WO2009030516A2 - Pastel coloring - Google Patents

Abstract

A method for changing the color of keratinic fibers, particularly human hair, that substantially avoids damage to the hair and is able to at least partially “repair” damage that has already occurred, which is to say strengthen the hair structure, comprises these steps that directly follow each other without further intermediate steps: (i) Applying a bleaching agent composition to the keratin fibers and allowing it to act over a period from one to 45 minutes, (ii) Rinsing the bleaching agent composition, (iii) Applying a coloring agent composition, comprising at least one natural colorant, (iv) Rinsing the coloring agent composition.

Description

 "Pastel color"

The invention relates to a bleaching and dyeing method for human hair.

Changing the shape and color of the hair is an important area of modern cosmetics. This allows the hair's appearance to be adapted to current fashion trends as well as to the individual wishes of the individual. In this case, permanent wave and other hair-changing methods can be used almost independently of the type of hair to be treated. In contrast, dyeing and in particular bleaching processes are limited to certain initial hair colors. So for lightening procedures, the so-called Blondierverfahren, essentially only dark blond or lighter hair. The basics of the bleaching processes are known to those skilled in the art and may be described in relevant monographs, e.g. by Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, be read.

Thus, solid or paste-like preparations with solid oxidizing agents are usually mixed with a dilute hydrogen peroxide solution immediately before use. This mixture is then applied to the hair and rinsed again after a certain exposure time.

The present invention also relates to agents for dyeing and whitening keratin-containing fibers, in particular human hair. Conventional hair dyes usually consist of at least one developer and at least one coupler substance and possibly even contain direct dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

The developer components are usually primary aromatic amines with a further, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5 Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, A-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.

In particular α-naphthol, 1, 5, 2,7 and 1, 7 are suitable as coupler substances. Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmanns Blau), 1 Phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro 6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

For temporary dyeings usually dyeing or tinting agents are used, which contain as coloring component so-called direct drawers. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible "discoloration" occurs much faster.

Prior to their application to human hair hair dye with oxidation dye precursors are mixed with dilute aqueous hydrogen peroxide solution. The duration of exposure to the hair to achieve complete coloration is between about 30 and 40 minutes. It is obvious that users of these hair dyes have a need to reduce this exposure time.

The color change of non-blond hair towards brighter shades is usually due to oxidative lightening (bleaching) and simultaneous or subsequent staining. However, the potential for damage to the keratinic fibers is very high due to the concentrated use of oxidizing agents. The opening of the cuticle, which is necessary for the whitening result, can in individual cases be accompanied by damage to the inner hair structure (corneum), in particular if bleaching is done frequently, for a very long time, or with very strong bleaching agents. This damage is due, for example, to the destruction and / or elution of melanin particles in the hair structure.

There is a parallel with the need to change hair color, usually the desire not to neglect the care state of the fibers. Therefore, conventionally, the fibers are treated with a separately formulated conditioner immediately after the color-changing treatment.

Recently, there have always been efforts to incorporate the care components already in the application preparation. However, this frequently led to problems, since the applied care substances are not sufficiently stable under the aggressive conditions (strong oxidizing agents, high pH value) of the lightening preparation. It is an object of the present invention to provide a process for modifying keratinic fibers, in particular human hair, which largely avoids damage to the hair or which is able to at least partially "repair" damage that has already occurred, ie the hair structure strengthen.

Surprisingly, it has now been found that the use of a two-stage process leads to a significantly reduced damage

A first object of the present invention is a process for dyeing and whitening keratin fibers, characterized by the direct and without further intermediate steps successive steps

(i) applying a bleaching agent formulation to the keratin fibers and allowing to act for a period of from one to 45 minutes, (ii) rinsing the bleaching preparation, (iii) applying a colorant formulation containing at least one natural dye, (iv) rinsing the colorant preparation.

In the first step of the process according to the invention, a bleaching agent preparation is applied to the keratinic fibers. This can be taken directly from a package, but it is also possible and preferred to mix them together prior to application of two or more separately packaged precursors. This serves in particular the separation of incompatible ingredients and the better shelf life of the products.

Accordingly, processes according to the invention are particularly preferred in which, in a first step (i), a preparation A comprising at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid carriers, optionally with a preparation B containing at least one

Bleaching power, o optionally mixed with a preparation C to an application preparation and o is applied to the keratinic fibers.

Step (ii) of the method according to the invention is the rinsing out of the bleaching agent preparation after a contact time t-i which is one to 45 minutes.

In the process according to the invention, a bleaching agent preparation (application mixture) is applied to the keratinic fibers whose color is to be changed. In the simplest case, the sales product already contains this packaged application mixture in the form of Preparation A containing at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid supports.

In order to produce stronger color changes, it has proven useful to incorporate so-called bleaching power amplifiers into the application mixture. Since these substances are usually not stable in aqueous solution and / or adversely affect the storage stability of hydrogen peroxide-containing solutions or dispersions, it is preferred to provide them in the sales product separately from the preparation A and the consumer the application preparation by mixing the preparation A with the bleaching power amplifier or the preparation containing the bleaching power enhancer (Preparation B) should be prepared immediately before use.

If further substances are to be incorporated in the application mixture which are incompatible with both hydrogen peroxide and with the bleaching power enhancer, it is appropriate to provide them in the sales product in a third preparation C and to provide the consumer with the application preparation by mixing the preparation A with the bleaching power amplifier or bleach booster the preparation containing the bleaching power enhancer (Formulation B) and the preparation containing the other substance (Formulation C) are made directly before use.

Of course, the case described above can also be realized without additional bleaching power amplifier. In this case, preparation C is a second preparation in the commercial product, and the consumer prepares the preparation for use by mixing preparation A with the preparation containing the other substance (preparation C) directly before use.

If a sales packaging contains a preparation B and / or a preparation C in addition to preparation A, the application preparation is prepared by mixing and applied to the keratinic fibers (step 1 of the process according to the invention) and rinsed off again after a contact time t-i.

In the Blondiermitteln in the market, the separation in at least two preparations A (hereinafter also called "developer" or "developer dispersion") and B (hereinafter also "Blondierpulver" or "Blondiermittel" called), enforced.

The bleaching agents preferably contain a solid peroxo compound. The selection of this peroxo compound is in principle not limited; customary peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate,

Potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium persulfate,

Sodium persulfate, percarbonates such as magnesium percarbonate, peroxides and perborates, urea peroxide and melamine peroxide. Among these peroxo compounds, which can also be used in combination, according to the invention are the inorganic compounds prefers. Particularly preferred are the peroxydisulfates, in particular combinations of at least two peroxydisulfates.

Preferred bleaching agents (and thus preferred bleaching compositions used in the process according to the invention) are therefore characterized in that the solid peroxo compound is selected from ammonium and alkali metal persulfates and peroxidisulfates, with particularly preferred compositions according to the invention containing at least 2 different peroxydisulfates.

A particularly preferred bleaching agent (and thus a particularly preferred bleaching composition used in the process according to the invention) is characterized in that the bleaching powder contains as bleaching agent a solid bleaching agent selected from hydrogen peroxide addition compounds to solid supports, ammonium and alkali metal persulfates and peroxydisulfates.

The peroxo compounds are present in the bleaching agents (and thus bleaching preparations used in the process according to the invention) preferably in amounts of from 1 to 80% by weight, preferably from 5 to 70% by weight, particularly preferably from 20 to 65% by weight and in particular from 35 to 60% by weight, based in each case on the total agent.

As a further component, the bleaching agents (and thus preferred bleaching compositions used in the process according to the invention) may contain an alkalizing agent which serves to adjust the alkaline pH of the application mixture. In accordance with the invention, the usual alkalizing agents known to the person skilled in the art for bleaching agents, such as ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, hydroxycarbonates, silicates, in particular metasilicates and alkali metal phosphates, can be used. In a preferred embodiment, the bleaching agents (and thus preferred bleaching compositions used in the process according to the invention) comprise at least two different alkalizing agents. In this case, mixtures of, for example, a metasilicate and a hydroxycarbonate may be preferred.

The bleaching agents (and thus preferred bleaching compositions used in the process according to the invention) comprise alkalizing agents, preferably in amounts of from 5 to 30% by weight, in particular from 15 to 25% by weight.

The bleaching agents (and thus preferred bleaching compositions used in the process according to the invention) may contain further ingredients, for example complexing agents, phosphates, surfactants, emulsifiers, etc. These substances are described below since they may also be part of the developer dispersion, for example. A particularly preferred group of ingredients that may be part of the bleaching powder are the bleach boosters. Bleach boosters are preferably used to increase the bleaching action of the oxidizing agent, in particular the hydrogen peroxide. Suitable bleach boosters are (BV-i) compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids and / or optionally substituted perbenzoic acid, and / or

(BV-ii) carbonate salts and / or bicarbonate salts, and / or

(BV-iii) organic carbonates, and / or

(BV-iv) carboxylic acids, and / or (BV-v) peroxo compounds.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry oxygen- and / or nitrogen-bonded acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

The carbonate or bicarbonate salts are preferably selected from at least one compound of the group consisting of ammonium, alkali (especially sodium and potassium), and Erdalkalicarbonatsalzen and bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate, potassium bicarbonate, dipotassium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

With the bleach boosters, too, care must be taken that the compounds used are water-soluble. Preferably usable organic carbonates are selected from at least one compound of the group of carbonic acid monoesters and / or from at least one compound of the group of carbonic acid monoamides.

Preferably usable carbonic acid monoesters are the carbonic acid monoesters of the formula (BV-1),

R-O-C-OH Il 0 (BV-1) in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (BV-1), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a Ci_ ₆ alkyl group. Examples of C ₁ -C 6 -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Compositions particularly preferably used according to the invention are characterized in that the radical R in formula (BV-1) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, ferf Butyl and hydroxymethyl and hydroxyethyl radicals.

Preferred carbonic acid monoamides are the compounds of the formula (BV-2),

R- N- C- OH H Il

⁰ (BV-2) in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (BV-2), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably R is a C-. _6- alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl. Bleach enhancers of the formula (BV-2) which are particularly preferred according to the invention are characterized in that the radical R in formula (BV-2) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, ferf-butyl and hydroxymethyl and hydroxyethyl radicals.

The acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention. Carbonic acid monoesters or the carbonic acid monoamides which are present in completely or partially neutralized form, preferably in the form of the alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt, are preferred according to the invention.

As the bleach-enhancing carboxylic acid, in the compositions of the present invention, at least one compound selected from the group consisting of acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and orthophthalic acid may preferably be contained.

The bleach boosters are present in the bleaching agents (and thus in preferred bleaching preparations used in the process according to the invention) preferably in amounts of from 5 to 30% by weight, in particular in amounts of from 8 to 20% by weight, based in each case on the weight of the ready-to-use agent, contain.

The bleaching agent preparations are preferably obtained by mixing a bleaching powder with a developer dispersion. This developer dispersion preferably contains at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants and emulsifiers for the compositions 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 as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants and emulsifiers are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 ° C Atoms (soaps),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 16, acylsarcosides having 8 to 24 C Atoms in the acyl group, acyltaurides having 8 to 24 carbon atoms in the acyl group, Acyl isethionates having 8 to 24 carbon atoms in the acyl group, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefin sulfonates having 8 to 24 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

Acylglutamates of the formula (I),

XOOC-CH ₂ CH ₂ CH-COOX (I)

I HN-COR ¹

in which R ¹ CO is a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, for example acylglutamates, which are derived from fatty acids having 6 to 22, preferably 12 to 18, carbon atoms, for example C _12/14 or C _12/18 coconut _fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid, in particular sodium N-cocoyl and sodium N-stearoyl-L-glutamate,

Esters of a hydroxy-substituted di- or tricarboxylic acid of the general formula (II),

X

HO - C - COOR ¹ (II)

Y - CH - COOR ²

wherein X is H or a -CH ₂ COOR group, Y is H or -OH, under the condition that Y is H when X-CH ₂ COOR, R, R ¹ and R ^{2 are} independently Hydrogen atom, an alkali or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group of etherified (C ₆ -C ₈ ) alkyl polysaccharides having 1 to 6 monomers Saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R, R ¹ or R ^{2 is} a radical Z, esters of sulfosuccinic acid or Sulfosuccinates of the general formula (III), H ₂ C - COOR ¹ (III)

I

_M (n ₊ / n) -Q ₃₈ _ _CH _ COOR ²

in which M ^{(n + / n)} for n = 1 represents a hydrogen atom, an alkali metal cation, an ammonium group or the cation of an ammonium organic base and for n = 2 an alkaline earth metal cation and R ¹ and R ² independently of one another represent a hydrogen atom, an alkali metal cation or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group consisting of etherified (C ₆ -C ₁₈ ) -alkyl polysaccharides having 1 to 6 monomeric saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R ¹ or R ^{2 is} a radical Z,

Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R- (O-CH ₂ -CH ₂ ) _X -OSO ₃ H, in which R is a preferably linear alkyl group of 8 to 30 carbon atoms and x = 0 or 1 to 12, mixed hydroxysulfonate surfactants according to DE-A-37 25 030, esters of tartaric acid and citric acid with alcohols, the addition products of about 2- 15 molecules of ethylene oxide and / or propylene oxide to C ₈ . _{22 are} fatty alcohols, alkyl and / or alkenyl ether phosphates, sulfated fatty acid alkylene glycol esters, monoglyceride sulfates and monoglyceride ether sulfates.

Preferred anionic surfactants and emulsifiers are acylglutamates, acyl isethionates, acyl sarcosinates and acyl taurates, each with a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, which in particularly preferred embodiments of an octanoyl, decanoyl, lauroyl , Myristoyl, palmitoyl and stearoyl radical, esters of tartaric acid, citric acid or succinic acid or of the salts of these acids with alkylated glucose, in particular the products with the INCI name Disodium Coco-Glucoside Citrate, Sodium Coco-Glucoside Tartrate and Disodium Coco-glucosides sulfosuccinates, alkyl polyglycol ether sulfates and ether carboxylic acids having 8 to 18 carbon atoms in the alkyl group and up to 12 ethoxy groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl ester having 8 to 18 C atoms in the alkyl group and 1 to 6 ethoxy groups. Zwitterionic surfactants and emulsifiers are surface-active compounds which have at least one quaternary ammonium group and at least one COO ⁽⁾ or -SO ₃ '^"' group in the molecule, particularly suitable zwitterionic surfactants and Emulsifiers are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-ol Hydroxyethylimidazoline each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants and emulsifiers are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylaminopropionic 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 24 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Nonionic surfactants and emulsifiers contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms

Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,

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

Polyol fatty (partial) ester as Hydagen ^® HSP (Cognis) or Sovermol ^® - types (Cognis), especially of saturated C. _{8 3} o-fatty acids, alkoxylated triglycerides, alkoxylated fatty acid alkyl esters,

Amine oxides,

Fatty acid alkanolamides, fatty acid N-alkylglucamides and fatty amines and their ethylene oxide or polyglycerol addition products,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Zuckerfettsäureester and methylglucoside fatty acid esters and their ethylene oxide or

Polyglycerol addition products,

Alkylpolyglycosides corresponding to the general formula RO- (Z) _x wherein R is alkyl, Z is

Sugar and x represents the number of sugar units.

Particular preference is given to those alkylpolyglycosides in which R consisting essentially of C ₈ and C ₁₀ alkyl groups, consisting essentially of C ₁₂ and C ₁₄ alkyl groups, essentially of C ₈ to C ₁₆ alkyl groups or substantially of C ₂ to C ₆ alkyl groups or consisting essentially of Ci ₆ to Ci ₈ 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 alkylpolyglycosides which can be used according to the invention contain on average 1, 1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 8.

Mixtures of alkyl (oligo) glucosides and fatty alcohols, eg. B. Montanov ^® 68,

Sterols, e.g. Ergosterol, stigmasterol, sitosterol and mycosterols,

Phospholipids, e.g. B. lecithins or phosphatidylcholines,

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

(Dehymuls ^® PGPH) or Triglycerindiisostearat (Lameform ^® TGI), alkoxylated polydialkylsiloxanes (INCI name: dimethicone copolyol).

Preferred nonionic surface-active substances have been the alkylpolyglycosides, optionally in admixture with fatty alcohols, alkoxylated polydialkylsiloxanes, alkylene oxide amide products of saturated linear fatty alcohols and fatty acids with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid.

Also usable according to the invention are cationic surfactants 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 trialkylmethylammonium chlorides. The long alkyl chains of these surfactants preferably have 10 to 18 carbon atoms, such as. In cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride. Further preferred cationic surfactants are the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.

In addition to the surfactant (s), the developer dispersion preferably contains polymer (s). In a preferred embodiment, therefore, polymers are added to the developer dispersions, with both cationic, anionic, amphoteric and nonionic polymers having proven effective.

Cationic or amphoteric polymers are preferably usable according to the invention. Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Homopolymers of the general formula (G1-I),

R ¹

I - [CH ₂ -CJ _n X ^" (G 1-1)

I CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C 1-4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers preferably, 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 has the value 2.

Suitable physiologically acceptable counterions X ^' are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

A particularly suitable homopolymer is the, if desired cross-linked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium- 37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous 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 about 50% polymer content, additional components: 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, additional 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 Designation: PPG-1-trideceth-6)) are commercially available.

Copolymers with monomer units of the formula (G1-I) contain, as nonionic monomer units, preferably acrylamide, methacrylamide,

and methacrylic acid-C-ι_ ₄ -alkyl. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred 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.

Further preferred cationic polymers are, for example

quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, such as in particular the products sold under the trade name Cosmedia guar ^® and Jaguar ^® products, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride Acrylamide copolymer) commercially available products are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27, having quaternary Nitrogen atoms in the polymer backbone.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ^® LM 200), known polymers. , Gaffix ^® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, preferably usable zwitterionic polymers are composed essentially together

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A < ^- ) ( ^{Z ~} ')

In the R ¹ and R ² independently of one another are hydrogen or a methyl group and R, R and R independently represent alkyl groups having 1 to 4 carbon atoms, Z is one

NH group or an oxygen atom, n is an integer from 2 to 5 and A "is the anion of an organic or inorganic acid

and

B) monomeric carboxylic acids of the general formula (Z-II),

R ⁶ -CH = CR ⁷ -COOH (Z-II) in which R "and R independently of one another are hydrogen or methyl groups.

Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide,

Dimethylaminopropylmethacrylamide and diethylaminoethylacrylamide when Z is an NH group or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The monomers containing a tertiary amino group are then quaternized in a known manner, methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents. The quaternization reaction can be carried out in aqueous solution or in the solvent.

Advantageously, such monomers of formula (Z-I) will be the derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Likewise preferred are those

Monomers of the formula (Z-I) in which R, R ^ and R ^ are methyl groups.

The acrylamidopropyltrimethylammonium chloride is a most preferred monomer of formula (Z-I).

Suitable monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (ZI) and (Z-II) by polymerization processes known per se. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution. The alcohols used are alcohols having 1 to 4 carbon atoms, preferably isopropanol, which simultaneously serve as polymerization regulators. However, other components than regulators may also be added to the monomer solution, eg. For example, formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the aid of free-radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such. As azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are z. B. combinations of hydrogen peroxide, potassium or ammonium oxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component. The polymerization can be carried out isothermally or under adiabatic conditions, depending on the concentration ratios by the heat of polymerization released, the temperature range for the course of the reaction between 20 and 200 ⁰ C may vary, and the reaction may optionally be carried out under autogenous pressure. Preferably, the reaction temperature is between 20 and 100 ⁰ C.

The pH during the copolymerization may vary within a wide range. Advantageously, polymerization is carried out at low pH values; however, pH values above the neutral point are also possible. After the polymerization is treated with an aqueous base, for. As sodium hydroxide, potassium hydroxide or ammonia, to a pH between 5 and 10, preferably 6 to 8 set. Further details of the polymerization process can be found in the examples.

Be particularly effective, such polymers have been found in which the monomers of the formula (Z-I) were present in excess over the monomers of formula (Z-II). It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (ZI) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, in particular from 75:25 to 95: 5 , consist.

The cationic or amphoteric polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

The anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic 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 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer can be found to be particularly effective, it being possible for the sulfonic acid group to be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt ,

More preferably, 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 embodiment, it may be preferable 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 esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are 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 may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin) and a nonionic emulsifier (laureth-7), has proved to be particularly advantageous within the scope of the teaching according to the invention.

Also sold under the name Simulgel ^® 600 as a compound with isohexadecane and polysorbate 80 Natriumacryloyldimethyltaurat copolymers have proven to be particularly effective according to the invention.

Likewise 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 trademark Carbopol ^® commercially.

Copolymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are also dye-retaining polymers. A 1, 9-decadiene crosslinked maleic acid-methyl vinyl ether copolymer is available under the name Stabileze® QM ^® commercially available.

In another embodiment, the agents according to the invention may contain nonionic polymers (G4).

Suitable nonionic polymers are, for example:

Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers. Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose Methylhy-, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALON) and Natrosol ^® grades (Hercules).

Starch and its derivatives, in particular starch, such as Structure XL ^® (National Starch), a multifunctional, salt-tolerant starch;

shellac

Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF).

Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ^° C. under normal pressure. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups.

Glycosidically substituted silicones.

It is also possible according to the invention that the preparations comprise a plurality of, in particular two, different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.

The polymers (G) are contained in the developer dispersions preferably in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly preferred.

Other active ingredients, auxiliaries and additives which may be present both in the bleaching agent and in the developer dispersion are, for example

nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes; cationic polymers such as quaternized cellulose ethers and other solid state compounds; zwitterionic and amphoteric polymers which are stable as solids

Commercial products are available, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids and

Vinyl acetate / crotonic acid copolymers, provided that they are stable as solids or preferably in

Trade are available,

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 polyvinyl alcohol, structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean lecithin, egg lecithin and cephalins, and silicone oils

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, dimethyl isosorbide and cyclodextrins, colorants for coloring the preparations,

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

Cholesterol,

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

Fatty alcohols and fatty acid esters,

fatty,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

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

The compositions of the invention may also contain other ingredients. For example, the use of so-called oil components proved to be advantageous.

With particular preference the agents according to the invention additionally contain an oil component (D). Oil components are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which may be in solid form as well as liquid in aqueous dispersion, and natural and synthetic cosmetic oil components.

As fatty acids (D1) it is possible to use 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 acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from the Roelen oxo synthesis 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 - 15 wt.%, Based on the total mean. The amount is preferably 0.5-10% by weight, with amounts of 1-5% by weight being particularly advantageous.

As fatty alcohols (D2) it is possible to use saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ -C ₃₀ -, preferably C ₁₀ -C ₂₂ -and very particularly preferably C ₁₂ -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 reduction of 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 30% by weight, based on the total preparation, preferably in amounts of from 0.1 to 20% by weight.

As natural or synthetic waxes (D3) it is possible according to the invention to use solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, fruit waxes such as, for example, apple wax or citrus wax, microwaxes of PE or PP. Such waxes are available, for example, from Kahl & Co., Trittau. The amount used is 0.1-50 wt.% Based on the total agent, preferably 0.1 to 20 wt.% And particularly preferably 0.1 to 15 wt.% Based on the total agent.

Particularly preferred are so-called cosmetic oil bodies as ingredients of the compositions according to the invention.

The natural and synthetic cosmetic oil bodies (D4) include, for example: vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils. liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of from 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether Di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl-n Undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products 1, 3-di- (2-ethyl-hexyl) - cyclohexan (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred. Esteröle. Ester oils are to be understood as meaning the esters of C ₆ - C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and 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 oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. According to the invention, particularly preferred are isopropyl myristate (IPM Rilanit ^®), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ^® LC), n-butyl stearate, oleyl erucate (Cetiol ^® J 600), isopropyl palmitate (IPP Rilanit ^®), oleyl Oleate (Cetiol ^®), hexyl laurate (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM), Cetearyl Isononanoate (Cetiol ^® SN), decyl oleate (Cetiol ^® V).

Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol diisostearate,

Propylene glycol di-pelargonat, butanediol di-isostearate, Neopentylglykoldicaprylat, symmetrical, asymmetric or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,

Fatty acid partial glycerides, ie monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides. The partial glycerides preferably follow the formula (D4-I),

CH ₂ O (CH ₂ CH ₂ O) _m R ¹

I CHO (CH ₂ CH ₂ O) _n R ² (D4-I)

I CH ₂ O (CH ₂ CH ₂ O) _q R ³

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{1 is} an acyl radical and R ² and R ^{3 are} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic , Elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, oleic acid monoglycerides are used.

In summary, agents according to the invention are particularly preferred which additionally contain an inert oil component, preferably from the group of esters of long-chain fatty acids, more preferably from the group of alkyloleates and / or alkyl stearates. Following the rinsing out of the blonding agent spread, a colorant preparation containing at least one natural dye is applied to the fibers without further intermediate treatment of the keratinic fibers.

Suitable natural dyes are all dyes contained in plants, animals and microorganisms and recoverable from these, in particular those which have already been used for dyeing keratin fibers or hair. An overview of natural dyes can be taken from Ullmann's Encyclopadie der technischen Chemie, 4th Edition (19), Volume 11, pages 100-134.

Natural dyes which are particularly preferred according to the invention are selected from henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, sedre and alkana root.

Corresponding methods according to the invention in which the natural dye (s) is / are selected from henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, seder and alkana root preferred according to the invention.

In addition to the natural dyestuffs mentioned or in their place, further natural dyestuffs may be present in the dyestuff preparation used in the process according to the invention. Here, corresponding methods according to the invention are preferred in which the natural dye (s) is / are selected from cinnamon, devil's claw, licorice, beetroot, blackberry, ratanhia, red sandalwood, blueberry, chamomile, rhubarb, cornflower, senna, galangal.

Thus, it may be particularly preferred according to the invention to use at least one natural product selected from henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre, alcano root, cinnamon , Devil's claw, liquorice, beetroot, blackberry, ratanhia, red sandalwood, blueberry, chamomile, rhubarb, cornflower, senna and galangal.

For further coloration and / or for shading, the colorant preparation used in the process according to the invention may contain substantive dyes.

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% by weight, 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) (CI 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 (Cl.

19,140; Food Yellow No. 4; Acid Yellow 23), 3 - [(4-

Phenylamino) -phenyl] -azobenzenesulfonic acid sodium salt (CI 13,065; Ki406; Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45,350; Acid Yellow 73; D & C Yellow No 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (Cl.10, 385; Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) azo] -benzenesulfonic acid, sodium salt (Cl Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (Cl 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [( 2,4-dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170, Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (Cl. Acid Red 4), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (Cl 14.720; Acid Red No.14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (Cl 16,255, Ponceau 4R, Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1) yl) azo] -2,7-naphthalene-disulfonic acid trinatriu Msalz (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-tetraiododibenzopyran- 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-ethyleneamine ammonium hydroxide, inner salt, sodium salt (CI 45, 100, Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27,290; Acid Red 73), 2 ', 4', 5 ', 7'-tetrabromo-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one disodium salt (Cl 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-sulfonaphylene-azole) -naphthalenecarboxylic acid calcium salt (Cl 15.850: 1; Pigment Red 57: 1). , 3 - [(2,4-Dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (Cl 14.700, Food Red No. 1, Ponceau SX, FD & C Red No. 4), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (Cl. 61, 570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3, 7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50), bis [4- (diethylamino) -phenyl] (2,4-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 internal 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-ethylbenzene methanaminium hydroxide, inner salt, sodium salt (Cl. 42.080; Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt

Betaine (CI 42,090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62,055, Acid Blue 25), i-amino ^ ^ cyclohexylamino ^ θ.iO-anthraquinone ^ -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-sulfophenyl) 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 (Cl.60,730, D & C Violet No. 2, Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] sulfone (Cl.10,410 Acid Brown 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) -azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1). , 3-Hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene-sulfonic acid chromium complex (3: 2) (Cl 15.711; Acid Black 52), 4- (Ace tylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7-naphthalenedisulfonic acid, tetrasodium salt (Cl. 28.440; Food Black no. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonphthalein (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 (Cl.11, 154, Basic Blue 41 ), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3 (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (Cl 56.059, Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride ( Cl. 42,535; Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (Cl 42,520, Basic Violet 2), tri [4- (dimethylamino) -phenyl] 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, 510 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.1 1, 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 hydrochloride (CI 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- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (Cl 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogen sulfate (1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholinium-propylamino) -4-hydroxy-9 , 10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle containing at least one quaternary Having 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) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1- [ (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl- 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1 - (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

Suitable red nitro dyes are in particular:

1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1, 4-diamino-2-nitrobenzene ( Cl., 76,070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino 4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2 -Hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) 2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) - amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2 ), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4- [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1, 4- [di (2,3-dihydroxypropyl) ami no] -2-nitrobenzene (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino ] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2, 5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino- 6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) 3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1, 4- benzoxazine (HC Red 14).

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-methylamino-4-nitrobenzene, 2,3- ( Dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [( 2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4- nitrobenzene, 1-amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4- [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yello w 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3- nitro-benzonitrile (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 (CI 61,554, 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) -amino] -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 n (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- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500 , Natural Brown 7), 2-hydroxy-1, 4-naphthoquinone (CI 75,480, Natural Orange 6), 1, 2-dihydro-2- (1,3-dihydro-3-oxo-2H-indole-2 ylidene) -3H-indol-3-one (Cl 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4.5 -dihydro-5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:

1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (Cl. 11, 210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino ] -4 - [(4-nitrophenyl) azo] -benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7 2,6-diamino-3- [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, 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-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2- Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

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

Although in the colorant preparation may also be contained oxidation dye precursors of the coupler and developer type, which are oxidatively developed to the dye molecule, this is much less preferred because of the possible damage potential associated therewith. Preferred processes according to the invention are characterized in that the colorant preparation contains no oxidation dye precursors.

The colorant preparation used in the process according to the invention may optionally contain ammonia (hereinafter always calculated as 100% NH ₃ ), the amount of which is preferably limited to a maximum of 2% by weight, based on the total composition or in the case of multi-component compositions, based on the ready-to-use mixture is. Preferred colorant formulations or application mixtures used in the process according to the invention comprise a maximum of 1. 8% by weight of ammonia, more preferably of at most 1.5% by weight of ammonia, even more preferably not more than 1.25% by weight of ammonia, more preferably not more than 1, 0 wt .-% ammonia and in particular a maximum of 0.5 wt .-% ammonia. In a further preferred embodiment of the present invention, the agents are ammonia-free.

According to the invention particularly preferred methods are therefore characterized in that the colorant preparation does not contain ammonia.

A waiver of amines in the colorant preparation leads to a reduced damage in the third step. Therefore, methods of the invention wherein the colorant formulation does not contain amines are preferred.

Similarly, a content of the colorant preparation of hydrogen peroxide is contraindicated because of possible damage to the preloaded keratinic fibers. Further preferred methods according to the invention are characterized in that the colorant preparation contains no hydrogen peroxide.

This concept can be extended to all oxidizing agents. Particularly preferred methods according to the invention are therefore characterized in that the colorant preparation contains no peroxo compounds. A further improvement of the method according to the invention can be to add further components to the colorant preparation which care for the fibers stressed by the bleaching.

Here, some care substances have proven to be particularly compatible with natural dyes, so that their use in the colorant preparation is particularly preferred.

As a further optional constituent, the colorant preparations used in the process according to the invention may contain from 0.01 to 10% by weight of at least one polymer from the group of cationic and / or amphoteric polymers.

Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

In addition to cationic polymers or in their place, the colorant formulations used in the process according to the invention may also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers.

Preferably, the polymer or polymers are used within narrower ranges. Thus, colorant preparations used in the process according to the invention are preferred which, based on their weight, are from 0.05 to 7.5% by weight, preferably from 0.1 to 5% by weight, particularly preferably from 0.2 to 3.5% by weight. % and in particular 0.25 to 2.5% by weight of amphoteric polymer (s).

Regardless of whether or not amphoteric polymers are present in the compositions, further preferred colorant preparations used in the process according to the invention are characterized in that they contain, based on their weight, from 0.05 to 7.5% by weight, preferably from 0.1 to 5 wt .-%, particularly preferably 0.2 to 3.5 wt .-% and in particular 0.25 to 2.5 wt .-% cationic (s) polymer (s) included.

Cationic polymers which can preferably be used according to the invention are described below: Homopolymers of the general formula (G1-I),

R ¹

I - [CH ₂ -CJ _n X ^" (G 1-1)

CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C 1-4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers preferably, 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 has the value 2.

Suitable physiologically acceptable counterions X ^' are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

A particularly suitable homopolymer is the optionally crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium 37. Such products are (Cosmetic Rheologies) and Synthalen ^® CR (Ethnichem), for example under the names Rheocare ^® CTH are commercially available. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous 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 about 50% polymer content, additional components: 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, additional 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)) are commercially available.

Copolymers contain monomer units having the formula (G1-I) as a non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid-C - ^ - alkyl ester and methacrylic acid-C-ι- ₄ -alkyl. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred 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.

Further preferred cationic polymers are, for example

quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, such as in particular the products sold under the trade name Cosmedia guar ^® and Jaguar ^® products, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27, having quaternary Nitrogen atoms in the polymer backbone.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ^® LM 200), known polymers. Also usable according to the invention are the copolymers of vinylpyrrolidone, as they are known as Commercial products Copolymer 845 (manufacturer: ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110 Luviquat.RTM ^® 8155 and Luviquat.RTM ^® MS are available 370th

Cationic protein hydrolysates may also be used as cationic polymers, preferred agents being one or more cationic protein hydrolyzates from the group Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimon Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurodimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurodimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrol yzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

In summary, methods according to the invention are preferred in which the colorant preparation - based on their weight - 0.05 to 7.5 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.2 to 3.5 wt. % and in particular 0.25 to 2.5% by weight of cationic polymer (s), with preferred cationic polymer (s) being / being selected from

Poly (methacryloyloxyethyltrimethylammonium chloride) (INCI: Polyquaternium-37) and / or; quaternized cellulose derivatives (INCI: Polyquaternium 10) and / or cationic alkylpolyglycosides and / or cationised honey and / or cationic guar derivatives and / or polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid and / or

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate and / or

Vinylpyrrolidone-vinylimidazolium methochloride copolymers and / or quaternized polyvinyl alcohol and / or Polyquaternium 2 and / or Polyquaternium-7 and / or Polyquaternium 17 and / or Polyquaternium 18 and / or Polyquaternium 24 and / or Polyquaternium 27.

In addition to the cationic polymers or in their place, the colorant formulations used in the process according to the invention may contain amphoteric polymers. In the context of the present invention preferably usable amphoteric polymers are composed essentially together

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ fiSr) ( ^{Z ~} ')

In the R ¹ and R ² independently represent hydrogen or a methyl group and R, R and R ^ independently represent alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A ^ 'is the anion of an organic or inorganic acid

and

B) monomeric carboxylic acids of the general formula (Z-II),

R ⁶ -CH = CR ⁷ -COOH (Z-II)

in which R ^ and R ^ independently of one another are hydrogen or methyl groups.

Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide,

Dimethylaminopropylmethacrylamide and diethylaminoethylacrylamide when Z is an NH group or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The monomers containing a tertiary amino group are then quaternized in a known manner, methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents. The quaternization reaction can be carried out in aqueous solution or in the solvent.

Advantageously, such monomers of formula (Z-I) will be the derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Likewise preferred are those

Monomers of the formula (Z-I) in which R, R ^ and R ^ are methyl groups.

The acrylamidopropyltrimethylammonium chloride is a most preferred monomer of formula (Z-I).

Suitable monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (Z-I) and (Z-II) by polymerization processes known per se. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution. The alcohols used are alcohols having 1 to 4 carbon atoms, preferably isopropanol, which simultaneously serve as polymerization regulators. However, other components than regulators may also be added to the monomer solution, eg. For example, formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the aid of free-radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such. As azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are z. B. combinations of hydrogen peroxide, potassium or ammonium oxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The polymerization can be carried out isothermally or under adiabatic conditions, depending on the concentration ratios by the heat of polymerization released, the temperature range for the course of the reaction between 20 and 200 ⁰ C may vary, and the reaction may optionally be carried out under autogenous pressure. Preferably, the reaction temperature is between 20 and 100 ⁰ C. The pH during the copolymerization may vary within a wide range. Advantageously, polymerization is carried out at low pH values; however, pH values above the neutral point are also possible. After the polymerization is treated with an aqueous base, for. As sodium hydroxide, potassium hydroxide or ammonia, to a pH between 5 and 10, preferably 6 to 8 set. Further details of the polymerization process can be found in the examples.

Be particularly effective, such polymers have been found in which the monomers of the formula (Z-I) were present in excess over the monomers of formula (Z-II). It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (ZI) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, in particular from 75:25 to 95: 5 , consist.

Colorant preparations preferably used in the process according to the invention are characterized in that the amphoteric polymer (s) comprise monomers A) and B), wherein A) and B) are selected from

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A < ^- ) ( ^{Z -} ') in which R ¹ and R ² independently of one another represent hydrogen or one

Methyl group and R, R 1 and R 4 are independently alkyl groups of 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A "is the anion of an organic or inorganic acid and

B) monomeric carboxylic acids of the general formula (Z-II),

R ^{6 is} -CH = CR ⁷ -COOH (Z-II) R 7 in which R and R independently of one another are hydrogen or methyl groups.

With particular preference, the amphoteric polymers used in the colorant preparations used in the process according to the invention contain monomers from the group of the acrylamides and / or methacrylamides with alkylammonium groups. Acrylic acid and / or methacrylic acid and / or crotonic acid and / or 2-methyl-crotonic acid have proven useful as monomers with anionic groups which are additionally present in the polymers.

In summary, colorant preparations used in the process according to the invention are preferred in which the amphoteric polymer (s) are co-polymers of at least one of the monomers

Trimethylammoniumethylacrylamide and / or

Trimethylammoniumethylmethacrylamid and / or

Trimethylammoniumpropylacrylamid and / or Trimethylammoniumpropylmethacrylamid and / or Trimethylammoniumethylacrylamid and / or trimethylammoniumethylacrylate and / or trimethylammoniumethyl and / or trimethylammoniumethylacrylate and / or Ethyldimethylammoniumethylacrylamid and / or Ethyldimethylammoniumethylmethacrylamid and / or Ethyldimethylammoniumpropylacrylamid and / or Ethyldimethylammoniumpropylmethacrylamid and / or Ethyldimethylammoniumethylacrylamid and / or Ethyldimethylammoniumethylacrylat and / or Ethyldimethylammoniumethylmethacrylat and / or Ethyldimethylammoniumethylacrylat with mindetsnes one of the monomers acrylic acid and / or methacrylic acid and / or crotonic acid and / or 2-methyl crotonic acid are.

Particularly preferred amphoteric polymers according to the invention are:

Copolymers of trimethylammoniumethylacrylamide with crotonic acid Copolymers of trimethylammoniumethylacrylamide with crotonic acid Copolymers of trimethylammoniumethylacrylamide with acrylic acid Copolymers of trimethylammoniumethylmethacrylamide with methacrylic acid Copolymers of trimethylammoniumethylmethacrylamide with crotonic acid Copolymers of trimethylammoniumethylmethacrylamide with 2-methylcrotonic acid Copolymers of Trimethylammoniumpropylacrylamide with acrylic acid Copolymers of trimethylammoniumpropylacrylamide with methacrylic acid Copolymers of trimethylammoniapropylacrylamide with crotonic acid Copolymers of trimethylammoniumpropylacrylamide with 2-methylcrotonic acid Copolymers of trimethylammoniumpropylmethacrylamide with acrylic acid Copolymers of trimethylammoniumpropylmethacrylamide with methacrylic acid Copolymers of trimethylammoniumpropylm ethacrylamide with crotonic acid Copolymers of trimethylammoniumpropylmethacrylamide with 2-methylcrotonic acid Copolymers of trimethylammoniumethylacrylamide with acrylic acid Copolymers of trimethylammoniumethylacrylamide with methacrylic acid Copolymers of trimethylammoniumethylacrylamide with crotonic acid Copolymers of trimethylammoniumethylacrylamide with 2-methylcrotonic acid Copolymers of Trimethylammonium Ethyl Acrylate with Acrylic Acid Copolymers of Trimethyl Ammonium Ethyl Acrylate with Crotonic Acid Copolymers of Trimethyl Ammonium Ethyl Acrylate with 2-Methylcrotonone Copolymers of Trimethyl Ammonium Ethyl Methacrylate with Acrylic Acid Copolymers of Trimethyl Ammonium Ethyl Methacrylate with Methacrylic Acid Copolymers of Trimethyl Ammonium Ethyl Methacrylate with Crotonic Acid Copolymers of Trimethyl Ammonium Ethyl Methacrylate with 2-Methylcrotonone Copolymers of Trimethylammonium ethyl acrylate with acrylic acid Copolymers of trimethyl ammonium ethyl acrylate with methacrylic acid Copolymers of trimethyl ammonium ethyl acrylate with crotonic acid Copolymers of trimethyl ammonium ethyl acrylate with 2-methylcrotonic acid Copolymers of ethyldimethyl ammonium ethyl acrylamide with acrylic acid Copolymers of ethyl dimethyl ammonium ethyl acrylamide with methacrylic acid Copolymers of ethyl dimethyl ammonium ethyl acrylamide with crotonic acid C opolymere of Ethyldimethylammoniumethylacrylamid with 2-methyl-crotonic acid copolymers of Ethyldimethylammoniumethylmethacrylamid with acrylic acid, copolymers of Ethyldimethylammoniumethylmethacrylamid with methacrylic acid, copolymers of Ethyldimethylammoniumethylmethacrylamid with crotonic acid copolymers of Ethyldimethylammoniumethylmethacrylamid with 2-methyl-crotonic acid copolymers of Ethyldimethylammoniumpropylacrylamid with acrylic acid, copolymers of Ethyldimethylammoniumpropylacrylamid with methacrylic acid, copolymers of Ethyldimethylammoniumpropylacrylamid with crotonic acid copolymers of Ethyldimethylammoniumpropylacrylamide with 2-methyl-crotonic acid Copolymers of ethyldimethylammoniumpropylmethacrylamide with acrylic acid Copolymers of ethyldimethylammoniumpropylmethacrylamide with methacrylic acid Copolymers of ethyldimethylammoniumpropylmethacrylamide with crotonic acid Copolymers of ethyldimethylammoniumpropylmethacrylamide with 2-methylcrotonic acid Copolymers of ethyldimethylammonium methylacrylamide with acrylic acid Copolymers of ethyldimethylammoniumethylacrylamide with crotonic acid Copolymers of ethyldimethylammoniumethylacrylamide with 2-methylcrotonic acid Copolymers of ethyldimethylammoniumethylacrylate with acrylic acid Copolymers of ethyldimethylammoniumethylacrylate with methacrylic acid Copolymers of ethyldimethylammoniumethylacrylate with crotonic acid Copolymers of ethyldimethylammoniumethylacrylate with 2-methylcrotonic acid Copolymers of ethyldimethylammoniumethylmethacrylate with Acrylic acid Copolymers of ethyldimethylammoniumethylmethacrylate with methacrylic acid Copolymers of ethyldimethylammoniumethylmethacrylate with crotonic acid Copolymers of ethyldimethylammoniumethylmethacrylate with 2-methylcrotonic acid Copolymers of ethyldimethylammoniumethylacrylate with acrylic acid Copolymers of ethyldimethylammoniumethylacrylate with methacrylic acid Copolymers of ethyldimethylammoniumethylacrylate with crotonic acid Copolymers of ethyldimethylammoniumethylacrylate with 2-methylcrotonic acid

As a further ingredient, the colorant preparations used in the process according to the invention may with particular preference contain one or more amino acids. Particularly preferred amino acids which can be used according to the invention are from the group glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine, β Alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-Cyss), L-carnitine, L-citrulline, L-theanine, 3 ', 4'-dihydroxy-L-phenylalanine (L-dopa), 5'-hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine-sulfoxide (L-alliin), L-frans-4-hydroxyproline, L-5-oxoproline ( L-pyroglutamic acid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine, whereby both the individual amino acids and mixtures can be used.

Preferred colorant preparations used in the process according to the invention comprise one or more amino acids in narrower quantitative ranges. Here, preferred processes according to the invention are characterized in that the colorant preparation - based on their weight - 0.01 to 5 wt .-%, preferably 0.02 to 2.5 wt .-%, particularly preferably 0.05 to 1, 5 wt .-%, more preferably 0.075 to 1 wt .-% and in particular 0.1 to 0.25 wt .-% amino acid (s), preferably from the group of glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine.

Another preferred group of ingredients of the colorant preparations used in the process according to the invention are vitamins, provitamins or vitamin precursors. These are described below:

The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration. The agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total preparation.

The vitamin B group or the vitamin B complex include vitamin B ₁ (thiamine) vitamin B ₂ (riboflavin)

Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent. Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Panthenol and / or pantolactone are preferably used in the context of this group. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829. The said compounds of the vitamin B ₅ type are preferably contained in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5 wt .-% are particularly preferred. Vitamin B ₆ (pyridoxine and pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total agent. Use in the form of palmitic acid ester, glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as the acetate, the nicotinate, the phosphate and the succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent.

Vitamin F. The term "vitamin F" is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-cf] - imidazole-4-valeric acid, for which, however, the trivial name biotin has meanwhile prevailed. Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.

In summary, methods according to the invention are preferred in which the colorant preparation contains, based on its weight, from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight, particularly preferably from 0.25 to 3.5% by weight. , more preferably 0.5 to 3 wt .-% and in particular 0.5 to 2.5 wt .-% vitamins and / or pro-vitamins and / or vitamin precursors, preferably the groups A, B, C, E, Panthenol ((±) -2,4-dihydroxy-Λ / - (3-hydroxypropyl) -3,3-dimethyl-butyramide, provitamin B ₅ ) and / or pantothenic acid (vitamin B ₃ , Vitamin B ₅ ) and / or niacin, niacinamide or nicotinamide (vitamin B ₃ ) and / or L-ascorbic acid (vitamin C) and / or thiamine (vitamin B ₁ ) and / or riboflavin (vitamin B ₂ , vitamin G) and / or biotin (vitamin B ₇ , vitamin H) and / or folic acid (vitamin B ₉ , vitamin B _c or vitamin M) and / or vitamin B ₆ and / or vitamin B ₁₂ .

It has been found that the use of certain quinones enhances anti-dandruff and anti-hair loss effects as well as combability and gloss benefits. When Further constituents used in the process according to the invention can therefore be from 0.0001 to 5% by weight of at least one biochinone of the formula (Ubi-I)

contained in the

X, Y, Z are independently -O- or -NH- or NR ⁴ - or a chemical bond

R ¹ , R ² , R ³ independently of one another represent a hydrogen atom or an optionally substituted aryl group or an optionally substituted (C ₁ -C ₆ ) -alkyl group or a hydroxyalkyl group or a polyhydroxyalkyl group or an optionally substituted (C ₁ -C ₆ ) -alkylene group, or a (C 1 -C ₆ ) -acyl radical, preferred radicals being selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₂ , -CH (CH ₃ ) ₂ , - (CH ₂ ) ₃ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃

R ⁴ is -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₂ , -CH (CH ₃ ) ₂ , - (CH ₂ ) ₃ CH ₃ ,

-CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ n is from 1 to 20, preferably from 2 to 15 and in particular from 5, 6, 7 , 8, 9, 10.

Preferred compounds of the formula (I) according to the invention are, for example

)

in which

R ¹ , R ² , R ³ are each independently of one another -H, -CH ₃ , -CH ₂ CH ₃ , - (CΗ ₂ ) ₂ CΗ ₂ , -CΗ (CΗ ₃ ) ₂ , - (OH ₂ J ₃ OH ₃ , - (_ / H ((_ / H ₃ ) (- / H ₂ (- / H ₃ , -CΗ ₂ (_ / H ((- / H ₃ ) ₂ , -C (CH ₃ ) ₃

R ⁴ is -CH ₃ , or -CH ₂ CH ₃ , or - (CH ₂ ) ₂ CH ₂ , or -CH (CH ₃ ) ₂ n is from 1 to 20, preferably from 2 to 15 and especially for 5, 6, 7, 8, 9, 10.

Particularly preferred methods according to the invention are characterized in that the colorant preparation - based on their weight - 0.0001 to 1 wt .-%, preferably 0.001 to 0.5 wt .-% and particularly preferably 0.005 to 0, 1 wt .-% at least a ubiquinone and / or contain at least one ubiquinol and / or at least one derivative of these substances, preferred agents containing a ubiquinone of the formula (Ubi)

in which n stands for the values = 6, 7, 8, 9 or 10, particularly preferably 10 (coenzyme Q10).

As an alternative to the particularly preferred ubiquinones or in addition to them, the colorant preparations used in the process according to the invention may also contain plastoquinones. Here, preferred colorant preparations used in the process according to the invention are characterized by being from 0.0002 to 4% by weight, preferably from 0.0005 to 3% by weight, particularly preferably from 0.001 to 2% by weight, more preferably from 0.0015 to 1 and in particular 0.002 to 0.5 wt .-% of at least one plastoquinone of the formula (Ib)

in which n stands for values of 1 to 20, preferably of 2 to 15 and in particular for 5, 6, 7, 8, 9, 10, whereby particularly preferred means Plastochinon PQ-9 of the formula

contain.

To improve the elasticity and strengthen the internal structure of the hair colorants treated with the colorant preparations used in the process according to the invention, the colorant preparations used in the process according to the invention may contain purine and / or purine derivatives. In particular, the combination of purine and / or purine derivatives with ubiquinones and / or plastoquinones means that the hairs treated with appropriate agents show, inter alia, higher measured values in differential thermal analysis and improved wet and dry combabilities. As a further ingredient, the colorant preparations used in the process according to the invention may therefore contain purine and / or derivative (s) of the purine. Purine (7H-imidazo [4,5-cf] pyrimidine) does not occur freely in nature, but forms the main body of the purines. Purines, in turn, are a group of important compounds of widespread nature involved in human, animal, plant and microbial metabolic processes, which differ from the parent by substitution with OH, NH ₂ , SH in the 2-, 6-, and 8-positions and / or with CH ₃ in 1-, 3-, 7-position derived. Purine can be prepared, for example, from aminoacetonitrile and formamide. Purines and purine derivatives are often isolated from natural products, but are also synthetically accessible in many ways.

Preferred colorant preparations used in the process according to the invention contain purine and / or purine derivatives in narrower quantitative ranges. Here, in the process according to the invention, preferably used colorant preparations are characterized in that they contain, based on their weight, from 0.001 to 2.5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.005 to 0.5% by weight. % and in particular 0.01 to 0.1% by weight of purine (s) and / or purine derivative (s).

Among purine, the purines and the purine derivatives, some representatives are particularly preferred according to the invention. According to preferred methods are therefore characterized in that the colorant preparation - based on their weight - 0.001 to 2.5 wt .-%, preferably 0.0025 to 1 wt .-%, particularly preferably 0.005 to 0.5 wt .-% and in particular from 0.01 to 0.1% by weight of purine (s) and / or purine derivative (s), preferred agents containing purine and / or purine derivative (s) of formula (Pur-I)

(Pur-I) in which the radicals R ¹ , R ² and R ^{3 are} independently selected from -H, -OH, NH ₂ , -SH and the radicals R ⁴ , R ⁵ and R ⁶ are selected independently of one another from H, -CH ₃ and -CH ₂ -CH ₃ , where the following compounds are preferred:

Purine (R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Adenine (R ¹ = NH ₂ , R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Guanine (R ¹ = OH, R ² = NH ₂ , R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Uric acid (R ¹ = R ² = R ³ = OH, R ⁴ = R ⁵ = R ⁶ = H)

Hypoxanthine (R ¹ = OH, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

6-purethiol (R ¹ = SH, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

6-thioguanine (R ¹ = SH, R ² = NH ₂ , R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Xanthine (R ¹ = R ² = OH, R ³ = R ⁴ = R ⁵ = R ⁶ = H) Caffeine (R ¹ = R ² = OH, R ³ = H, R ⁴ = R ⁵ = R ⁶ = CH ₃ )

- Theobromine (R ¹ = R ² = OH, R ³ = R ⁴ = H, R ⁵ = R ⁶ = CH ₃ )

Theophylline (R ¹ = R ² = OH, R ³ = H, R ⁴ = CH ₃ , R ⁵ = CH ₃ , R ⁶ = H).

It is also advantageous to use purine or purine derivatives and biochinones in a certain ratio to each other. Agents according to the invention are preferred in which the weight ratio of ingredients a) and b) is from 10: 1 to 1: 100, preferably from 5: 1 to 1:50, particularly preferably from 2: 1 to 1:20 and in particular from 1: 1 to 1 : 10.

As already mentioned, caffeine is a particularly preferred purine derivative, and coenzyme Q10 is a particularly preferred biochinone. Particularly preferred colorant preparations used in the process according to the invention are therefore characterized in that they contain, based on their weight, from 0.001 to 2.5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.005 to 0.5% by weight. -% and in particular 0.01 to 0.1 wt .-% caffeine and 0.0002 to 4 wt .-%, preferably 0.0005 to 3 wt .-%, particularly preferably 0.001 to 2 wt .-%, more preferably 0.0015 to 1 and in particular 0.002 to 0.5 wt .-% coenzyme Q10 included.

As a further component, the colorant preparations used in the process according to the invention may contain at least one carbohydrate from the group of monosaccharides, disaccharides and / or oligosaccharides. Here, according to the invention preferred methods are characterized in that the colorant preparation - based on their weight - 0.01 to 5 wt .-%, preferably 0.05 to 4.5 wt .-%, particularly preferably 0.1 to 4 wt. %, more preferably 0.5 to 3.5 wt .-% and in particular 0.75 to 2.5 wt .-% of carbohydrate (s), selected from monosaccharides, disaccharides and / or oligosaccharides containing preferred carbohydrates are selected from Monosaccharides, in particular

D-ribose and / or

D-xylose and / or

L-arabinose and / or

D-glucose and / or

D-mannose and / or

D-galactose and / or

D-fructose and / or

Sorbose and / or

L-fucose and / or

L-Rhamnose disaccharides, in particular

Sucrose and / or

Maltose and / or

Lactose and / or

Trehalose and / or Cellobiose and / or gentiobiose and / or isomaltose.

Particularly preferred colorant preparations used in the process according to the invention contain, based on their weight

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of glucose monohydrate,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of sucrose,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of fructose.

As already mentioned, preferred colorant preparations used in the process according to the invention contain one amino acid (s).

Particularly preferred amino acids which can be used according to the invention are from the group of glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine, β Alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-Cyss), L-carnitine, L-citrulline, L-theanine, 3 ', 4'-dihydroxy-L-phenylalanine (L-dopa), 5'-hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine-sulfoxide (L-alliin), L-frans-4-hydroxyproline, L-5-oxoproline ( L-pyroglutamic acid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine, whereby both the individual amino acids and mixtures can be used.

Preferred colorant preparations used in the process according to the invention comprise one or more amino acids in narrower quantitative ranges. Here, preferred colorant preparations used in the process according to the invention are characterized in that they additionally contain from 0.05 to 5 wt.%, Preferably from 0.1 to 2.5 wt.%, Particularly preferably from 0.15 to 1 wt in particular 0.2 to 0.5 wt .-% amino acid (s), preferably (one) amino acid (s) from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine ,

Particularly preferred colorant preparations used in the process according to the invention contain, based on their weight

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of glucose monohydrate and 0.1 to 0.25% by weight of glycine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of sucrose and 0.1 to 0.25% by weight of glycine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of fructose and 0.1 to 0.25% by weight of glycine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of glucose monohydrate and 0.1 to 0.25% by weight of alanine, 0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of sucrose and 0.1 to 0.25% by weight of alanine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of fructose and 0.1 to 0.25% by weight of alanine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of glucose monohydrate and 0.1 to 0.25% by weight of valine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of sucrose and 0.1 to 0.25% by weight of valine,

0.005 to 0.015% by weight of caffeine and 0.75 to 1.5% by weight of fructose and 0.1 to 0.25% by weight of valine.

According to preferred methods are characterized in that the colorant preparation - based on their weight - 0.01 to 15 wt .-%, preferably 0.025 to 12.5 wt .-%, particularly preferably 0.05 to 10 wt .-%, further preferably 0.1 to 7.5% by weight and in particular 0.5 to 5% by weight of at least one 2-furanone derivative of the formula (Fur-I) and / or of the formula (Fur-II)

contains, in which the radicals R ¹ to R ^{10 are} independently of one another for

Hydrogen, -OH, a methyl, methoxy, aminomethyl or hydroxymethyl radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,

- a group -NR ¹² R ¹³ , wherein R ¹² and R ¹³ each independently represent hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbon hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbyl radical,

- a group -CONR ¹⁵ R ¹⁶ , wherein R ¹⁵ and R ¹⁶ each represent hydrogen, methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ - saturated mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

a group -COR ¹⁶ , wherein R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or a diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

- a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ - saturated or on or - polyunsaturated, branched or linear mono-, di-, tri- or Polyhydroxykohlenwasserstoffrest, a -C ₂ - C ₃₀ - saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical, with the proviso in that, when R ⁷ and R ^{8 are} -OH and at the same time R ⁹ or R ^{10 is} hydrogen, the remaining group R ⁹ or R ¹⁰ does not represent a dihydroxyethyl radical.

The compounds of the formulas (Fur-I) and (Fur-II) are used as intermediates in the synthesis of natural products and in the preparation of medicaments and vitamins. The preparation of the active compounds according to the formulas (Fur-I) and (Fur-II) can be carried out, for example, by reacting primary alcohols with acrylic acids. Furthermore, compounds of the formula (Fur-I) are obtained by reactions starting from hydroxypivaldehyde. Also, carbonylations of alkynes lead to substituted 2-furanones of the formula (Fur-I) or (Fur-II). Finally, the compounds of the formula (Fur-I) or of the formula (Fur-II) can be obtained by intramolecular esterification of the corresponding hydroxycarboxylic acids. For example, the following compounds are on any of the previously indicated Synthetic pathways obtained: 2,5-dihydro-5-methoxy-2-furanone,

Tetrahydro-5-oxo-2-furancarboxylic acid, dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone, or 3,4-dimethyl-5-pentylidenedihydro-2 (5H) -furanone or 4-hydroxy -2,5-dimethyl-3 (2H) -furanone. Of course, the 2-furanones according to the invention include all possible stereoisomers as well as their mixtures. By the 2-furanones according to the invention, the odor of the cosmetic products is not permanently affected, so that a perfuming of the funds must be done separately.

Preferred compounds of the formula (fur-I) and / or of the formula (fur-II) can be compounds in which the substituents R ¹ , R ² and R ⁷ independently of one another represent:

Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxyhydrocarbyl radical,

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or triaminocarbon radical,

a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxy-hydrocarbon radical, a group -NR ¹² R ¹³ , where R ¹² and R ¹³ each independently represent hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical,

a group -COOR ¹⁴ , wherein R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbon hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

a group -COR ¹⁶ , wherein R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or a diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

- a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a - C ₂ - C ₃₀ - saturated or on or - polyunsaturated, branched or linear mono-, di-, tri- or Polyhydroxyalkylrest, or a -C ₂ - C ₃₀ - saturated or on or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical.

In a further embodiment of the teaching according to the invention it has been found that the compounds of the formula (Fur-I) or formula (Fur-Il), the radicals R ^3, R ⁴ and R ⁸ are preferably each independently stand for:

Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl, a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear

Hydrocarbon radical, a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxy-hydrocarbon radical or a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear

Mono, di or triaminocarbon radical.

Furthermore, it may be preferred for the radicals R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in the active substance according to the formula (I) and / or formula (II) according to the invention to stand independently of one another for:

Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Hydrocarbon radical,

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxyhydrocarbyl radical or

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono, di or triaminocarbon radical.

In a particularly preferred embodiment of the teaching according to the invention, a compound of the formula (Fur-I) is used. In this case, it may be preferred that in a compound of the formula (fur-I) the radicals R ¹ and R ² independently of one another represent:

Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,

- a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxyhydrocarbyl radical,

a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,

a group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,

a group -COR ¹⁶ , where R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,

- a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a - C ₂ - C ₃₀ - saturated or on or - polyunsaturated, branched or linear mono-, di-, tri- or Polyhydroxykohlenwasserstoffrest.

Furthermore, in this particularly preferred embodiment of the teaching according to the invention, it may be advantageous if in the compounds of the formula (Fur-I) the radicals R ³ and R ⁴ independently of one another represent:

Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl, a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxyhydrocarbyl radical, a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or or diunsaturated, branched or linear mono-, di- or

Trihydroxy hydrocarbon residue, a group -COOR ¹⁴ , wherein R ¹⁴ is hydrogen, a methyl, a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear

Hydrocarbon radical, a -C ₂ -C ₄ - saturated mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a

C ₂ - C ₃₀ - saturated or mono- or polyunsaturated, branched or linear

Mono-, di-, tri- and / or polyhydroxy hydrocarbon residue.

In this preferred embodiment, it may furthermore be advantageous for the compounds of the formula (Fur I) for the radicals R 5 and R _{6 to} stand independently for: a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear

Mono-, di- or trihydroxyhydrocarbyl radical, a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or or diunsaturated, branched or linear mono-, di- or

Trihydroxykohlenwasserstoffrest.

In a particularly preferred embodiment of the teaching according to the invention is used as the compound according to the formula (Fur-I)

(R) - (-) - 4-hydroxymethyl-Y-butyrolactone and / or

D, L-4-hydroxymethyl-γ-butyrolactone and / or

(S) - (+) - 4-hydroxymethyl-γ-butyrolactone and / or R - (-) - 2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or

D, L-2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or

S (+) - 2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or

4-hydroxy-2,5-dimethyl-3 (2H) -furanone and / or

Tetrahydro-5-oxo-2-furancarbonsäure and / or

Tetrahydro-5-oxo-2-furancarboxylic acid, Na salt and / or

Tetrahydro-5-oxo-2-furancarboxylic acid, K-salt and / or

2,5-dihydro-5-methoxy-2-furanone and / or

Dihydro-3-hydroxy-4,4-dimethyl-2 (3 / - /) - furanone used. In a very particularly preferred embodiment of the teaching according to the invention is used as a compound according to the formula (Fur-I) dihydro-3-hydroxy-4,4-dimethyl-2 (3H) - furanone.

Another preferred care substance having activating properties is taurine. Processes preferred according to the invention are therefore characterized in that the colorant preparation - based on their weight - 0.01 to 15 wt .-%, preferably 0.025 to 12.5 wt .-%, particularly preferably 0.05 to 10 wt .-%, more preferably 0.1 to 7.5 wt .-% and in particular 0.5 to 5 wt .-% taurine (2-aminoethanesulfonic acid).

Also preferred is the additional use of bisabolol and / or bisabolol oxides.

Processes preferred according to the invention are characterized in that the colorant preparation additionally contains 0.001 to 5 wt.%, Preferably 0.01 to 4 wt.%, Particularly preferably 0.02 to 2.5 wt.% And in particular 0.1 to 1 , 5% by weight of bisabolol and / or oxides of bisabolol, preferably (-) - alpha-bisabolol

contains.

Following the dyeing process, which may take one to 60 minutes, preferably 2 to 45 minutes, more preferably 5 to 40 minutes, more preferably 8 to 35 minutes and especially 10 to 30 minutes, depending on the composition of the colorant preparation, the colorant spreading from the rinsed out keratinic fibers.

By the method according to the invention, a whitening color is achieved which less damages the hair and gives it a healthier appearance.

Claims

claims

1. A method for dyeing and whitening keratin fibers, characterized by the directly and without further intermediate steps successive steps

(i) applying a bleaching agent formulation to the keratin fibers and allowing to act for a period of from one to 45 minutes, (ii) rinsing the bleaching preparation, (iii) applying a colorant formulation containing at least one natural dye, (iv) rinsing the colorant preparation.

2. The method according to claim 1, characterized in that the natural dye (s) is / are selected from henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre, alcano root, cinnamon, devil's claw, liquorice, beetroot, blackberry, ratanhia, red sandalwood, blueberry, chamomile, rhubarb, cornflower, senna and galangal.

3. The method according to any one of claims 1 to 2, characterized in that the colorant preparation contains no oxidation dye precursors.

4. The method according to any one of claims 1 to 3, characterized in that the colorant preparation does not contain ammonia.

5. The method according to any one of claims 1 to 4, characterized in that the colorant preparation contains no amines.

6. The method according to any one of claims 1 to 5, characterized in that the colorant preparation contains no hydrogen peroxide.

7. The method according to any one of claims 1 to 6, characterized in that the colorant preparation contains no peroxo compounds.

8. The method according to any one of claims 1 to 7, characterized in that the colorant preparation - based on their weight - 0.05 to 7.5 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0, From 2 to 3.5% by weight, and more preferably from 0.25 to 2.5% by weight, of cationic polymer (s), with preferred cationic polymer (s) being selected

Poly (methacryloyloxyethyltrimethylammonium chloride) (INCI: Polyquaternium-37) and / or; quaternized cellulose derivatives (INCI: Polyquaternium 10) and / or cationic alkyl polyglycosides and / or cationised honey and / or cationic guar derivatives and / or polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid and / or

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate and / or

Vinylpyrrolidone-vinylimidazolium methochloride copolymers and / or quaternized polyvinyl alcohol and / or Polyquaternium 2 and / or Polyquaternium-7 and / or Polyquaternium 17 and / or Polyquaternium 18 and / or Polyquaternium 24 and / or Polyquaternium 27.

9. The method according to any one of claims 1 to 8, characterized in that the Därbemittelzubereitung- based on their weight - 0.01 to 5 wt .-%, preferably 0.02 to 2.5 wt .-%, particularly preferably 0, 05 to 1, 5 wt .-%, more preferably 0.075 to 1 wt .-% and in particular 0.1 to 0.25 wt .-% amino acid (s), preferably from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine.

10. The method according to any one of claims 1 to 9, characterized in that the colorant preparation - based on their weight - 0.1 to 5 wt .-%, preferably 0.2 to 4 wt .-%, particularly preferably 0.25 to Contains 3.5 wt .-%, more preferably 0.5 to 3 wt .-% and in particular 0.5 to 2.5 wt .-% vitamins and / or pro-vitamins and / or vitamin precursors, preferably the groups A , B, C, E, F and H, preferred agents being panthenol ((±) -2,4-dihydroxy-Λ / - (3-hydroxypropyl) -3,3-dimethylbutyramide, provitamin B ₅ ) and or pantothenic acid (vitamin B ₃ , vitamin B ₅ ) and / or niacin, niacinamide or nicotinamide (vitamin B ₃ ) and / or L-ascorbic acid (vitamin C) and / or thiamine (vitamin B ₁ ) and / or riboflavin ( Vitamin B ₂ , vitamin G) and / or biotin (vitamin B ₇ , vitamin H) and / or folic acid (vitamin B ₉ , vitamin B _c or vitamin M) and / or vitamin B ₆ and / or vitamin B ₁₂ .

11. The method according to any one of claims 1 to 10, characterized in that the colorant preparation - based on their weight - 0.0001 to 1 wt .-%, preferably 0.001 to 0.5 wt .-% and particularly preferably 0.005 to 0, 1 wt .-% of at least one ubiquinone and / or at least one ubiquinol and / or at least one derivative of these substances, preferred agents containing a ubiquinone of the formula (Ubi)

in which n stands for the values = 6, 7, 8, 9 or 10, particularly preferably 10 (coenzyme Q10).

12. The method according to any one of claims 1 to 11, characterized in that the colorant preparation - based on their weight - 0.001 to 2.5 wt .-%, preferably 0.0025 to 1 wt .-%, particularly preferably 0.005 to 0, Contains 5 wt .-% and in particular 0.01 to 0.1 wt .-% purine (s) and / or purine derivative (s), wherein preferred agents purine and / or purine derivative (s) of the formula (Pur-I)

in which the radicals R ¹ , R ² and R ^{3 are} independently selected from -H, - OH, NH ₂ , -SH and the radicals R ⁴ , R ⁵ and R ^{6 are} independently selected from -H, -CH ₃ and -CH ₂ -CH ₃ , where the following compounds are preferred:

Purine (R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Adenine (R ¹ = NH ₂ , R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Guanine (R ¹ = OH, R ² = NH ₂ , R ³ = R ⁴ = R ⁵ = R ⁶ = H)

Uric acid (R ¹ = R ² = R ³ = OH, R ⁴ = R ⁵ = R ⁶ = H)

Hypoxanthine (R ¹ = OH, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = H)

6-Purinethiol (R '= SH, R 2 ^ _ = _D R 3 ^ό _ = n Rt ⁴ - = R ⁰ _ = R ^D = H)

6-thioguanine (R ¹ = SH, R ₃ 2 ^ _ = NH ₂ , R 3 ^ό _ = _D R ^{4 4} _ = n R 5 ⁰ _ = R ^D = H) xanthine (R ¹ = R ² = OH, R ³ = R ⁴ = R ⁵ = R ⁶ = H) Caffeine (R ¹ = R ² = OH, R ³ = H, R ⁴ = R ⁵ = R ⁶ = CH ₃ ) Theobromine (R ¹ = R ² = OH, R ³ = R ⁴ = H, R ⁵ = R ⁶ = CH ₃ ) Theophylline (R ¹ = R ² = OH, R ³ = H, R ⁴ = CH ₃ , R ⁵ = CH ₃ , R ⁶ = H).

13. The method according to any one of claims 1 to 12, characterized in that the colorant preparation - based on their weight - 0.01 to 5 wt .-%, preferably 0.05 to 4.5 wt .-%, particularly preferably 0, From 1 to 4% by weight, more preferably from 0.5 to 3.5% by weight and in particular from 0.75 to 2.5% by weight carbohydrate (s) selected from monosaccharides, Disaccharides and / or oligosaccharides containing preferred carbohydrates are selected from

Monosaccharides, in particular

D-ribose and / or

D-xylose and / or

L-arabinose and / or

D-glucose and / or

D-mannose and / or

D-galactose and / or

D-fructose and / or

Sorbose and / or

L-fucose and / or

L-Rhamnose disaccharides, in particular

Sucrose and / or

Maltose and / or

Lactose and / or

Trehalose and / or

Cellobiose and / or

Gentiobiose and / or

Isomaltose.

14. The method according to any one of claims 1 to 13, characterized in that the colorant preparation - based on their weight - 0.01 to 15 wt .-%, preferably 0.025 to 12.5 wt .-%, particularly preferably 0.05 to 10 wt .-%, more preferably 0.1 to 7.5 wt .-% and in particular 0.5 to 5 wt .-% of at least one 2-furanone derivative of the formula (Fur-I) and / or the formula (fur- Il)

contains, in which the radicals R ¹ to R ^{10 are} independently of one another for

Hydrogen, -OH, a methyl, methoxy, aminomethyl or hydroxymethyl radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,

--C ₂ - C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical, a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,

- a group -NR ¹² R ¹³ , wherein R ¹² and R ¹³ each independently represent hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,

a group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbon hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbyl radical,

- a group -CONR ¹⁵ R ¹⁶ , wherein R ¹⁵ and R ¹⁶ each represent hydrogen, methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ - saturated mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

a group -COR ¹⁶ , wherein R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or a diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,

- a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ - saturated or on or - polyunsaturated, branched or linear mono-, di-, tri- or Polyhydroxykohlenwasserstoffrest, a -C ₂ - C ₃₀ - saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical, with the proviso in that, when R ⁷ and R ^{8 are} -OH and at the same time R ⁹ or R ^{10 is} hydrogen, the remaining group R ⁹ or R ¹⁰ does not represent a dihydroxyethyl radical.

15. The method according to any one of claims 1 to 14, characterized in that the colorant preparation - based on their weight - 0.01 to 15 wt .-%, preferably 0.025 to 12.5 wt .-%, particularly preferably 0.05 to 10 wt .-%, more preferably 0.1 to 7.5 wt .-% and in particular 0.5 to 5 wt .-% taurine (2-aminoethanesulfonic acid).