DE102023201743A1 - Gel for oxidative color change of keratin fibers with improved application properties - Google Patents

Abstract

The present invention relates to a gel for the oxidative color change of keratin fibers with improved application properties, which is based on a selected natural polysaccharide.

Description

The present invention relates to an agent for oxidative color change for keratin fibers, which has optimized application properties and/or improved coloring performance, and to a method for oxidative color change using an oxidative color change agent with optimized application properties and/or optimized coloring performance. So-called oxidation colorants are used for permanent, intensive coloring with corresponding fastness properties. Oxidative colorants usually consist of two components: one component usually contains oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents, in particular hydrogen peroxide, which are only added to the first component shortly before application to the hair, or of atmospheric oxygen among themselves or by coupling with one or more coupler components. Primary aromatic amines with an additional free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are usually used as developer components. m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are usually used as coupler components. The oxidation dyes are characterized by excellent, long-lasting color results. Conventional oxidative dyes have a more alkaline pH value, which is significantly above 9.0, to stabilize the dye precursors during storage and to accelerate the reaction during oxidative application. This is adjusted using alkalizing agents such as alkanolamines, ammonia or inorganic bases. Ammonia in particular enables good color results, but also reveals disadvantages for the user due to its smell and potential for irritation to skin and mucous membranes. The alkalizing agent causes the keratin fibers to swell, which allows the dye precursors to penetrate the hair well. However, the alkaline pH value also increases the damaging effect of the oxidizing agent on the hair structure. The damage to the hair structure, which is particularly quickly noticeable, affects the flaking of the cuticle, i.e. the outer layer of the keratin fiber. This is noticeable in greater roughness, poorer feel, reduced shine and poorer stability of the fiber. The roughened structure of the cuticle allows small molecules such as water to escape more quickly. This causes damaged hair to lose even more suppleness and elasticity. But the color fastness properties are also impaired by the roughened fiber surface.

Therefore, special efforts are being made to develop efficient oxidative color-changing agents, in particular agents for lightening and/or coloring keratin fibers, which achieve good coloring and lightening results despite a moderately alkaline pH value.

Furthermore, special efforts are being made to develop efficient oxidative color-changing agents, in particular agents for lightening and/or coloring keratin fibers, which have improved application properties, in particular with regard to the application behavior and the viscosity during the exposure time on the keratin fibers.

During oxidation coloring, the pigment melanin in the fiber is destroyed by the oxidizing agent. The keratin fibers are thereby lightened or bleached. If oxidation dye precursors and/or direct dyes are added to the oxidative color-changing agent, even darker hair can be colored in many fashionable shades, which are often lighter than the original color of the fiber.

Oxidative colour-changing agents that are adjusted to a slightly alkaline or even slightly acidic pH value are not preferred by consumers because of the often less satisfactory colour result.

Fats or silicones are often used to reduce hair damage caused by an alkaline oxidative color change agent. The formulation of such color change agents brings with it numerous problems, because the fatty alkalizing cream must be able to be easily mixed with the hydrogen peroxide developer, which has a high water content, and applied to the hair at the latest when the application mixture is prepared. This usually requires the use of large amounts of surfactants or emulsifiers, which can also contribute to hair damage. The water-insoluble fats, oils, waxes or silicones can prevent the explicitly desired swelling of the hair during the exposure time of the color change agent and thus the penetration of the oxidizing agent and the dye precursors. products into the keratin fibers. The more water-insoluble components such as fats and oils the color-changing agents contain, the more difficult they are to wash out after the exposure time. In addition, low-fat and fat-free oxidative color-changing agents can be easily formulated transparently, a dosage form that is currently preferred by a large group of consumers.

The present application was therefore based on the object of providing an agent for the oxidative color change of keratin fibers with improved application properties, in particular with improved rheological application properties. The present application was also based on the object of providing an agent for the oxidative color change of keratin fibers with improved storage stability and/or improved application properties, in particular with improved rheological application properties, which does not contain any petrochemically based thickeners.

A further object of the present application was to provide an agent for the oxidative color change of keratin fibers with improved coloring properties, in particular with regard to color intensity and balancing ability.

It has now been found that an oxidative color-changing agent containing an iota-carrageenan-based gel in combination with an alkyl mono- and oligoglycoside has excellent application properties, so that the use of petrochemical-based thickeners can be dispensed with.

State of the art

The disclosure document DE102017223233A1 discloses gel-like color-changing agents for keratin fibers that are thickened with a mixture of carbomer and xanthan. FR2977157B1 discloses gel-like skin treatment agents which contain, in addition to at least 70% by weight of water, carrageenan, hyaluronic acid and a diol having 2 to 10 carbon atoms. WO2021026572A1 discloses foaming cleaning agents for the body and hands which, in addition to at least 70% by weight of water, further contain 6 - 11% by weight of C8-C10 alkyl glucoside surfactants, carrageenan and xanthan and have an acidic pH of about pH 4.

• - mehr als 80 Gew.-% bis 99 Gew.-% Wasser,
• - 0,1 bis 1,5 Gew.-% iota-Carrageen,
• - 0,05 bis 0,5 Gew.-% Kaliumionen in Form von mindestens einem Kaliumsalz,
• - mindestens ein Alkalisierungsmittel,
• - mindestens ein nichtionisches Tensid, ausgewählt aus Alkylmono- und -oligoglycosiden der Formel R⁴O-[G]_p, in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine positive rationale Zahl im Bereich von 1 bis 6 steht, in einer Gesamtmenge von 0,1 bis weniger als 3 Gew.-%,
• - null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
• - optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,

wobei das Mittel einen pH-Wert im Bereich von 7 bis 11, bevorzugt im Bereich von 7,5 bis 10,7, besonders bevorzugt im Bereich von 8 bis 10, außerordentlich bevorzugt 8,5 bis 9,5, aufweist, jeweils gemessen bei einer Temperatur von 22 °C.The present invention relates, in a first embodiment, to an agent for the oxidative color change of keratin fibers, in particular human hair, containing, in each case based on its weight,

• - more than 80 wt.% to 99 wt.% water,
• - 0.1 to 1.5% by weight iota carrageenan,
• - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt,
• - at least one alkalizing agent,
• - at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3% by weight,
• - zero to less than 0.1% by weight of peroxide compounds,
• - optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,

wherein the agent has a pH in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C.

The agent according to the invention contains, in each case based on its weight, more than 80 wt.% to 99 wt.%, preferably 82-95 wt.%, particularly preferably 85-90 wt.%, extremely preferably 86-88 wt.% water.

The agent according to the invention is a water-based gel with iota-carrageenan as a thickener. The agent according to the invention also represents the alkalizing component of a two-part oxidati ven dyeing or lightening agent which is mixed with an aqueous hydrogen peroxide solution shortly before use and then applied to the hair.

Surprisingly, it was found that a gel based on iota-carrageenan in the presence of potassium ions is excellently suited to tolerating the salt load associated with the addition of oxidation dye precursors without compromising viscosity stability. The agent according to the invention therefore contains, as further obligatory ingredients, 0.1 to 1.5% by weight of iota-carrageenan and - for its gelling - 0.05 to 0.5% by weight of potassium ions in the form of at least one potassium salt, based on its weight. Agents preferred according to the invention contain, based on their weight, 0.2 to 1.0% by weight, preferably 0.3 to 0.8% by weight, particularly preferably 0.4 to 0.7% by weight, extremely preferably 0.5 to 0.6% by weight of iota-carrageenan. Further agents preferred according to the invention contain, based on their weight, 0.1 to 0.4% by weight, preferably 0.15 to 0.35% by weight, particularly preferably 0.2 to 0.3% by weight, extremely preferably 0.21 to 0.25% by weight of potassium ions in the form of at least one potassium salt. Suitable potassium salts are selected from potassium chloride, potassium hydrogen sulfate, dipotassium sulfate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, tripotassium phosphate, potassium hydroxide, potassium tartrate, potassium lactate, potassium succinate and mixtures of these salts. Preferred potassium salts are selected from the inorganic salts potassium chloride, potassium hydrogen sulfate, dipotassium sulfate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, tripotassium phosphate and potassium hydroxide and mixtures of these salts.

Color-changing agents preferred according to the invention have a viscosity in the range of 6000 - 15000 mPas, preferably 6500 - 14000 mPas, particularly preferably 7000 - 13000 mPas, extremely preferably 8000 - 12000 mPas, each measured at 20°C with a Haake model MVII rheometer at a shear rate of 7.2 revolutions per second. In comparison to the DE102017223233A1 Compared to known gel-like color-changing agents for keratin fibers, which are thickened with a mixture of carbomer and xanthan, the gel-like color-changing agent according to the invention has a firmer structure with thixotropic behavior. The agents according to the invention therefore adhere better to the keratin fibers during the exposure time than the known agents.

Oxidative color change processes on keratin fibers usually take place in a neutral to alkaline environment. Therefore, the pH value of the agent according to the invention is in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C.

As a further obligatory ingredient, the agent according to the invention therefore contains at least one alkalizing agent.

The alkalizing agents preferably suitable for adjusting the pH value of the agents according to the invention are selected from ammonia, alkanolamines, alkali hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali phosphates and dialkali monohydrogen phosphates and mixtures of these substances.

Preferred color-changing agents according to the invention are characterized in that they do not contain ammonia and ammonium hydroxide.

Particularly preferred alkalizing agents are selected from alkanolamines, alkali hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali phosphates and dialkali monohydrogen phosphates and mixtures of these substances. The alkali metal ions in the aforementioned alkalizing salts are preferably lithium, sodium or potassium, in particular sodium or potassium.

The basic amino acids that can be used as alkalizing agents are preferably selected from the group L-arginine, D-arginine, D,L-arginine, L-lysine, D-lysine, D,L-lysine and mixtures thereof. Particularly preferred basic amino acids are L-arginine, L-lysine and mixtures thereof.

The alkali hydroxides that can be used as alkalizing agents are preferably selected from sodium hydroxide and potassium hydroxide and mixtures thereof. Potassium hydroxide is particularly preferred according to the invention.

The alkanolamines that can be used as alkalizing agents preferably have 2 to 9 carbon atoms in the molecule and are particularly preferably selected from primary amines with a C ₂ -C ₆ alkyl parent structure that carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group which is formed from 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutane-1-ol, 5-aminopentane-1-ol, 1-aminopropane-2-ol, 1-aminobutane-2-ol, 1-aminopentane-2-ol, 1-aminopentane-3-ol, 1-aminopentane-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, and 2-amino-2-methylpropane-1,3-diol, and mixtures thereof. Alkanolamines which are particularly preferred according to the invention are selected from the group 2-aminoethane-1-ol, 2-amino-2-methylpropane-1-ol and 2-amino-2-methylpropane-1,3-diol; 2-aminoethane-1-ol is extremely preferred. However, secondary amines such as diisopropanolamine (1,1'-iminodipropane-2-ol) are also suitable alkalizing agents according to the invention. Agents that are particularly preferred according to the invention contain 2-aminoethane-1-ol, potassium hydroxide, L-arginine, L-lysine and mixtures thereof as alkalizing agents. Extremely preferred agents according to the invention for changing color contain a mixture of 2-aminoethane-1-ol, potassium hydroxide, L-arginine and L-lysine.

Color-changing agents preferred according to the invention are characterized in that at least one alkalizing agent is contained in a total amount of 0.5 - 10 wt. %, preferably 0.7 - 7 wt. %, particularly preferably 1.0 - 5 wt. %, extremely preferably 1.2 - 3 wt. %, in each case based on the weight of the color-changing agent.

The agents according to the invention are intended for use in the context of an oxidative color change of keratin fibers, in particular human hair. In oxidative color change processes, the agent according to the invention (M1), which is neutral or alkaline and preferably contains one or more oxidation dye precursors and optionally one or more direct dyes, is usually mixed with an aqueous hydrogen peroxide-containing composition (M2) which has an acidic pH immediately before application to the keratin fibers to form a ready-to-use colorant and is applied to the keratin fibers immediately after mixing. The neutral to alkaline medium of the application mixture leads to the activation of the hydrogen peroxide, which breaks down the melanin in the keratin fibers. If the agent according to the invention (M1) contains oxidation dye precursors, the hydrogen peroxide causes these to react with one another and form permanent dyes. To prevent this dye formation from occurring during storage of the agent, the agents according to the invention contain, based on their weight, zero to less than 0.1% by weight of peroxide compounds.

As a further obligatory component, the color-changing agents according to the invention contain at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ stands for an alkyl or alkenyl radical having 4 to 22 carbon atoms, G for a sugar radical having 5 or 6 carbon atoms and p for a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3 wt.%.

Surfactants and emulsifiers in the sense of the present application are amphiphilic (bifunctional) compounds that consist of at least one hydrophobic and at least one hydrophilic molecular part. The hydrophobic residue is preferably a hydrocarbon group with 8-28 carbon atoms, which can be saturated or unsaturated, linear or branched. This C ₈ -C ₂₈ alkyl group is particularly preferably linear. Basic properties of surfactants and emulsifiers are oriented absorption at interfaces as well as aggregation to form micelles and the formation of lyotropic phases.

When selecting surfactants suitable according to the invention, it may be preferable to use a mixture of surfactants in order to optimally adjust the stability and/or the application properties of the agents according to the invention.

Preferred sugars from which the sugar residue G of the nonionic surfactant of the formula R ⁴ O-[G] _p is selected are erythrose, threose, erythrulose, ribose, deoxyribose, arabinose, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose, fucose and rhamnose, particularly preferably glucose, galactose, fructose, fucose and rhamnose, extremely preferably glucose.

The alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical with 4 to 22 carbon atoms, G is a sugar radical with 5 or 6 carbon atoms and p is a positive rational number from 1 to 6, contain G a sugar radical with 5 or 6 carbon atoms which is derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl mono- and oligoglycosides are thus alkyl mono- and oligoglucosides. The index number p in the general formula indicates the degree of oligomerization (DP), i.e. the distribution of mono- and oligoglycosides, and stands for a positive rational number between 1 and 6. While p in the individual molecule must always be an integer and can assume the values p = 1 to 6, the value p for an alkyl oligoglycoside produced on an industrial scale is an analytically determined calculated value that is usually a fractional number. Alkyl mono- and oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0, preferably 1.5 to 2.0, are preferably used. From an application point of view, alkyl mono- and oligoglycosides whose degree of oligomerization is less than 1.7 and in particular in the range from 1.2 to 1.6 are preferred. The alkyl radical R ⁴ is derived from primary alcohols having 4 to 22, preferably 8 to 18, particularly preferably 8 to 12 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol as well as their technical mixtures, such as those obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides with a chain length of C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as first run in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and can be contaminated with a proportion of less than 6% by weight of C ₁₂ alcohol, as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). These are commercially available under the INCI name Caprylyl/Capryl Glucoside. Also preferred is an alkyl oligoglucoside commercial product whose alkyl radical R ⁴ is derived from technical C ₈ -C ₁₈ coconut fatty alcohol and which is available under the INCI name Coco-Glucoside. The alkyl radical R ⁴ can also be derived from primary alcohols with 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof, which can be obtained as described above. Alkyl oligoglucosides based on lauryl alcohol with a DP of 1 to 3 are preferred.

Agents preferred according to the invention are characterized in that at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, is contained in a total amount of 0.3 to 2.5% by weight, preferably 0.5 to 2.0% by weight, particularly preferably 0.8 to 1.5% by weight, extremely preferably 1.0 to 1.2% by weight, in each case based on the weight of the agent.

Further agents preferred according to the invention are characterized in that at least one alkyl oligoglycoside of the formula R ⁴ O-[G] _p , in which R ⁴ stands for an alkyl radical having 8 to 18, preferably 8 to 12 carbon atoms, G stands for a glucose radical and p stands for positive rational numbers from 1.1 to 2, is contained in a total amount of 0.1 to less than 3% by weight, based on the weight of the agent.

Further agents preferred according to the invention are characterized in that at least one alkyl oligoglycoside of the formula R ⁴ O-[G] _p , in which R ⁴ stands for an alkyl radical having 8 to 18, preferably 8 to 12 carbon atoms, G stands for a glucose radical and p stands for positive rational numbers from 1.1 to 2, is contained in a total amount of 0.3 to 2.5 wt.%, preferably 0.5 to 2.0 wt.%, particularly preferably 0.8 to 1.5 wt.%, extremely preferably 1.0 to 1.2 wt.%, in each case based on the weight of the agent.

In a preferred embodiment, the agent according to the invention for changing the color of keratin fibers contains at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type.

Oxidation dye precursors can be divided into two categories based on their reaction behavior, so-called developer components and coupler components. Coupler components do not form a significant color on their own during oxidative dyeing, but always require the presence of developer components. Developer components can form the actual dye with themselves.

The developer and coupler components are usually used in free form. However, in the case of substances with amino groups, it may be preferable to use them in salt form, particularly in the form of hydrochlorides or hydrobromides or sulfates.

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

Very particularly preferred developer components are selected from 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine and mixtures of these compounds and their physiologically acceptable salts. 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine and mixtures of these compounds and their physiologically acceptable salts are particularly preferred.

Preferably, at least one developer component is present in a total amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight, particularly preferably 0.2 to 2.5% by weight, in each case based on the weight of the oxidation colorant (M1) according to the invention.

Preferably, at least one coupler component is present in a total amount of 0.001 to 4% by weight, preferably 0.01 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, in each case based on the weight of the oxidation colorant (M1) according to the invention.

• - 3-Aminophenol (m-Aminophenol) und/oder dessen Derivate,
• - 3-Aminoanilin (m-Diaminobenzol) und/oder dessen Derivate,
• - 2-Aminoanilin (1,2-Diaminobenzol; o-Diaminobenzol) und/oder dessen Derivate,
• - 2-Aminophenol (o-Aminophenol) und/oder dessen Derivate,
• - Naphthalinderivate mit mindestens einer Hydroxygruppe,
• - Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• - Pyridinderivate,
• - Pyrimidinderivate,
• - Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• - Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• - Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Morpholinderivate, wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Aminobenzomorpholin,
• - Chinoxalinderivate, wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Coupler components in the sense of the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. In this case, a covalent bond is formed between the coupler and developer components. Couplers are preferably cyclic compounds that carry at least two groups on the cycle, selected from (i) optionally substituted amino groups and/or (ii) hydroxyl groups. If the cyclic compound is a six-membered ring (preferably aromatic), the said groups are preferably in the ortho position or meta position to one another. Preferred agents according to the invention are characterized in that the at least one oxidation dye precursor of the coupler type is selected from one of the following classes:

• - 3-aminophenol (m-aminophenol) and/or its derivatives,
• - 3-aminoaniline (m-diaminobenzene) and/or its derivatives,
• - 2-aminoaniline (1,2-diaminobenzene; o-diaminobenzene) and/or its derivatives,
• - 2-aminophenol (o-aminophenol) and/or its derivatives,
• - Naphthalene derivatives containing at least one hydroxy group,
• - Di- or trihydroxybenzene and/or their derivatives,
• - pyridine derivatives,
• - pyrimidine derivatives,
• - monohydroxyindole derivatives and/or monoaminoindole derivatives,
• - monohydroxyindoline derivatives and/or monoaminoindoline derivatives,
• - Pyrazolone derivatives, such as 1-phenyl-3-methylpyrazol-5-one,
• - Morpholine derivatives, such as 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• - Quinoxaline derivatives, such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

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

Additional coupler components which are particularly preferred according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)amino-2-methylphenol, 1-beta-hydroxyethyl-3,4-methylenedioxyaniline, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene (= 2-amino-4-hydroxyethylaminoanisole), 1,3-bis(2,4-diaminophe-nyl)propane, 2,6-Bis(2'-hydroxyethylamino)-1- methylbenzene, 2-({3-[(2-Hydroxyethyl)amino]-4-meth-oxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}-amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3- Morpholin-4-ylphenyl)amino]ethanol, 3-amino-4-(2-methoxyethoxy)-5-methylphenylamine, 1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxy pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred are 3-aminophenol, resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene, 2-amino-3-hydroxypyridine, 1-naphthol and 1-beta-hydroxyethyl-3,4-methylenedioxyaniline, as well as their physiologically acceptable salts and mixtures of the components mentioned.

The at least one coupler component is preferably contained in a total amount of 0.01 - 20 wt.%, particularly preferably 0.2 - 10 wt.%, and extremely preferably 0.6 - 5 wt.%, in each case based on the weight of the oxidation colorant according to the invention.

In order to achieve a balanced and subtle nuance formation or to mattify undesirable residual color impressions caused by melanin degradation products, in particular in the reddish or bluish range, it is preferred according to the invention if further color-imparting components are contained in the oxidative color-changing agent according to the invention.

In a further embodiment, the oxidative color-changing agents according to the invention can therefore additionally contain at least one direct dye. These are dyes that are absorbed directly into the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

Direct dyes can be anionic, cationic or non-ionic. The direct dyes are preferably contained in an amount of 0.001 to 2% by weight, based on the weight of the oxidative color-changing agent.

Preferred anionic direct dyes are the compounds known under the international names 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, Acid Black 52, Bromophenol Blue and Tetrabromophenol Blue. Preferred cationic direct dyes are cationic triphenylmethane dyes, for example Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems which are substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes, such as HC Blue 16 (Bluequat B) and direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic direct dyes which are sold under the trademark Arianor are also preferred cationic direct dyes according to the invention. Nonionic direct dyes which are particularly suitable are nonionic nitro and quinone dyes and neutral azo dyes. Preferred non-ionic direct dyes are the compounds known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, as well as 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. According to the invention, it is very particularly preferred to contain at least one cationic direct dye selected from Basic Blue 7, Basic Blue 26, Basic Violet 2, Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16, Basic Brown 17, HC Blue 16 (Bluequat B), Basic Yellow 87, Basic Orange 31 and Basic Red 51 and mixtures thereof.

Particularly preferred oxidative color-changing agents according to the invention contain, in addition to the at least one alkyl mono- or oligoglycoside of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical with 4 to 22 carbon atoms, G is a sugar radical with 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, at least one further nonionic surfactant. The additional nonionic surfactants are preferably contained in a total amount of 0.1 - 5 wt.%, particularly preferably 0.2 - 4 wt.%, further particularly preferably 0.5 - 2 wt.%, in each case based on the weight of the color-changing agent according to the invention.

Additional nonionic surfactants preferred according to the invention are selected from addition products of 6 to 12 ethylene oxide units and one to two propylene oxide units with divalent C10-16 alkane glycols, further selected from castor oil ethoxylated with 20 - 100 moles of ethylene oxide per mole, ethoxylated _{C8 -C24} alkanols with 10 - 100 moles of ethylene oxide per mole, sorbitan monoesters of linear saturated and unsaturated C12 - _C30 carboxylic acids ethoxylated with ₂₀ - 100 moles of ethylene oxide per mole, which may be hydroxylated, in particular those of myristic acid, palmitic acid, stearic acid or mixtures of these fatty acids, as well as mixtures of the aforementioned substances.

Particularly preferred additional nonionic surfactants are selected from addition products of 6 to 12 ethylene oxide units and one to two propylene oxide units to divalent C10-16 alkane glycols, wherein preferred divalent C10-16 alkane glycols are selected from 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol (lauryl glycol), 1,2-tridecanediol, 1,2-tetradecanediol, 1,2-pentadecanediol and 1,2-hexadecanediol and mixtures thereof. Particularly preferred nonionic surfactants are selected from addition products of 6 to 12, preferably 8-9 ethylene oxide units and one to two propylene oxide units with 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol (lauryl glycol), 1,2-tridecanediol, 1,2-tetradecanediol, 1,2-pentadecanediol or 1,2-hexadecanediol and mixtures thereof. A nonionic surfactant of this class which is particularly preferred according to the invention is PPG-1-PEG-9 lauryl glycol ether, which is available, for example, under the trade name Eumulgin L from BASF.

The ethoxylated C ₈ -C ₂₄ alkanols preferably used according to the invention have the formula R ¹ O(CH ₂ CH ₂ O) _n H, where R ¹ stands for a linear or branched alkyl and/or alkenyl radical having 8 - 24 carbon atoms and n, the average number of ethylene oxide units per molecule, for numbers from 10 - 100, preferably 10 - 30, particularly preferably 15 to 25 moles of ethylene oxide per molecule of caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical mixtures thereof. Adducts of 10 - 100 moles of ethylene oxide with technical fatty alcohols with 12 - 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol, are also suitable. Laureth-10, Laureth-12, Laureth-15, Laureth-20, Laureth-30, Laureth-100, Myreth-10, Myreth-12, Myreth-15, Myreth-20, Myreth-30, Myreth-100, Ceteth-10, Ceteth-12, Ceteth-15, Ceteth-20, are particularly preferred , Ceteth-50, Ceteth-100, Steareth-10, Steareth-12 Steareth-15, Steareth-20, Steareth-30, Steareth-50, Steareth-100, Oleth-10, Oleth-12, Oleth-15, Oleth-20, Oleth-30, Oleth-50, Oleth-100,Ceteareth-10, Ceteareth-15, Ceteareth-12, Ceteareth-15, Ceteareth-20, Ceteareth-30, Ceteareth-50, Ceteareth-100 and Coceth-10, Coceth-12, Coceth-15, Coceth-20, Coceth-30, Coceth-50 and Coceth-100. A nonionic surfactant of this class which is particularly preferred according to the invention is Steareth-100, which is preferably contained in an amount of 0.1 - 2% by weight, particularly preferably 0.2 - 1% by weight, further particularly preferably 0.3 - 0.5% by weight, in each case based on the weight of the color-changing agent according to the invention.

Preferred color-changing agents according to the invention contain the additional nonionic surfactant PPG-1-PEG-9 lauryl glycol ether, which is preferably contained in an amount of 0.1 - 3 wt.%, particularly preferably 0.2 - 2 wt.%, further particularly preferably 0.5 - 1.0 wt.%, in each case based on the weight of the color-changing agent according to the invention.

Further preferred color-changing agents according to the invention contain PPG-1-PEG-9 lauryl glycol ether, steareth-100 and at least one alkyl oligoglycoside of the formula R ⁴ O-[G] _p , in which R ⁴ stands for an alkyl radical having 8 to 18, preferably 8 to 12 carbon atoms, G stands for a glucose radical and p stands for numbers from 1.1 to 2.

Further oxidative color-changing agents (M1) preferred according to the invention are characterized in that only nonionic surfactants are contained.

Further oxidative color-changing agents (M1) preferred according to the invention are characterized in that they do not contain any ionic surfactant.

Further oxidative color-changing agents (M1) preferred according to the invention are characterized in that they contain no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane, that is to say that, based on their weight, 0.0 wt. % of the aforementioned (co)polymers are contained in (M1).

Further oxidative color-changing agents (M1) preferred according to the invention are characterized in that, in addition to iota-carrageenan, they contain at least one further polysaccharide as a thickening polymer.

Additional polysaccharide thickening polymers preferred according to the invention are selected from xanthan, hyaluronic acid, salts of hyaluronic acid, in particular sodium hyaluronate, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof. Xanthan, hyaluronic acid, salts of hyaluronic acid and mixtures thereof are extremely preferred according to the invention.

Surprisingly, it was found that oxidative colorings with high fastness properties can be achieved with iota-carrageenan and xanthan. Synergistic effects were also observed in the application properties, in particular with regard to the applicability and gel stability during the exposure time on the keratin fibers. Oxidative color-changing agents that are particularly preferred according to the invention are therefore characterized in that they contain, in each case based on the weight of the color-changing agent according to the invention, 0.05 - 1.5% by weight, preferably 0.1 - 1.2% by weight, particularly preferably 0.5 - 1% by weight, extremely preferably 0.6 - 0.9% by weight of xanthan.

In order to further optimize the application and coloring properties of the color-changing agents according to the invention, it has surprisingly proven useful if, in addition to iota-carrageenan or in addition to iota-carrageenan and xanthan, they contain at least one further thickening polymer selected from hyaluronic acid, salts of hyaluronic acid, in particular sodium hyaluronate, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof. The thickening polymer selected from hyaluronic acid, salts of hyaluronic acid, in particular sodium hyaluronate, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof, is preferably contained in a total amount of 0.005 - 1.0% by weight, particularly preferably 0.01 - 0.5% by weight, in each case based on the weight of the color-changing agent according to the invention. Color-changing agents which are particularly preferred according to the invention are characterized in that they contain, in each case based on their weight, 0.05 - 1.5% by weight, preferably 0.1 - 1.2% by weight, particularly preferably 0.5 - 1% by weight, extremely preferably 0.6 - 0.9% by weight, of xanthan and at least one further thickening polymer selected from hyaluronic acid, salts of hyaluronic acid, in particular sodium hyaluronate, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof. Further color-changing agents which are particularly preferred according to the invention are characterized in that they contain, in each case based on their weight, 0.05 - 1.5% by weight, preferably 0.1 - 1.2% by weight, particularly preferably 0.5 - 1% by weight, extremely preferably 0.6 - 0.9% by weight, of xanthan and at least one salt of hyaluronic acid in a total amount of 0.005 to 0.05% by weight, preferably 0.01 - 0.03% by weight.

Color-changing agents that are particularly preferred according to the invention are characterized in that they additionally contain, based on their weight, 0.005 to 0.05% by weight, preferably 0.01 to 0.03% by weight, hyaluronic acid or at least one salt of hyaluronic acid. Hyaluronic acid or its salts further optimize the application properties of the color-changing agents according to the invention, in particular the gel properties during application, as well as the coloring properties, in particular with regard to color intensity and balancing power.

Furthermore, it was surprisingly found that the application properties of the color-changing agents according to the invention are further optimized, in particular the gel properties during storage and during use, as well as the coloring properties, in particular with regard to color intensity and balancing power, if they additionally contain at least one polyol other than compounds of the formula R ⁴ O-[G] _p , selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, the carbon atom chain of which can be interrupted by one or more oxygen atoms.

Oxidative color-changing agents preferred according to the invention are therefore characterized in that they additionally contain at least one polyol other than compounds of the formula R ⁴ O-[G] _p , selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain can be interrupted by one or more oxygen atoms.

Polyols of this type preferred according to the invention are selected from glycerin, 1,2-propylene glycol, 2-methyl-1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, pentylene glycols such as 1,2-pentanediol and 1,5-pentanediol, hexanediols such as 1,6-hexanediol, hexantriols such as 1,2,6-hexanetriol, 1,2-octanediol, 1,8-octanediol, dipropylene glycol, tripropylene glycol, diglycerin, triglycerin, erythritol, sorbitol, PEG-3, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, fructose, glucose, maltose, maltitol, xylitol, mannitol, inositol, sucrose, Trehalose and xylose and mixtures thereof, with glycerin, 1,2-propylene glycol, PEG-8, 1,3-butylene glycol, 1,6-hexanediol, dipropylene glycol and xylitol and mixtures thereof being preferred. Glycerin, 1,2-propylene glycol, PEG-8 and mixtures thereof are particularly preferred polyols according to the invention; glycerin is extremely preferred.

Particularly preferred oxidative color-changing agents according to the invention are characterized in that the at least one polyol different from compounds of the formula R ⁴ O-[G] _p , which is selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain can be interrupted by one or more oxygen atoms, is contained in a total amount of 0.5 - 20 wt.%, preferably 1 - 15 wt.%, particularly preferably 3 - 10 wt.%, extremely preferably 5 - 8 wt.%, in each case based on the weight of the color-changing agent according to the invention.

In a further preferred embodiment of the invention, the color-changing agents (M1) are transparent. According to the invention, transparent color-changing agents (M1) are understood to mean color-changing agents which have an NTU value (nephelometric turbidity value) of zero to 150 NTU, preferably of a maximum of 80 NTU, particularly preferably of a maximum of 60 NTU, extremely preferably of a maximum of 40 NTU, each measured at 22°C. The NTU value here is a measurement value for the transparency and is a turbidity of the color-changing agent measured with a calibrated nephelometer. The NTU value of the color-changing agents according to the invention can be determined, for example, using a turbidimeter, as in the published application WO2016012327 A2 Color-changing agents (M1) preferred according to the invention have a turbidity measured at 22 °C EN ISO 7027 (C2) 2016-11 from 0 to 150 NTU, preferably up to 80 NTU, more preferably up to 60 NTU, even more preferably up to 40 NTU, further preferably up to 30 NTU.

Other oxidative color-changing agents preferred according to the invention have a transmission of at least 80%, preferably 85 or more, particularly preferably 92% - 100%, determined at 22 °C and 500 nm light wavelength. According to the invention, a spectrophotometer such as LICO 400 (Lange) can be used to determine the transmission.

Oxidative color-changing agents that are particularly preferred according to the invention are in the form of a water-based gel that, based on its weight, contains a total of zero to a maximum of 2% by weight, preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight of fatty substances. Fatty substances according to the invention are lipophilic organic substances that have a water solubility of a maximum of 0.5% by weight or less, preferably a maximum of 0.1% by weight or less, at 20°C. According to the invention, these fatty substances include in particular oils, fats, waxes, fatty alcohols and fatty acids. Essential oils and perfume oils or fragrances are not counted as fatty substances in the sense of the present invention.

According to the invention, a wax is understood to be an organic compound which is soluble in bidistilled water to less than 0.5% by weight under normal conditions, melts at over 40 °C and then forms a liquid with a low viscosity of 1 to 800 mPas at 20 °C. According to the definition of the German Society for Fat Science, a wax is still kneadable at 20 °C, solid to brittle-hard, has a coarse to finely crystalline structure, is translucent to opaque in color, but not glassy, has a consistency and solubility that is strongly dependent on temperature and can be polished under light pressure.

Fatty alcohols are 1-alkanols with at least 4 carbon atoms, which can be linear (e.g. cetyl alcohol) or branched (e.g. 2-ethylhexan-1-ol). Fatty acids are 1-carboxylic acids with at least 4 carbon atoms, which can be linear (e.g. oleic acid) or branched (e.g. 2-ethylhexanoic acid).

All information on the physical states of substances (solid, liquid, gaseous) in this application refers to standard conditions. “Standard conditions” in the sense of this application are a temperature of 20°C and a pressure of 1013.25 mbar.

Since the agents according to the invention preferably contain fatty substances in a total amount of zero to 2% by weight, preferably 0.01 - 1.5% by weight, particularly preferably 0.1 - 1.0% by weight, extremely preferably 0.2 - 0.5% by weight, in each case based on the weight of the oxidative color-changing agent, preferably no ammonia or ammonium hydroxide is contained as an alkalizing agent. Oxidative color-changing agents with ammonia or ammonium hydroxide that are low in fatty substances release larger amounts of ammonia during the color-changing process than oxidative color-changing agents that are rich in fatty substances, so that non-volatile alkalizing agents, i.e. all alkalizing agents other than ammonia or ammonium hydroxide, are preferred according to the invention.

Essential oils and perfume oils or fragrances are not considered fatty substances in the sense of the present invention. Essential oils are understood according to the invention to be mixtures of volatile components that are produced by steam distillation from plant raw materials, such as citrus oils. If a cosmetic oil is mentioned in the present application, this always refers to a cosmetic oil that is neither a fragrance nor an essential oil, is liquid under normal conditions and is not miscible with water.

The definition of a fragrance in the sense of the present application corresponds to the definition commonly used by experts, as can be found in the RÖMPP Chemistry Lexicon, as of December 2007. According to this, a fragrance is a chemical compound with an odor and/or taste that stimulates the receptors of the hair cells of the olfactory system (adequate stimulus). The physical and chemical properties required for this are a low molecular weight of a maximum of 300 g/mol, a high vapor pressure, minimal water and high lipid solubility, as well as weak polarity and the presence of at least one osmophoric group in the molecule. In order to distinguish volatile, low molecular weight substances which are usually and also in the sense of the present application not regarded and used as fragrances but primarily as solvents, such as ethanol, propanol, isopropanol and acetone, from fragrances according to the invention, fragrances according to the invention have a molecular weight of 74 to 300 g/mol, contain at least one osmophoric group in the molecule and have an odor and/or taste, i.e. they excite the receptors of the hair cells of the olfactory system.

Particularly preferred oxidative color-changing agents according to the invention are characterized in that at least one essential oil, perfume oil or fragrance is contained, preferably in a total amount of 0.1 - 3 wt.%, particularly preferably 0.2 - 1 wt.%, extremely preferably 0.5 - 0.8 wt.%, in each case based on the weight of the color-changing agent according to the invention.

It is further preferred that the oxidative color-changing agents according to the invention contain at least one cationic polymer. Preferably, no cationic polymers or copolymers with acrylate-, methacrylate- or vinyl-containing monomers and no cationic polyurethane are used.

The cationic polymers are preferably homo- or copolymers or polymers based on natural polymers, where the quaternary nitrogen groups are present either in the polymer chain or, preferably, as a substituent on one or more of the monomers. The monomers containing ammonium groups can be copolymerized with non-cationic monomers. Other cationic monomers suitable according to the invention, although less preferred, are unsaturated, radically polymerizable compounds which carry at least one cationic group, in particular ammonium-substituted vinyl monomers, such as trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic groups containing cationic nitrogen, such as pyridinium, imidazolium or quaternary pyrrolidones, e.g. alkylvinylimidazolium, alkylvinylpyridinium, or alkylvinylpyrrolidone salts. The alkyl groups of these monomers are preferably lower alkyl groups such as C1 to C7 alkyl groups, particularly preferably C1 to C3 alkyl groups.

The monomers containing ammonium groups can be copolymerized with non-cationic monomers. Suitable comonomers are, for example, acrylamide, methacrylamide; alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl caprolactam, vinyl pyrrolidone, vinyl esters, e.g. vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, where the alkyl groups of these monomers are preferably C1 to C7 alkyl groups, particularly preferably C1 to C3 alkyl groups.

• - polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Besonders bevorzugte Polymere dieses Typs sind Dimethyldiallylammoniumchlorid-Acrylamid-Copolymere, insbesondere solche mit der INCI-Bezeichnung Polyquaternium-7. Polyquaternium-7 ist zum Beispiel als Handelsprodukt Merquat^®550 erhältlich. Ein anderes bevorzugtes Polymer dieses Typs ist das Homopolymer Poly(dimethyldiallylammoniumchlorid), insbesondere die Homopolymere mit der INCI-Bezeichnung Polyquaternium-6. Polyquaternium-6 ist zum Beispiel als Handelsprodukt Merquat^®100 erhältlich. Weitere bevorzugte Polymere dieses Typs sind Terpolymere aus Dimethyldiallylammoniumchlorid, Acrylamid und Ammoniumacrylat, insbesondere solche mit der INCI-Bezeichnung Polyquaternium-39. Polyquaternium-39 ist zum Beispiel als Handelsprodukt Merquat^®3330 und Merquat^®3331 erhältlich. Weitere bevorzugte Polymere dieses Typs sind Copolymere aus Dimethyldiallylammoniumchlorid und Acrylsäure, insbesondere solche mit der INCI-Bezeichnung Polyquaternium-22. Polyquaternium-22 ist zum Beispiel als Handelsprodukt Merquat^®280 erhältlich.
• - Homopolymere der allgemeinen Formel -{CH₂-[CR¹COO-(CH₂)_mN⁺R²R³R⁴]}_n X^-, in der R¹= -H oder -CH₃ ist, R², R³ und R⁴ unabhängig voneinander ausgewählt sind aus C1-4-Alkyl-, C1-4-Alkenyl- oder C1-4-Hydroxyalkylgruppen, m = 1, 2, 3 oder 4, n eine natürliche Zahl und X^- ein physiologisch verträgliches organisches oder anorganisches Anion ist. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt: R¹ steht für eine Methylgruppe, R², R³ und R⁴ stehen für Methylgruppen, m hat den Wert 2.Als physiologisch verträgliches Gegenionen X^- kommen beispielsweise Halogenidionen, Sulfationen, Phosphationen, Methosulfationen sowie organische Ionen wie Lactat-, Citrat-, Tartrat- und Acetationen in Betracht. Bevorzugt sind Methosulfate und Halogenidionen, insbesondere Chlorid.

Of the multitude of these polymers, the following have proven to be particularly effective components of the agents according to the invention:

• - polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Particularly preferred polymers of this type are dimethyldiallylammonium chloride-acrylamide copolymers, in particular those with the INCI name Polyquaternium-7. Polyquaternium-7 is available, for example, as the commercial product Merquat ^® 550. Another preferred polymer of this type is the homopolymer poly(dimethyldiallylammonium chloride), in particular the homopolymers with the INCI name Polyquaternium-6. Polyquaternium-6 is available, for example, as the commercial product Merquat ^® 100. Other preferred polymers of this type are terpolymers of dimethyldiallylammonium chloride, acrylamide and ammonium acrylate, in particular those with the INCI name Polyquaternium-39. Polyquaternium-39 is available, for example, as the commercial products Merquat ^® 3330 and Merquat ^® 3331. Other preferred polymers of this type are copolymers of dimethyldiallylammonium chloride and acrylic acid, in particular those with the INCI name Polyquaternium-22. Polyquaternium-22 is available, for example, as the commercial product Merquat ^® 280.
• - Homopolymers of the general formula -{CH ₂ -[CR ¹ COO-(CH ₂ ) _m N ⁺ R ² R ³ R ⁴ ]} _n X ^- , in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ⁴ are independently selected from C1-4 alkyl, C1-4 alkenyl or C1-4 hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^- is a physiologically acceptable organic or inorganic anion. Within the scope of these polymers, those are preferred according to the invention for which at least one of the following conditions applies: R ¹ stands for a methyl group, R ² , R ³ and R ⁴ stand for methyl groups, m has the value 2. Examples of physiologically acceptable counterions X ^- are halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Methosulfates and halide ions, in particular chloride, are preferred.

in der Xsteht für Chlorid, Sulfat, Methosulfat, und A2) Monomere aus der Gruppe Acrylsäure, Methacrylsäure sowie den Alkalimetall- und Ammoniumsalzen dieser Säuren, wobei das Monomere A2 50 bis 99,9 %, vorzugsweise 50 bis 90 % (bezogen auf die Gesamt-Anzahl an Monomeren im Copolymer) des Copolymers ausmacht; enthalten.Other preferably suitable cationic polymers derived from synthetic polymers are, for example, copolymers of A1) 0.1 to 50%, preferably 10 to 50% (based on the total number of monomers in the copolymer) monomers of the formula (la)

in which X stands for chloride, sulfate, methosulfate, and A2) monomers from the group acrylic acid, methacrylic acid and the alkali metal and ammonium salts of these acids, where the monomer A2 makes up 50 to 99.9%, preferably 50 to 90% (based on the total number of monomers in the copolymer) of the copolymer.

A particularly suitable homopolymer is poly(methacryloyl-oxyethyltrimethylammonium chloride), cross-linked if desired, with the INCI name Polyquaternium-37. Such products are commercially available under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen ^® CR (3V Sigma).

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion. Such polymer dispersions are commercially available under the names Salcare ^® SC 95 and Salcare ^® SC 96.

Suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example cationic derivatives of cellulose, starch or guar. Chitosan and chitosan derivatives are also suitable. Cationic polysaccharides have the general formula GOB-N+R _a R _b R _c A ^-
G is an anhydroglucose residue, for example starch or cellulose anhydroglucose;
B is a divalent linking group, for example alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene;
R _a , R _b and R _c are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having up to 18 C atoms, wherein the total number of C atoms in R _a , R _b and R _c is preferably a maximum of 20;
A ^- is a common counter anion, preferably chloride.

Cationic, i.e. quaternized, celluloses are available on the market with different degrees of substitution, cationic charge density, nitrogen content and molecular weights. For example, Polyquaternium-67 is sold under the names Polymer ^® SL or Polymer ^® SK (Amerchol). Another highly preferred cellulose is sold under the trade name Mirustyle ^® CP by Croda. This is a cellulose derivatized as Trimonium and Cocodimonium Hydroxyethylcellulose with the INCI name Polyquaternium-72. Polyquaternium-72 can be used both in solid form and pre-dissolved in an aqueous solution.

Other cationic celluloses are known under the names Polymer JR ^® 400 (Amerchol, INCI name Polyquaternium-10) and Polymer Quatrisoft ^® LM-200 (Amerchol, INCI name Polyquaternium-24). Other commercial products are the compounds Celquat ^® H 100 and Cel-quat ^® L 200. Particularly preferred cationic celluloses are Polyquaternium-10, Polyquaternium-24, Polyquaternium-67 and Polyquaternium-72.

Suitable cationic guar derivatives are preferably selected from compounds with the INCI name Guar Hydroxypropyltrimonium Chloride.

A suitable chitosan is, for example, sold by Kyowa Oil & Fat, Japan, under the trade name Flonac ^® . A preferred chitosan salt is chitosonium pyrrolidone carboxylate, which is sold, for example, under the name Kytamer ^® PC by Amerchol, USA. Other chitosan derivatives are available under the trade names Hydagen ^® CMF,

Hydagen ^® HCMF and Chitolam ^® NB/101 are commercially available.

Finally, cationic polymers based on sugars can also be used with preference according to the invention. Such compounds are, for example, cationic alkyl oligoglucosides as shown in the following figure.

In the formula shown above, the radicals R independently of one another represent a linear or branched C6 to C30 alkyl radical, a linear or branched C6 - C30 alkenyl radical, preferably the radical R represents a radical R selected from: lauryl, myristyl, cetyl, stearyl, oleyl, behenyl or arachidyl.

The radicals R1 independently represent a linear or branched C6 to C30 alkyl radical, a linear or branched C6 to C30 alkenyl radical, preferably the radical R represents a radical selected from butyl, capryl, caprylyl, octyl, nonyl, decanyl, lauryl, myristyl, cetyl, stearyl, oleyl, behenyl or arachidyl. Particularly preferably, the radicals R1 are identical. Even more preferably, the radicals R1 are selected from technical mixtures of the fatty alcohol cuts of C6/C8 fatty alcohols, C8/C10 fatty alcohols, C10/C12 fatty alcohols, C12/C14 fatty alcohols, C12/C18 fatty alcohols, and most preferably those technical fatty alcohol cuts which are of plant origin.

Particularly preferred examples of the cationic alkyl oligoglucosides are the compounds with the INCI names Polyquaternium-77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-80, Polyquaternium-81 and Polyquaternium-82. The cationic alkyl oligoglucosides with the names Polyquaternium-77, Polyquaternium-81 and Polyquaternium-82. Such compounds can be obtained, for example, under the name Poly Suga® Quat from Colonial Chemical Inc.

The cationic alkyl oligoglucosides are preferably contained in a total amount of 0.01 to 6% by weight, particularly preferably 0.05 - 4% by weight, extremely preferably 0.1 - 3.5% by weight, in each case based on the weight of the agent according to the invention. The invention of course also includes the use of mixtures of cationic alkyl oligoglucosides. In this case, it is preferred if one long-chain and one short-chain cationic alkyl oligoglucoside are contained simultaneously.

Another cationic polymer can be obtained on the basis of ethanolamine. The polymer is commercially available under the name Polyquaternium-71.

This polymer can be purchased, for example, under the name Cola® Moist 300 P from Colonial Chemical Inc.

Polyquaternium-71 is preferably contained in an amount of 0.01 - 6 wt.%, particularly preferably 0.05 - 4 wt.%, extremely preferably 0.1 - 3.5 wt.%, in each case based on the weight of the agent according to the invention.

• - kationisierter Honig, beispielsweise das Handelsprodukt Honeyquat^® 50,
• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie zum Beispiel unter den Bezeichnungen Luviquat^® FC 370, FC 550 und der INCI-Bezeichnung Polyquaternium-16 sowie FC 905 und HM 552 angeboten werden,
• - quaternisiertes Vinylpyrrolidon/Dimethylaminoethylmethacrylat, zum Beispiel Vinylpyrrolidon/ Dimethylaminoethylmethacrylatmethosulfat Copolymer, das unter den Handelsbezeichnungen Gafquat^® 755 N und Gafquat^® 734 von der Firma Gaf Co., USA vertrieben wird und die INCI-Bezeichnung Polyquaternium-11 hat,
• - quaternierter Polyvinylalkohol,
• - sowie die unter den Bezeichnungen Polyquaternium-2, Polyquaternium-17, Polyquaternium-18 und Polyquaternium-27 bekannten Polymere mit quartären Stickstoffatomen in der Polymerhauptkette,
• - Vinylpyrrolidon-Vinylcaprolactam-Acrylat-Terpolymere, wie sie mit Acrylsäureestern und Acrylsäureamiden als drittem Monomerbaustein im Handel beispielsweise unter der Bezeichnung Aquaflex^® SF 40 angeboten werden.

Other preferred cationic polymers are, for example,

• - cationized honey, for example the commercial product Honeyquat ^® 50,
• - Vinylpyrrolidone-vinylimidazolium methochloride copolymers, such as those sold under the names Luviquat ^® FC 370, FC 550 and the INCI name Polyquaternium-16 as well as FC 905 and HM 552,
• - quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate, for example vinylpyrrolidone/dimethylaminoethyl methacrylate methosulfate copolymer, which is sold under the trade names Gafquat ^® 755 N and Gafquat ^® 734 by Gaf Co., USA and has the INCI name Polyquaternium-11,
• - quaternized polyvinyl alcohol,
• - as well as the polymers known under the names Polyquaternium-2, Polyquaternium-17, Polyquaternium-18 and Polyquaternium-27 with quaternary nitrogen atoms in the polymer main chain,
• - Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, such as those commercially available with acrylic acid esters and acrylic acid amides as the third monomer building block, for example under the name Aquaflex ^® SF 40.

In a particularly preferred embodiment of the invention, the agent according to the invention or used according to the invention contains, in each case based on its weight, at least one cationic polymer in a total amount of 0.01 - 2 wt.%, preferably 0.05 - 1 wt.%, particularly preferably 0.1 - 0.7 wt.%, extremely preferably 0.2 - 0.5 wt.%.

In a further particularly preferred embodiment of the invention, the agent according to the invention or used according to the invention contains, in each case based on its weight, at least one cationic polymer selected from dimethyldiallylammonium chloride-acrylamide copolymers, in particular those with the INCI name Polyquaternium-7, poly(dimethyldiallylammonium chloride), terpolymers of dimethyldiallylammonium chloride, acrylamide and ammonium acrylate, in particular those with the INCI name Polyquaternium-39, and copolymers of dimethyldiallylammonium chloride and acrylic acid, in particular those with the INCI name Polyquaternium-22, and mixtures thereof, in a total amount of 0.01 - 2 wt.%, preferably 0.05 - 1 wt.%, particularly preferably 0.1 - 0.7 wt.%, extremely preferably 0.2 - 0.5 wt.%.

1. a) mindestens einen Container (C1), enthaltend ein Mittel zur oxidativen Farbveränderung keratinischer Fasern, enthaltend:
   • - mehr als 80 Gew.-% bis 99 Gew.-% Wasser,
   • - 0,1 bis 1,5 Gew.-% iota-Carrageen,
   • - 0,05 bis 0,5 Gew.-% Kaliumionen in Form von mindestens einem Kaliumsalz,
   • - mindestens ein nichtionisches Tensid, ausgewählt aus Alkylmono- und - oligoglycosiden der Formel R⁴O-[G]_p, in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine positive rationale Zahl im Bereich von 1 bis 6 steht, in einer Gesamtmenge von 0,1 bis weniger als 3 Gew.-%,
   • - mindestens ein Alkalisierungsmittel,
   • - null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
   • - optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
   • - wobei das Mittel einen pH-Wert im Bereich von 7 bis 11, bevorzugt im Bereich von 7,5 bis 10,7, besonders bevorzugt im Bereich von 8 bis 10, außerordentlich bevorzugt 8,5 bis 9,5, aufweist, jeweils gemessen bei einer Temperatur von 22 °C, und
2. b) mindestens einen Container (C2), enthaltend eine Oxidationsmittelzubereitung (M2), die 40
   • - 96 Gew.-%, bevorzugt 65 - 90 Gew.-%, besonders bevorzugt 70 - 80 Gew.-%, Wasser, weiterhin Wasserstoffperoxid in einer Gesamtmenge von 0,5 bis 23 Gew.-%, weiter bevorzugt 2,5 bis 21 Gew.-%, besonders bevorzugt 4 bis 20 Gew.-%, ganz besonders bevorzugt 5 bis 18 Gew.-% und außerordentlich bevorzugt 6 bis 12 Gew.-%, enthält und einen pH-Wert im Bereich von 2,0 bis 6,5, bevorzugt 2,5 - 5,5, besonders bevorzugt 2,8 bis 4,5, aufweist, jeweils gemessen bei 20°C, wobei sich die Gew.-%-Angaben jeweils auf das Gewicht der Oxidationsmittelzubereitung (M2) beziehen, wobei optional mindestens ein Öl und/oder mindestens ein Tensid enthalten sind. Bezüglich weiterer bevorzugter Ausführungsformen des erfindungsgemäßen Kits gilt mutatis mutandis das zu den erfindungsgemäßen Mitteln zur oxidativen Farbveränderung Gesagte.

Another object of the present invention is a packaging unit (kit of parts) which - packaged separately - comprises the following:

1. a) at least one container (C1) containing an agent for the oxidative colour change of keratin fibres, containing:
   • - more than 80 wt.% to 99 wt.% water,
   • - 0.1 to 1.5% by weight iota carrageenan,
   • - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt,
   • - at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3% by weight,
   • - at least one alkalizing agent,
   • - zero to less than 0.1% by weight of peroxide compounds,
   • - optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
   • - wherein the agent has a pH in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C, and
2. b) at least one container (C2) containing an oxidizing agent preparation (M2) containing 40
   • - 96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, of water, furthermore hydrogen peroxide in a total amount of 0.5 to 23% by weight, more preferably 2.5 to 21% by weight, particularly preferably 4 to 20% by weight, very particularly preferably 5 to 18% by weight and extremely preferably 6 to 12% by weight, and has a pH in the range of 2.0 to 6.5, preferably 2.5-5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C, wherein the % by weight information relates in each case to the weight of the oxidizing agent preparation (M2), optionally containing at least one oil and/or at least one surfactant. With regard to further preferred embodiments of the kit according to the invention, what has been said about the agents according to the invention for oxidative color change applies mutatis mutandis.

A further subject of the present invention is the use of an agent according to one of claims 1 to 12 for the oxidative color change of keratin fibers, in particular human hair. With regard to further preferred embodiments of the use according to the invention, what has been said about the agents according to the invention for oxidative color change applies mutatis mutandis.

• i) Bereitstellen eines kosmetischen Mittels (M1) zur oxidativen Haarfärbung keratinischer Fasern, enthaltend
  • - mehr als 80 Gew.-% bis 99 Gew.-% Wasser,
  • - 0,1 bis 1,5 Gew.-% iota-Carrageen,
  • - 0,05 bis 0,5 Gew.-% Kaliumionen in Form von mindestens einem Kaliumsalz,
  • - 0,1 bis weniger als 3 Gew.-% mindestens eines nichtionischen Tensids, ausgewählt aus Alkylmono- und -oligoglycosiden der Formel R⁴O-[G]_p, in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine positive rationale Zahl im Bereich von 1 bis 6 steht,
  • - mindestens ein Alkalisierungsmittel,
  • - null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
  • - optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
  • - wobei das Oxidationsfärbemittel bevorzugt einen pH-Wert im Bereich von 8 bis 11, insbesondere im Bereich von 8,5 bis 10,7, besonders bevorzugt im Bereich von 9 bis 10,3, außerordentlich bevorzugt 9,5 bis 9,7, aufweist, jeweils gemessen bei einer Temperatur von 22 °C, und
• ii) Bereitstellen einer Oxidationsmittelzubereitung (M2), enthaltend 40 - 96 Gew.-%, bevorzugt 65 - 90 Gew.-%, besonders bevorzugt 70 - 80 Gew.-%, Wasser, weiterhin Wasserstoffperoxid in einer Gesamtmenge von 0,5 bis 23 Gew.-%, weiter bevorzugt 2,5 bis 21 Gew.-%, besonders bevorzugt 4 bis 20 Gew.-%, ganz besonders bevorzugt 5 bis 18 Gew.-% und außerordentlich bevorzugt 6 bis 12 Gew.-%, und einen pH-Wert im Bereich von 2,0 bis 6,5, bevorzugt 2,5 - 5,5, besonders bevorzugt 2,8 bis 4,5, aufweisend, jeweils gemessen bei 20°C, wobei sich die Gew.-%-Angaben jeweils auf das Gewicht der Oxidationsmittelzubereitung (M2) beziehen, wobei optional mindestens ein Tensid und/oder ein Öl enthalten sind,
• iii) Vermischen des kosmetischen Mittels (M1) mit der Oxidationsmittelzubereitung (M2), bevorzugt in einem Gewichtsverhältnis (M1):(M2) im Bereich von 1:0,8 bis 1:2,5, bevorzugt 1:1 bis 1:2, direkt anschließend
• iv) Applizieren der in Schritt iii) erhaltenen Mischung auf die Haare und Belassen dieser Mischung für eine Zeit von 1 bis 60 Minuten, bevorzugt von 20 bis 45 Minuten, bei Raumtemperatur und/oder bei 30 - 60°C, bevorzugt bei 32 - 50°C auf den Haaren,
• v) Spülen der Haare mit Wasser und/oder einer reinigenden Zusammensetzung, und
• vi) gegebenenfalls Applizieren eines Nachbehandlungsmittels auf die Haare und gegebenenfalls Ausspülen, anschließend Trocknen.

Another object of the present invention is a process for oxidative hair coloring, which comprises the following process steps:

• i) Providing a cosmetic agent (M1) for the oxidative hair coloring of keratin fibers, containing
  • - more than 80 wt.% to 99 wt.% water,
  • - 0.1 to 1.5% by weight iota carrageenan,
  • - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt,
  • - 0.1 to less than 3% by weight of at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6,
  • - at least one alkalizing agent,
  • - zero to less than 0.1% by weight of peroxide compounds,
  • - optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
  • - wherein the oxidation colorant preferably has a pH in the range from 8 to 11, in particular in the range from 8.5 to 10.7, particularly preferably in the range from 9 to 10.3, extremely preferably 9.5 to 9.7, in each case measured at a temperature of 22 °C, and
• ii) providing an oxidizing agent preparation (M2) containing 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, of water, furthermore hydrogen peroxide in a total amount of 0.5 to 23% by weight, more preferably 2.5 to 21% by weight, particularly preferably 4 to 20% by weight, very particularly preferably 5 to 18% by weight and extremely preferably 6 to 12% by weight, and having a pH in the range of 2.0 to 6.5, preferably 2.5-5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C, wherein the wt% data in each case refer to the weight of the oxidizing agent preparation (M2), wherein optionally at least one surfactant and/or one oil are contained,
• iii) mixing the cosmetic agent (M1) with the oxidizing agent preparation (M2), preferably in a weight ratio (M1):(M2) in the range from 1:0.8 to 1:2.5, preferably 1:1 to 1:2, immediately thereafter
• iv) applying the mixture obtained in step iii) to the hair and leaving this mixture on the hair for a time of 1 to 60 minutes, preferably 20 to 45 minutes, at room temperature and/or at 30 - 60°C, preferably at 32 - 50°C,
• v) rinsing the hair with water and/or a cleansing composition, and
• vi) if necessary, apply a post-treatment product to the hair and, if necessary, rinse and then dry.

For oxidative hair dyeing processes, the agent according to the invention (M1), which contains one or more oxidation dye precursors and optionally one or more direct dyes, is usually mixed with an aqueous oxidizing agent-containing composition (M2) to form the ready-to-use dye immediately before application to the hair and is then applied to the hair. In most cases, the agent according to the invention (M1) and the oxidizing agent-containing composition (M2) are coordinated with one another in such a way that, with a mixing ratio of 1 to 1, based on parts by weight, the finished application mixture has an initial concentration of hydrogen peroxide of 0.5 - 12% by weight, preferably 2 - 10% by weight, particularly preferably 3 - 6% by weight of hydrogen peroxide (calculated as 100% H ₂ O ₂ ), in each case based on the weight of the application mixture. However, it is equally possible to match the agent according to the invention (M1) and the oxidizing agent-containing composition (M2) to one another in such a way that the concentrations required in the ready-to-use oxidizing colorant (application mixture) are obtained by mixing ratios other than 1:1, for example by a weight-related mixing ratio of 1:2 or 1:3 or even 2:3.

According to the invention, preferred weight-related mixing ratios (M1):(M2) are in the range from 1:0.8 to 1:2.5, particularly preferably in the range from 1:1 to 1:2.

According to the invention, the term "room temperature" refers to the temperature in the room in which a person usually applies a hair dye or lightening agent, i.e. usually a bathroom or a hairdressing salon, in which a temperature in the range of 10 - 29 °C prevails. Leaving the coloring or lightening application mixture in process step iv) in the hair dyeing processes according to the invention or preferred according to the invention can also take place at at least 30 °C, preferably at 30 - 60 °C, particularly preferably at 32 - 50 °C, if the hair is heated, for example, with a heat cap or with a heat lamp.

The oxidation agents used in the color change kits according to the invention and preferred according to the invention as well as in the color change processes according to the invention and preferred according to the invention The composition (M2) contains, based on its weight, 40 - 96 wt. %, preferably 65 - 90 wt. %, particularly preferably 70 - 80 wt. %, of water.

The oxidizing agent preparation (M2) used in color change kits according to the invention and preferred according to the invention and in color change processes according to the invention and preferred according to the invention further contains, in each case based on its weight, 0.5 to 23% by weight, more preferably 2.5 to 21% by weight, particularly preferably 4 to 20% by weight, very particularly preferably 5 to 18% by weight and extremely preferably 6 to 12% by weight, of hydrogen peroxide. To stabilize the hydrogen peroxide, the oxidizing agent preparation (M2) has a pH in the range of 2.0 to 6.5, preferably 2.5 - 5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C.

Color-changing agents preferred according to the invention have a viscosity in the range of 6000 - 15000 mPas, preferably 6500 - 14000 mPas, particularly preferably 7000 - 13000 mPas, extremely preferably 8000 - 12000 mPas, in each case measured at 20°C with a Haake model MVII rheometer at a shear rate of 7.2 revolutions per second.

The ready-to-use color-changing agent, which is obtained by mixing the agent according to the invention (M1) with the oxidizing agent preparation (M2), has a viscosity in the range of 3500 - 8000 mPas, preferably 4000 - 7000 mPas, particularly preferably 4500 - 6500 mPas, extremely preferably 5000 - 6000 mPas, in each case measured at 20°C with a Haake model MVII rheometer at a shear rate of 7.2 revolutions per second. Higher-viscosity application mixtures are applied to the keratin fibers with a brush. Lower-viscosity application mixtures are applied to the keratin fibers using an application bottle.

Oxidative color change processes on keratin fibers usually take place in a neutral to alkaline environment; even a slightly acidic pH value produces acceptable color results. Therefore, the pH value of the agent according to the invention (M1) is in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C.

The ready-to-use color-changing agent obtained by mixing the agent (M1) according to the invention with the oxidizing agent preparation (M2) has a pH in the range of 6.5-10, preferably 7-9.5, particularly preferably 7.5-9, extremely preferably 7.5-8.5, further extremely preferably 7.5-8, in each case measured at a temperature of 22 °C.

Surprisingly, it has been found that an application mixture with a viscosity suitable for application and drip-free retention on the hair is obtained when the agent according to the invention or preferred according to the invention (M1) is mixed with an oxidizing agent preparation (M2) which contains xanthan, preferably 1 to 5% by weight, particularly preferably 1.5 to 4% by weight, extremely preferably 2-3% by weight of xanthan, in each case based on the weight of the oxidizing agent preparation (M2). The consistency of the application mixture achieved in this way leads to optimal application properties, for example for brush application. The application mixtures thus obtained, in particular with weight-related mixing ratios (M1):(M2) in the range from 1:0.8 to 1:2.5, particularly preferably in the range from 1:1 to 1:2, preferably have a viscosity in the range from 3500 - 8000 mPas, preferably 4000 - 7000 mPas, particularly preferably 4500 - 6500 mPas, extremely preferably 5000 - 6000 mPas, in each case measured at 20°C with a Haake model MVII rheometer at a shear rate of 7.2 revolutions per second.

Preferred oxidizing agent preparations (M2) used according to the invention contain at least one surfactant or one emulsifier. Preferred surfactants and emulsifiers in (M2) are selected from anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers and mixtures thereof.

Further oxidizing agent preparations (M2) preferably used according to the invention contain at least one zwitterionic and/or at least one amphoteric surfactant and/or at least one anionic surfactant.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl aminopropyl N,N-dimethylammonium glycinates, for example cocoacyl aminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines, each with 8 to 18 C atoms in the alkyl or acyl group, as well as cocoacyl aminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Amphoteric surfactants are those surface-active compounds which, in addition to a C ₈ -C ₂₄ alkyl or acyl group in the molecule, 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 amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 24 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Suitable anionic surfactants are all anionic surface-active substances suitable for use on the human body that have a water-solubilizing anionic group, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group with about 8 to 30 C atoms, preferably 8 to 24 C atoms in the molecule. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Examples of suitable anionic surfactants are, each in the form of sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts with 2 to 4 C atoms in the alkanol group, linear and branched fatty acids with 8 to 30 C atoms (soaps), polyethoxylated ether carboxylic acids, acyl sarcosides, acyl taurides, acyl isethionates, sulfosuccinic acid mono- and dialkyl esters and sulfosuccinic acid mono-alkylpolyoxyethyl esters with 1 to 6 ethylene oxide groups, linear alkanesulfonates, linear alpha-olefinsulfonates, sulfonates of unsaturated fatty acids with up to 6 double bonds, alpha-sulfofatty acid methyl esters of fatty acids, C ₈ -C ₂₀ alkyl sulfates and C ₈ -C ₂₀ alkyl ether sulfates with up to 15 oxyethyl groups, mixtures of surface-active Hydroxysulfonates, sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers, esters of tartaric acid or citric acid with ethoxylated or propoxylated fatty alcohols, optionally polyethoxylated alkyl and/or alkenyl ether phosphates, sulfated fatty acid alkylene glycol esters, and monoglyceride sulfates and monoglyceride ether sulfates. Preferred anionic surfactants are soaps, C ₈ -C ₂₀ alkyl sulfates, C ₈ -C ₂₀ alkyl ether sulfates and C ₈ -C ₂₀ ether carboxylic acids with 8 to 20 C atoms in the alkyl group and up to 12 ethylene oxide groups in the molecule. Sodium cetearyl sulfate is particularly preferred.

The total amount of surfactant or surfactants in the oxidizing agent preparations (M2) used according to the invention is preferably 0.1 - 5 wt.%, preferably 0.5 - 4 wt.% and particularly preferably 1 - 3.3 wt.%, in each case based on the weight of the oxidizing agent preparation (M2). Other particularly preferably used oxidizing agent preparations (M2) are characterized in that they contain, in each case based on their weight, at least one nonionic surfactant in a total amount of 0.1 - 5 wt.%, preferably 0.5 - 4 wt.% and particularly preferably 1 - 3.3 wt.%.

In a further preferred embodiment of the invention, the oxidizing agent preparation (M2) used according to the invention contains at least one cationic surfactant, preferably in a total amount of 0.05 - 3% by weight, particularly preferably 0.1 - 1.5% by weight, extremely preferably 0.3 - 0.9% by weight, in each case based on the weight of the oxidizing agent preparation (M2). Cationic surfactants are understood to be surfactants, i.e. surface-active compounds, each with one or more positive charges. Cationic surfactants contain exclusively positive charges. These surfactants are usually made up of a hydrophobic part and a hydrophilic head group, whereby the hydrophobic part generally consists of a hydrocarbon framework (e.g. consisting of one or two linear or branched alkyl groups), and the positive charge(s) are located in the hydrophilic head group. Cationic surfactants adsorb at interfaces and aggregate in aqueous solution above the critical micelle formation concentration to form positively charged micelles.

According to the invention, cationic surfactants of the quaternary ammonium compound, esterquat and alkylamidoamine type are preferred. Preferred quaternary ammonium compounds are ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, trialkylmethylammonium chlorides, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. Other preferred quaternary ammonium compounds are tetraalkylammonium salts, such as in particular Quaternium-52, a poly(oxy-1,2- Ethanediyl), ((Octadecylnitrilio)tri-2,1-Ethanediyl)tris(Hydroxy)phosphate (1:1) salt, having the general structural formula (III) where x + y + z = 10

The long alkyl groups of the above-mentioned surfactants preferably have 10 to 22, particularly preferably 12 to 18 carbon atoms. Behenyltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride are particularly preferred, with stearyltrimethylammonium chloride being extremely preferred. Other cationic surfactants suitable according to the invention are quaternized protein hydrolysates. Alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound from this group of substances suitable according to the invention is Tegoamid ^® S 18 (stearamidopropyldimethylamine). Esterquats are substances that contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold under the trademarks Stepantex, Dehyquart and Armocare.

C10-C22 alkyltrimethylammonium chlorides have proven to be particularly suitable in terms of optimal application properties and optimal color results. Particularly preferred oxidizing agent preparations (M2) used according to the invention are therefore characterized in that they contain at least one cationic surfactant in a total amount of 0.05 - 3 wt. %, particularly preferably 0.1 - 1.5 wt. %, extremely preferably 0.3 - 0.9 wt. %, each based on the weight of the oxidizing agent preparation (M2), wherein preferably at least one surfactant selected from C10-C22 alkyltrimethylammonium chlorides, in particular selected from behenyltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride and mixtures of these surfactants, is contained. Extraordinarily preferred oxidizing agent preparations (M2) used according to the invention contain stearyltrimethylammonium chloride in a total amount of 0.05 - 3 wt.%, particularly preferably 0.1 - 1.5 wt.%, extraordinarily preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

Another preferred packaging unit according to the invention (kit of parts) is characterized in that the oxidizing agent preparation (M2) contains at least one cationic surfactant, preferably in a total amount of 0.05 - 3 wt.%, particularly preferably 0.1 - 1.5 wt.%, extremely preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

Another preferred packaging unit according to the invention (kit of parts) is characterized in that the oxidizing agent preparation (M2) contains at least one cationic surfactant, which is preferably selected from stearyltrimethylammonium chloride, in a total amount of 0.05 - 3 wt.%, particularly preferably 0.1 - 1.5 wt.%, extremely preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

A preferred method for oxidative hair coloring according to the invention is characterized in that the oxidizing agent preparation (M2) contains at least one cationic surfactant, preferably in a total amount of 0.05 - 3 wt.%, particularly preferably 0.1 - 1.5 wt.%, extremely preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

Another preferred method according to the invention for the oxidative color change of keratin fibers is characterized in that the oxidizing agent preparation (M2) contains at least one cationic surfactant, which is preferably selected from stearyltrimethylammonium chloride, in a total amount of 0.05 - 3 wt.%, particularly preferably 0.1 - 1.5 wt.%, extremely preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

Surprisingly, it has been found that an application mixture with a viscosity suitable for application and drip-free retention on the hair is obtained when the agent according to the invention or preferred according to the invention (M1) is mixed with an oxidizing agent preparation (M2) which contains at least one oil, preferably at least one oil in a total amount of 0.5-40% by weight, preferably 1-25% by weight, particularly preferably 3-20% by weight, extremely preferably 5-17% by weight, in each case based on the weight of the oxidizing agent preparation (M2). The consistency of the application mixture thus achieved leads to optimal application properties, for example for brush application. The application mixtures thus obtained, in particular with weight-related mixing ratios (M1):(M2) in the range from 1:0.8 to 1:2.5, particularly preferably in the range from 1:1 to 1:2, preferably have a viscosity in the range from 3500 - 8000 mPas, preferably 4000 - 7000 mPas, particularly preferably 4500 - 6500 mPas, extremely preferably 5000 - 6000 mPas, in each case measured at 20°C with a Haake model MVII rheometer at a shear rate of 7.2 revolutions per second.

Further oxidizing agent preparations (M2) preferably used according to the invention contain at least one oil. The at least one oil is preferably selected according to the invention from mineral oils, branched fatty alcohols with 8 - 24 carbon atoms, dialkyl ethers with 6 to 18 carbon atoms in the alkyl groups, esters of linear or branched saturated or unsaturated fatty alcohols with 2 - 30 carbon atoms with linear or branched saturated or unsaturated fatty acids with 2 - 30 carbon atoms, which may be hydroxylated, and mixtures of the aforementioned substances. Mineral oil is particularly preferred.

According to the invention, preferred branched fatty alcohols with 8 - 24 carbon atoms are 2-octyl-1-dodecanol, 2-hexyl-1-decanol, 2-ethyl-1-hexanol and isostearyl alcohol and mixtures thereof. 2-octyl-1-dodecanol is particularly preferred.

Dialkyl ethers with 6 to 18 C atoms in the alkyl groups that are preferred according to the invention are di-n-alkyl ethers with a total of 12 to 36 C atoms, in particular 16 to 24 C atoms in the molecule, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, di-n-octadecyl 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. Dialkyl ethers that are also preferred are those with branched alkyl groups, each with 6 to 18 C atoms, in particular with alkyl groups that are substituted in the 2-position with an ethyl group. Preferred branched-chain dialkyl ethers with 6 to 18 C atoms in the alkyl group are selected from di-(2-ethylhexyl) ether and di-(2-ethyldecyl) ether. Particularly preferred is di-n-octyl ether (INCI: dicaprylyl ether), which is commercially available, for example, under the name Cetiol ^® OE from BASF.

According to the invention, preferred esters of linear or branched saturated or unsaturated fatty alcohols having 2 - 30 carbon atoms with linear or branched saturated or unsaturated fatty acids having 2 - 30 carbon atoms, which may be hydroxylated, are selected from 2-hexyldecyl stearate (Eutanol ^® G 16 S), 2-hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl palmitate (Cegesoft ^® C 24) and 2-ethylhexyl stearate (Cetiol ^® 868). Also preferred are isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl isostearate, isopropyl oleate, isooctyl stearate, isononyl stearate, isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate, cetearyl isononanoate, 2-ethylhexyl laurate, 2-ethylhexyl isostearate, 2-ethylhexyl cocoate, 2-octyldodecyl palmitate, butyloctanoic acid 2-butyloctanoate, diisotridecyl acetate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, ethylene glycol dioleate and ethylene glycol dipalmitate.

Kits, uses and methods preferred according to the invention are characterized in that the composition (M2) used for their preparation contains - based on its weight - at least one oil in a total amount of 0.5-40 wt.%, preferably 1-25 wt.%, particularly preferably 3-20 wt.%, extremely preferably 5-17 wt.%.

Further kits, uses and methods preferred according to the invention are characterized in that the composition (M2) used for their preparation contains - based on its weight - at least 0.5-40 wt. %, preferably 1-25 wt. %, particularly preferably 3-20 wt. %, extremely preferably 5-17 wt. %, mineral oil.

The oxidative color-changing agent (M1) according to the invention is mixed with an oxidizing agent preparation (M2) to form a ready-to-use agent which contains at least one oxidizing agent. Preferred oxidizing agents are selected from peroxo compounds, preferably selected from hydrogen peroxide, solid addition compounds of hydrogen peroxide to inorganic or organic compounds. compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, further selected from diammonium peroxodisulfate (also referred to as ammonium persulfate), disodium peroxodisulfate (also referred to as sodium persulfate) and dipotassium peroxodisulfate (also referred to as potassium persulfate) and from mixtures of these oxidizing agents. Oxidizing agents used particularly preferably according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; 6 to 12 percent by weight solutions in water are preferably used. Kits, uses and methods preferred according to the invention are characterized in that the composition (M2) used for their preparation contains - based on its weight - 1 - 24 wt.%, preferably 4 - 10 wt.%, particularly preferably 3 - 6 wt.% hydrogen peroxide (calculated as 100% H ₂ O ₂ ).

For processes for oxidative color change, the agent according to the invention (M1), which optionally contains one or more oxidation dye precursors and optionally one or more direct dyes, is usually mixed with an aqueous oxidizing agent-containing composition (M2) to form the ready-to-use agent shortly before application to the hair and then applied to the hair. The color change agent according to the invention (M1) and the oxidizing agent-containing composition (M2) are usually coordinated with one another in such a way that, with a mixing ratio of 1 to 1, based on parts by weight, the ready-to-use agent has an initial concentration of hydrogen peroxide of 0.5 - 12% by weight, preferably 2 - 10% by weight, particularly preferably 3 - 6% by weight of hydrogen peroxide (calculated as 100% H ₂ O ₂ ), based on the weight of the ready-to-use agent. However, it is just as possible to match the colorant (M1) according to the invention and the oxidizing agent-containing composition (M2) to one another in such a way that the concentrations required in the ready-to-use agent are obtained by mixing ratios other than 1:1, for example by a weight-related mixing ratio of 1:2 or 1:3 or even 2:3. Weight-related mixing ratios (M1):(M2) preferred according to the invention are in the range from 1:0.8 to 1:2.5, particularly preferably in the range from 1:1 to 1:2.

The ready-to-use color-changing agent obtained by mixing the agent (M1) according to the invention with the oxidizing agent preparation (M2) preferably has a pH in the range of 6.5-10, more preferably 7-9.5, particularly preferably 7.5-9, extremely preferably 7.5-8.5, further extremely preferably 7.5-8, in each case measured at a temperature of 22 °C.

For a coloring that requires a strong lightening of very dark hair, the use of hydrogen peroxide or its adducts with organic or inorganic compounds is often not sufficient. In these cases, a combination of hydrogen peroxide and peroxodisulfate salts (persulfate salts) is usually used. Preferred persulfate salts are ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, and mixtures thereof.

The at least one persulfate salt is preferably contained in a total amount of 0.1 to 25% by weight, particularly preferably in a total amount of 1 to 15% by weight, based on the weight of the ready-to-use agent.

With regard to further preferred embodiments of the method according to the invention, what has been said regarding the agents according to the invention and the oxidizing agent preparations used according to the invention applies mutatis mutandis.

Examples

1. The following dyes or compositions (M1) were prepared (gels, all amounts in wt.%):

inventive coloring gel (M1-1) Glycerine 5,000 2-Phenoxyethanol 1,000 Xanthan Gum 0.800 Sodium hyaluronate 0.030 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.800 Steareth-100 0.300 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.500 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.500 Potassium hydroxide 0.300 Succinic acid 0.400 L-Arginine 0.100 Lysine hydrochloride 0.100 Trisodium ethylenediamine disuccinate 0.050 Potassium dihydrogen phosphate 0.300 2-Methyl-p-phenylenediamine sulfate 0.100 2-methylresorcinol 0.045 2-Amino-3-hydroxypyridine 0.007 3-Aminophenol 0.005 2-Aminoethanol (Monoethanolamine) 0.160 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 1,000 Perfume 0.500 Water up to 100,00
Coloring gel according to the invention (M1-2) Glycerine 5,000 Xanthan Gum 0.900 Sodium hyaluronate 0.050 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.400 Steareth-100 0.500 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.400 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.400 Potassium hydroxide 0.200 Tetrasodium EDTA 0.250 Potassium dihydrogen phosphate 0.300 2-Methoxymethyl-p-phenylenediamine sulfate 0.150 2-methylresorcinol 0.045 2-Amino-3-hydroxypyridine 0.007 3-Aminophenol 0.020 2-Aminoethanol (Monoethanolamine) 0.300 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 0.500 Perfume 0.500 Water up to 100,00
inventive coloring gel (M1-3) Glycerine 7,500 Xanthan Gum 0.900 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.800 Steareth-100 1,000 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.800 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.800 Potassium hydroxide 0.300 Succinic acid 0.200 Trisodium ethylenediamine disuccinate 0.300 Potassium dihydrogen phosphate 0.300 2-beta-hydroxyethyl-p-phenylenediamine sulfate 0.200 2-methylresorcinol 0.045 2-Amino-3-hydroxypyridine 0.050 3-Aminophenol 0.005 2-Aminoethanol (Monoethanolamine) 0.400 Sodium sulphite 0.300 Perfume 0.500 Water up to 100,00
inventive coloring gel (M1-4) Glycerine 6,000 2-Phenoxyethanol 0.500 Xanthan Gum 0.800 Sodium hyaluronate 0.030 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.800 Steareth-100 0.300 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.500 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.500 Potassium hydroxide 0.300 Succinic acid 0.400 L-Arginine 0.100 Lysine hydrochloride 0.100 Trisodium ethylenediamine disuccinate 0.100 Potassium dihydrogen phosphate 0.300 p-Phenylenediamine 0.350 p-Aminophenol 0.150 N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate 0.450 4-Amino-3-methylphenol (4-amino-m-cresol) 0.500 m-Aminophenol 0.100 Hydroxyethyl-3,4-methylenedioxyaniline HCl 0.500 4-Amino-2-hydroxytoluen 0.100 2,4-Diaminophenoxyethanol HCl 0.010 1-Phenyl-3-methyl-5-pyrazolone 0.180 2-Aminoethanol (Monoethanolamine) 0.160 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 1,000 Perfume 0.500 Water up to 100,00
inventive coloring gel (M1-5) Glycerine 6,000 2-Phenoxyethanol 0.500 Xanthan Gum 0.800 Sodium hyaluronate 0.030 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.800 Steareth-100 0.300 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.500 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.500 Potassium hydroxide 0.300 Succinic acid 0.400 L-Arginine 0.100 Lysine hydrochloride 0.100 Trisodium ethylenediamine disuccinate 0.100 Potassium dihydrogen phosphate 0.300 1-Hydroxyethyl 4,5-diaminopyrazole sulfate 0.780 2-Methoxymethyl-p-phenylenediamine 1,800 m-Aminophenol 0.360 Hydroxyethyl-3,4-methylenedioxyaniline HCl 1,010 1-Naphthol 1,030 2-Aminoethanol (Monoethanolamine) 0.300 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 1,000 Perfume 0.500 Water up to 100,00
inventive coloring gel (M1-6) Glycerine 6,000 2-Phenoxyethanol 0.500 Xanthan Gum 0.800 Sodium hyaluronate 0.030 iota-Carrageenan Chondrus Crispus Powder (Carrageenan) 0.800 Steareth-100 0.300 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.500 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.500 Potassium hydroxide 0.300 Succinic acid 0.400 L-Arginine 0.100 Lysine hydrochloride 0.100 Trisodium ethylenediamine disuccinate 0.100 Potassium dihydrogen phosphate 0.300 2-(2,5-diaminophenyl)ethanol sulfate 1,546 1-Hydroxyethyl 4,5-diaminopyrazole sulfate 0.453 m-Aminophenol 0.002 2,7-Naphthalenediol 0.145 4-Amino-2-hydroxytoluen 0.257 Hydroxyethyl-3,4-methylenedioxyaniline HCl 1,100 2-Aminoethanol (Monoethanolamine) 0.300 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 1,000 Perfume 0.500 Water up to 100,00

The following oxidation compositions (M2) were prepared (all amounts in wt%):

Developer emulsion (M2-1) (9 wt.% H ₂ O ₂ ) mineral oil 17,00 Hydrogen peroxide 9.00 Cetearyl alcohol 3.50 PEG-40 Castor Oil 0.70 Sodium cetearyl sulfate 0.40 Etidronic acid 0.20 Potassium hydroxide 0.12 Disodium pyrophosphate 0.10 2,6-Dicarboxypyridine 0.10 Sodium benzoate 0.04 Sodium sulfate 0.01 Sodium chloride 0.01 Water 68.82
Developer emulsion (M2-2) (12 wt.% H ₂ O ₂ ) mineral oil 17,00 Hydrogen peroxide 12,00 Cetearyl alcohol 3.50 PEG-40 Castor Oil 0.70 Sodium cetearyl sulfate 0.40 Etidronic acid 0.20 Potassium hydroxide 0.12 Disodium pyrophosphate 0.10 2,6-Dicarboxypyridine 0.10 Sodium benzoate 0.04 Sodium sulfate 0.01 Sodium chloride 0.01 Water 65.82
Developer emulsion (M2-3) (4 wt.% H ₂ O ₂ ) Developers 4% Sodium benzoate 0.04 2,6-Dicarboxypyridine 0.10 Disodium pyrophosphate 0.10 Potassium hydroxide 0.15 Propanediol-1,2 1.50 Etidronic acid 0.24 Paraffinum Liquidum 0.30 Isopropyl alcohol 0.08 Steartrimonium Chloride 0.31 Ceteareth-20 1.00 Cetearyl Alcohol 3.40 Hydrogen peroxide 4.00 Perfume 0.10 Water, demineralized 88.68

2. Coloring

To produce ready-to-use oxidative colorants, one of the agents according to the invention (M1-1), (M1-2), (M1-3), (M1-4), (M1-5) or (M1-6) was mixed in a weight ratio of 1:1 with one of the oxidizing agent preparations (M2-1) or (M2-2) or (M2-3).

The oxidative dyes produced in this way were each applied in a defined amount (4 g oxidative dye per 1 g yak hair) to strands of yak hair lying down (12 strands per oxidative dye) and left on the hair strands for a period of 30 minutes at 32 °C. The remaining agents were then rinsed out of the hair strands with lukewarm water for 2 minutes, the strands were first dried with a towel and then blow-dried.

Intensely colored strands were obtained in each case.

When the above-mentioned dyes according to the invention were applied to the hair of test subjects, the products could be easily made homogeneous by mixing components (M1) and (M2) by hand, then effortlessly applied to the hair to be dyed and remained there for the 30-minute exposure time without dripping. Here too, intensive and homogeneous dyes were obtained along the entire length of the keratin fibers.

Non-inventive coloring gel (M1-7) Propane-1,2-diol 2,000 Xanthan Gum 0.900 Carbomer 0.900 C8-10 alkyl glucosides (caprylyl/capryl glucoside) 0.600 C10-16-alkyl polyglucoside DP 1.6 (coco-glucoside) 0.600 Potassium hydroxide 0.300 Succinic acid 0.400 L-Arginine 0.100 Lysine hydrochloride 0.100 Trisodium ethylenediamine disuccinate 0.050 Potassium dihydrogen phosphate 0.300 2-Methyl-p-phenylenediamine sulfate 0.100 2-methylresorcinol 0.045 2-Amino-3-hydroxypyridine 0.007 3-Aminophenol 0.005 2-Aminoethanol (Monoethanolamine) 1,500 Sodium sulphite 0.300 PPG-1-PEG-9 Lauryl Glycol Ether 0.500 Perfume 0.500 Water up to 100,00

To produce ready-to-use oxidative colorants, the non-inventive agent (M1-7) was mixed in a weight ratio of 1:1 with one of the oxidizing agent preparations (M2-1) or (M2-2) or (M2-3).

The oxidative dyes produced in this way were each applied in a defined amount (4 g oxidative dye per 1 g yak hair) to strands of yak hair lying down (12 strands per oxidative dye) and left on the hair strands for a period of 30 minutes at 32 °C. The remaining agents were then rinsed out of the hair strands with lukewarm water for 2 minutes, the strands were first dried with a towel and then blow-dried.

Intensely colored strands were obtained in each case.

When the above-mentioned dyes according to the invention were applied to the hair of test subjects, the products could be easily made homogeneous by mixing components (M1) and (M2) by hand. The subsequent application to the hair to be dyed was more difficult than with the dyes according to the invention because the gels formed were less stiff and adhered less well to the strands.

In addition, the dyes began to drip down from the hair about 10 minutes after application, and this increased during the 30-minute exposure time. The intensity and homogeneity of the dyes along the entire length of the keratin fibers were poorer than the dyes obtained with the dyes according to the invention.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions.

Cited patent literature

• DE 102017223233 A1 [0010, 0015]
• FR 2977157 B1 [0010]
• WO 2021026572 A1 [0010]
• WO 2016012327 A2 [0068]

Cited non-patent literature

• DIN EN ISO 7027 (C2) 2016-11 [0068]

Claims (15)

Agent for the oxidative color change of keratin fibers, in particular human hair, containing, in each case based on its weight, - more than 80 wt.% to 99 wt.% water, - 0.1 to 1.5 wt.% iota-carrageenan, - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt, - at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3 wt.%, - at least one alkalizing agent, - zero to less than 0.1 wt.% of peroxide compounds, - optionally at least one oxidation dye precursor of the developer type and at least one Oxidation dye precursor of the coupler type, wherein the agent has a pH in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C. Means according to Claim 1 , characterized in that the total content of surfactants is 0.1 to 4 wt.%, preferably 0.5 to 3 wt.%, particularly preferably 1 to 2.6 wt.%, in each case based on the weight of the agent. Means according to Claim 1 or 2 , characterized in that only non-ionic surfactants are contained. Remedy according to one of the Claims 1 until 3 , characterized in that it additionally contains 0.05 to 1.5 wt.% xanthan, based on the weight of the agent. Remedy according to one of the Claims 1 until 4 , characterized in that it additionally contains 0.005 to 0.05 wt.% hyaluronic acid or at least one salt of hyaluronic acid, based on the weight of the agent. Remedy according to one of the Claims 1 until 5 , characterized in that it additionally contains at least one polyol different from compounds of the formula R ⁴ O-[G] _p , selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain can be interrupted by one or more oxygen atoms. Means according to Claim 6 , characterized in that the at least one polyol which is different from compounds of the formula R ⁴ O-[G] _p is contained in a total amount of 0.5 - 20 wt.%, preferably 1 - 15 wt.%, particularly preferably 3 - 10 wt.%, extremely preferably 5 - 8 wt.%, in each case based on the weight of the agent. Remedy according to one of the Claims 1 until 7 , characterized in that fatty substances are contained in a total amount of zero to 2 wt.%, preferably 0.01 - 1.5 wt.%, particularly preferably 0.1 - 1.0 wt.%, extremely preferably 0.2 - 0.5 wt.%, in each case based on the weight of the agent. Remedy according to one of the Claims 1 - 8 , characterized in that the at least one alkalizing agent is selected from alkanolamines, alkali hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali phosphates and dialkali monohydrogen phosphates and mixtures of these substances. Remedy according to one of the Claims 1 until 9 , characterized in that it contains no ammonia and no ammonium hydroxide. Remedy according to one of the Claims 1 until 10 , characterized in that no ionic surfactant is included. Remedy according to one of the Claims 1 until 11 , characterized in that no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained. Use of a product according to one of the Claims 1 until 12 for the oxidative color change of keratin fibers, especially human hair. A method for oxidative color change, comprising the following method steps: i) providing a cosmetic agent (M1) for oxidative color change of keratin fibers according to one of the Claims 1 until 12 , containing - more than 80 wt.% to 99 wt.% water, - 0.1 to 1.5 wt.% iota-carrageenan, - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt, - at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3 wt.%, - at least one alkalizing agent, - zero to less than 0.1 wt.% of peroxide compounds, - optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, - wherein the agent has a pH in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C, and ii) providing an oxidizing agent preparation (M2) containing 40 - 96 wt.%, preferably 65 - 90 wt.%, particularly preferably 70 - 80 wt.%, water, furthermore hydrogen peroxide in a total amount of 0.5 to 23 wt.%, more preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, very particularly preferably 5 to 18 wt.% and extremely preferably 6 to 12 wt.%, and a pH in the range from 2.0 to 6.5, preferably 2.5 - 5.5, particularly preferably 2.8 to 4.5, each measured at 20 °C, wherein the wt.% figures refer in each case to the weight of the Oxidizing agent preparation (M2), optionally containing at least one oil and/or at least one surfactant, iii) mixing the cosmetic agent (M1) with the oxidizing agent preparation (M2), preferably in a weight ratio (M1):(M2) in the range from 1:0.8 to 1:2.5, preferably 1:1 to 1:2, immediately thereafter iv) applying the mixture obtained in step iii) to the hair and leaving this mixture on the hair for a time of 1 to 60 minutes, preferably from 20 to 45 minutes, at room temperature and/or at 30 - 60°C, preferably at 32 - 50°C, v) rinsing the hair with water and/or a cleansing composition, and vi) optionally applying an aftertreatment agent to the hair and optionally rinsing, then drying. Packaging unit (kit of parts) which - packaged separately - comprises the following: a) at least one container (C1) containing an agent for the oxidative colour change of keratin fibres according to one of the Claims 1 until 12 , containing: - more than 80 wt.% to 99 wt.% water, - 0.1 to 1.5 wt.% iota-carrageenan, - 0.05 to 0.5 wt.% potassium ions in the form of at least one potassium salt, - at least one nonionic surfactant selected from alkyl mono- and oligoglycosides of the formula R ⁴ O-[G] _p , in which R ⁴ is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a positive rational number in the range from 1 to 6, in a total amount of 0.1 to less than 3 wt.%, - at least one alkalizing agent, - zero to less than 0.1 wt.% of peroxide compounds, - optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, - wherein the agent has a pH in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range from 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C, and b) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40 - 96 wt.%, preferably 65 - 90 wt.%, particularly preferably 70 - 80 wt.%, water, furthermore hydrogen peroxide in a total amount of 0.5 to 23 wt.%, more preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, very particularly preferably 5 to 18 wt.% and extremely preferably 6 to 12 wt.%, and has a pH in the range from 2.0 to 6.5, preferably 2.5 - 5.5, particularly preferably 2.8 to 4.5, each measured at 20 °C, wherein the wt.% data refer in each case to the Weight of Oxi ation agent preparation (M2), optionally containing at least one oil and/or at least one surfactant.