl sarcosine. According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

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

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium 80th).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercially available product Glucquat ^® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride". The compounds used as surfactant with alkyl groups 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.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the agents used in the process according to the invention can be further active,

Auxiliaries and additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups,

Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylamino-ethylmethacrylate-vinylpyrrolidone copolymers,

Vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.

Butylaminoethyl methacrylate ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / 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. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as

Amylose, amylopectin and dextrins, clays such as Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean 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 agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate defoamers such as silicones, dyes for staining the agent,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines, substances for adjusting the pH, such as customary acids, especially edible acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and also 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, stinging 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 acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, 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,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants 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. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

In the context of the method according to the invention, the preparations are filled in two successive steps in a package.

In principle, all systems in question in which the hair color-changing preparations according to the invention can be stably stored are suitable for the purposes of the present invention.

As such, for example, crucibles, pots, sachets and tubes in question.

In a particularly preferred embodiment of the present invention, the packaging used is a tube.

The tube is preferably made of a material suitable for packaging tinting and coloring agents of this type. As particularly suitable according to the invention, laminated aluminum has proved itself both for the outer walls and for the inner walls. However, tubes made of plastic laminate (PE, PET, PP) or plastic coextrudates (PE, PET, PP) are also conceivable.

As a very particularly preferred according to the invention, a tube has been found, which is made of aluminum laminate, which is optionally still protected with a paint. Under aluminum laminate is understood according to the invention a coated with plastic aluminum layer. Aluminum tubes which are painted, for example with a phenolic resin, have also proved to be particularly preferred according to the invention.

In the context of this embodiment, it has proven to be particularly advantageous if tube sleeves are used in the context of the method according to the invention, which are already closed with a screw on the side on which the finished product can be removed later. Particularly preferably, this tube opening below the screw cap is further closed with an airtight foil, preferably made of laminated aluminum.

The tube sleeves prepared in this way are preferably not yet closed at their rear end before being filled, so that the tube walls form an open cylinder into which the preparations can be filled in the context of the method according to the invention.

In the context of the first step of the method according to the invention, the hair color-changing preparation is introduced into the rear opening of the tube sleeve. It makes preferably either the Tube itself or the nozzle from which the preparation exits, an upward-downward movement, so that a bubble-free bottom-upwards filling is guaranteed.

Subsequently, the second preparation containing at least one reducing agent is applied to the surface of the hair color-changing preparation.

It has proved to be particularly preferred according to the invention when the preparation used in the second step is sprayed on.

Depending on the particular embodiment of the present invention, the spraying may be carried out at room temperature or at elevated temperature. If the preparation applied in this step is solid at room temperature, it is heated to above its melting point and then applied by means of a heated spray nozzle in the warm state to the hair color-changing preparation.

If the composition containing the reducing agent is gaseous, it is preferred according to the invention if the surface of the hair color-changing preparation is rinsed with this preparation or this is applied to the surface. According to the invention, it may be particularly preferable if the dead space of the packaging is filled with the gaseous preparation. In the context of a first embodiment of the method according to the invention, the second preparation, which contains at least one reducing agent, is prepared at a clear time interval for spraying or application.

In the context of a second embodiment of the method according to the invention, it may be preferred if the preparation applied in the second step is produced only shortly before or during the application. In the context of this embodiment, the second preparation can be prepared both as a whole for spraying or in part preparations which are mixed only shortly before spraying. This mixing can preferably be carried out continuously, for example by means of dynamic, static or microstructured mixers or in the nozzle. It may be particularly preferred according to the invention if the part preparations mix only when introduced into the packaging, for example from several nozzles to the finished preparation.

In the third step of the method according to the invention, the packaging is closed. In the event that the packaging was filled from the side from which the product is to be removed later, this is preferably done by screwing or applying the cap. It is inventively preferred if the opening is initially provided with an airtight film, for example, laminated aluminum. If the packaging is a tube filled from the back, the tube will be welded (plastic or plastic laminate) or folded (aluminum) depending on the material of the tubes. During welding, preferably the hot air technique, the laser or high-frequency technology or the pressing jaw technology (heated pressing jaws compress the plastic tube) are used.

A second object of the present invention is the use of a solution containing at least one reducing agent to prevent oxidative changes of hair color-modifying agents in sales packages.

A third object of the present invention is the use of a solution containing at least one reducing agent for the protection of hair color-changing agents from oxidation by atmospheric oxygen.

With regard to the preferred uses according to the second and third articles of the present invention, mutatis mutandis, the said to the preferred method of the invention applies.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

Examples

The following information is expressed as a percentage by weight, unless otherwise specified.

The following formulations were prepared:

Hair color changing dye cream

2 second preparation

3 experimental procedure

In 8 aluminum tube sleeves painted with phenolic resin, 60 ml of the dyeing cream described under point 1) were respectively introduced under a nitrogen atmosphere. In each case 2 of the filled tubes immediately after one of the formulations A, B and C was sprayed onto the surface of the dyeing cream in a circular manner. In 2 tubes no aftertreatment was performed. Subsequently, all tube sleeves were folded under nitrogen atmosphere at the end.

After 6 weeks storage at room temperature, the tubes were cut at the folded end and the color of the surface of the staining cream was evaluated.

The untreated staining cream was discolored in the end. In comparison, the one with

Formulation B treated dye cream only a very slight staining. On the other hand, the dyeing creams treated with formulations A and C had no staining at all.

4 List of used commercial products

Acusol ^® OP 301 Acryl-Styrol-Copolymer about 39 to 41% active ingredient content in water, (INCI name: Styrene / Acrylates Copolymer) (Rohm & Haas)

Belsir ADM 1650 with aminoalkyl-modified polydimethylsiloxane (INCI name: Amodimethicone) (Wacker)

Crosilk ^® 1000 hydrolyzed silk protein (about 20-23% solids in water, INCI name: Aqua (Water), Hydrolyzed SiIk) (Croda)

Eumulgin ^® CS6 Cetylstearylalkohol with about 6 EO units (INCI name: Ceteareth-6) (Clariant)

Genamin ^® KDMP N, N, N-trimethyl-N (C ₂ o- ₂₂ alkyl) ammonium chloride (approximately 77-83% active ingredient in isopropanol; INCI name: Behentrimonium Chloride) (Clariant) Genapol ^® T 500 P cetylstearyl alcohol with approx. 50 EO units (INCI name: Ceteareth-

50) (Clariant)

Gluadin ^® WLM wheat protein hydrolyzate (about 21-24% solids, INCI name:

Hydrolyzed Wheat Protein) (Cognis)

Hydrosoy ^® 2000 hydrolysed soy protein (about 20-26% solids in water, INCI

Name: Aqua (Water), Hydrolyzed Soy Protein (Croda)

Lanette ^® 14 myristyl alcohol (INCI name: Myristyl Alcohol) (Cognis)

Lanette ^® OC ₁₆ -i ₈ fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

Merquat ^® 295 Dimethyldiallylammoniunnchlorid acrylic acid copolymer (about 35-

40% solids in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)

Sasol ^® wax 5205 refined paraffin (INCI name: paraffin) (Sasol)

Claims

Patent claims

1. A method for filling hair color-changing products in packaging, characterized in that in a first step, the hair color-changing preparation is filled in the package, in a second step, a preparation is applied to the surface of the hair color-changing preparation containing at least one reducing agent, and in a third step the packaging is closed.

2. The method according to claim 1, characterized in that the composition used in the second step is sprayed on.

3. The method according to any one of claims 1 or 2, characterized in that the applied in the second step preparation is completed only immediately before application or during the application itself.

4. The method according to any one of claims 1 to 3, characterized in that the applied in the second step preparation has a pH of 3 to 6.

5. The method according to any one of claims 1 to 4, characterized in that the applied in the second step preparation further contains a thickening polymer.

6. The method according to claim 5, characterized in that the thickening polymer contains as monomers acrylic acid and / or acrylic acid derivatives and / or methacrylic acid and / or methacrylic acid derivatives and optionally further comonomers.

7. The method according to any one of claims 1 to 6, characterized in that the applied in the second step preparation is solid at room temperature and has a melting point between 40 and 7O ⁰ C, preferably between 45 and 6O ⁰ C.

8. The method according to any one of claims 1 to 7, characterized in that the reducing agent is selected from lithium aluminum hydride, sodium sulfide, sodium sulfite, sodium dithionite, sodium thiosulfate and sodium borohydride.

9. The method according to any one of claims 1 to 8, characterized in that the hair color-changing preparation is an oxidative colorant containing at least one developer component.

10. The method according to any one of claims 1 to 9, characterized in that the hair color-changing preparation is an oxidative dye containing at least one indole and / or indoline derivative.

11. Use of a preparation containing at least one reducing agent to prevent oxidative changes of hair color-changing agents in sales packaging.

12. Use of a preparation containing at least one reducing agent, for the protection of hair color-changing agents from oxidation by atmospheric oxygen.