DE102023205848A1 - Oil-in-water emulsion for oxidative color change of keratin fibers with improved temperature stability - Google Patents

Abstract

The present invention relates to an agent for oxidative color change for keratin fibers in the form of an oil-in-water emulsion with improved stability, in particular improved temperature stability to higher temperatures, which also has optimized application properties and/or improved coloring performance, as well as a method for oxidative color change using the aforementioned oxidative color change agent in emulsion form.

Description

The present invention relates to an agent for oxidative color change for keratin fibers in the form of an oil-in-water emulsion with improved stability, in particular improved temperature stability to higher temperatures, which also has optimized application properties and/or improved coloring performance, as well as a method for oxidative color change using the aforementioned oxidative color change agent in emulsion form.
So-called oxidation dyes are used for permanent, intensive coloring with corresponding fastness properties. Oxidative dyes 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 another 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. The coupler components used are usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. 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 has disadvantages for the user due to its smell and potential for irritation to the skin and mucous membranes. The alkalizing agent causes the keratin fibers to swell, allowing 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 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 more suppleness and elasticity. The color fastness properties are also impaired by the roughened fiber surface.
Fats or oils are often used in these products to reduce hair damage caused by an alkaline oxidative color-changing agent. The content of oil and/or fat components can also reduce the release of ammonia after application to the hair when ammonium hydroxide and ammonium salts are used as alkalizing agents. The balancing ability of the hair dye can also be improved by a content of oil and/or fat components, so that the resulting color is less selective, i.e. it absorbs to approximately the same extent on both the damaged and undamaged parts of the keratin fibers.

Many of the oxidation dye precursors are aromatic amines. Some of these aromatic amines are preferably used in the form of their salts, especially in the form of sulfates and hydrogen sulfates, as these are more stable and easier to handle than the free amines. In the alkaline medium of the dye, the free amines are released from the salt and form the dyes. The oxidation dye precursors in salt form introduce an increased salt load into the dye component. This is particularly true for darker shades, which contain a higher overall concentration of oxidation dye precursors. Dye components that are in emulsion form are often less stable in storage due to this high salt concentration and tend to separate the oil and water phases over the course of storage. This phase separation is accelerated by increasing the storage temperature. However, thermal stability is essential for a mass product in emulsion form, as the product can be exposed to large temperature fluctuations during transport from production via various intermediate storage facilities to the point of sale in online or stationary retail. Both high and very low temperatures can be detrimental to emulsion stability. However, high temperatures of 50°C and more, which typically occur during ocean transport with container ships, are particularly problematic.
In the prior art, this problem was often addressed by adding a polymeric gelling agent, for example a polyacrylate. In the alkaline medium of water-containing compositions, such polymers form a gel network in the aqueous phase, which increases the viscosity of the aqueous phase. This stabilizes the dispersion of the emulsified oil phase droplets or fat phase particles. For ecological reasons, it is advisable to avoid polyacrylates and other polymer thickeners that are synthesized from petrochemical raw materials and/or that can be considered as so-called microplastics.
However, replacing petrochemically based synthetic polymers with natural or biogenic gelling agents, which may be chemically or physically modified, is not trivial. For example, the naturally based gelling agent sodium carboxymethylcellulose, also known as cellulose gum, provides insufficient emulsion stability in the alkaline pH ranges required for hair dyes and bleaches, especially under prolonged thermal stress.

The polymer sodium carboxymethylcellulose itself is also broken down in an aqueous alkaline medium when exposed to temperatures above 50°C for a long period of time. This is not a problem for the formulation of water-free bleaching powders and bleaching pastes, which is why sodium carboxymethylcellulose is used in many such products. However, sodium carboxymethylcellulose is unsuitable for the present highly water-containing, alkaline emulsions. Therefore, special efforts are being made to develop high-performance oxidative color-changing agents, in particular agents for lightening and/or coloring keratin fibers, which achieve good coloring and lightening results and have a high emulsion stability, especially with regard to thermal stress.
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. This lightens or bleaches the keratin fibers. 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.
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 emulsion stability, but also 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. The stabilizers should not impair the coloring properties, in particular with regard to color intensity and balancing ability.

State of the art

The use of iota-carrageenan or alginic acid in the form of their salts with polyvalent ions in oxidative hair color change was known from WO2017108364A1 This publication teaches the use of iota-carrageenan or alginic acid in the form of calcium salts as a release film, for example in the sense of a highlighting film. WO 2020234196A1 teaches oil-in-water macroemulsions that contain a hydrophobic active ingredient in the oil phase and are stabilized with a polymeric stabilizer. The list of polymeric stabilizers non-specifically mentions both synthetic polymers, such as polyacrylate and polymethacrylate thickeners, as well as natural and modified natural polymers, such as xanthan gum, gellan gum, guar gum, alginic acid, alginate, agar-agar, carrageenan, welan gum, locust bean gum, tragacanth, gum arabic, pectins, polyoses, starch, dextrin, gelatin, casein, modified starches and modified celluloses and mixtures thereof. In the examples of WO2020234196A1 Stable results have only been proven for the commercial products Vivapur CS Tex Sun and Vivapur MCG 811 F. Vivapur is a mixture of microcrystalline cellulose and cellulose gum, also known as sodium carboxymethylcellulose. This polymer is unsuitable for solving the problem according to the invention due to its lack of temperature stability in alkaline media.

It has now been found that an oxidative color-changing agent based on an oil-in-water emulsion thickened with iota-carrageenan or alginic acid has excellent thermal stability properties, so that the use of petrochemical-based thickeners and the use of microplastics can be dispensed with.

1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide,
3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator,
4. d) mindestens ein Alkalisierungsmittel,
5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,

wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist,
und
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, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, the following components:

1. a) 40 wt.% to 85 wt.% water,
2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides,
3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier,
4. d) at least one alkalizing agent,
5. e) zero to less than 0.1% by weight of peroxide compounds,
6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,

which does not contain any polymer or copolymer with acrylate, methacrylate or vinyl-containing monomers and no polyurethane,
and
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, 40 wt.% to 85 wt.%, preferably 45 - 75 wt.%, particularly preferably 50 - 70 wt.%, extremely preferably 55 - 65 wt.% water.
The agent according to the invention is an oil-in-water emulsion which is thickened and stabilized with at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides. The agent according to the invention also represents the alkalizing component of a two-part oxidative coloring 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 an oil-in-water emulsion thickened with iota-carrageenan or alginic acid, which is intended as an alkalizing component for an oxidative dye or brightening agent, has excellent thermal stability, especially under prolonged thermal stress and especially at higher salt concentrations, which may be associated with the addition of oxidation dye precursors. The oil-in-water emulsion thickened with iota-carrageenan or alginic acid tolerates the salt load without any loss of viscosity stability.

A preferred embodiment of the agent according to the invention is characterized in that the at least one polysaccharide selected from iota-carrageenan and alginic acid and the mixtures of these polysaccharides is contained in a total amount of 0.05 to 2.0 wt.%, preferably 0.1 to 1.5 wt.%, particularly preferably 0.2 to 1.2 wt.%, extremely preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent.
According to the invention, iota-carrageenan is extremely preferred, particularly preferably in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.2% by weight, extremely preferably 0.5 to 1.0% by weight, in each case based on the weight of the agent.
It is particularly advantageous that iota-carrageenan is introduced via the melted oil phase or via the hot aqueous phase during emulsion preparation to produce the emulsions according to the invention. The temperatures of the oil phase and the aqueous phase are in the range of 50-95°C, preferably in the range of 65-85°C, before mixing and emulsification.

The thickening of the iota-carrageenan or the alginic acid can be enhanced in the presence of at least one salt selected from potassium and calcium salts with a water solubility at 20°C of at least 500 mg/l. However, no uniform results could be determined for the inventive effect of temperature stabilization for the addition of a potassium or calcium salt.
As an optional ingredient, the agent according to the invention contains, in each case based on its weight, at least one potassium salt in a total amount of 0.05 to 0.5% by weight. Other agents preferred according to the invention contain at least one potassium salt in a total amount of 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, in each case based on the weight of the agent. Suitable potassium salts are selected from potassium stearate, 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.
The calcium chloride which is particularly preferred according to the invention has a water solubility of 740 g/l at 20°C. Other calcium salts which are particularly preferred according to the invention are selected from calcium acetate (water solubility 374 g/l), calcium lactate, calcium gluconate, calcium gluconate lactate.
Particularly preferably, the agent contains at least one salt selected from calcium chloride, calcium chloride, calcium lactate, calcium gluconate and calcium gluconate lactate and mixtures thereof in a total amount of 0.1 - 5 wt.%, particularly preferably 0.2 - 3 wt.%, extremely preferably 0.5 - 2.5 wt.%, in each case based on the weight of the agent (M1).

Another obligatory component of the agents according to the invention and those preferred according to the invention is a content of at least one non-ionic water-in-oil emulsifier in a total amount of 1-30% by weight, preferably 2-25% by weight, particularly preferably 5-20% by weight, extremely preferably 10-20% by weight, in each case based on the weight of the agent. Such water-in-oil emulsifiers are poorly or even not at all water-soluble and therefore at least partially form the emulsified oil or fat phase of the oil-in-water emulsion according to the invention. Other agents preferred according to the invention are characterized in that the at least one non-ionic water-in-oil emulsifier has an HLB value greater than 1.0 and less than or equal to 7.0.

1. i. linearen, gesättigten C₁₂ - C₃₀-Alkanolen,
2. ii. Ethylenglycolmono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
3. iii. Glycerinmono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
4. iv. Propylenglycolmono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
5. v. Sorbitanmono-, -di- und -triestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
6. vi. Pentaerythritylmono-, -di-, -tri- und -tetraestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
7. vii. Methylglucosemono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
8. viii. Glycerinmonoethern gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8 - 30, insbesondere 12 - 18 Kohlenstoffatomen,
9. ix. Partialestern von Polyglycerinen mit n = 2 bis 10 Glycerineinheiten und mit 1 bis 5 gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls hydroxylierten C₈ - C₃₀-Fettsäureresten verestert, die bevorzugt einen HLB-Wert von kleiner/gleich 7 aufweisen,
10. x. sowie Mischungen der vorgenannten Substanzen.

Nonionic water-in-oil emulsifiers preferred according to the invention, which preferably have an HLB value greater than 1.0 and less than or equal to 7.0, are selected from

1. i. linear, saturated C ₁₂ - C ₃₀ alkanols,
2. ii. Ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
3. iii. Glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
4. iv. Propylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
5. v. Sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
6. vi. Pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
7. vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
8. viii. Glycerol monoethers of saturated and/or unsaturated, branched and/or unbranched alcohols with a chain length of 8 - 30, in particular 12 - 18 carbon atoms,
9. ix. Partial esters of polyglycerols with n = 2 to 10 glycerol units and esterified with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ - C ₃₀ fatty acid residues, which preferably have an HLB value of less than or equal to 7,
10. x. and mixtures of the aforementioned substances.

• - lineare, gesättigte Alkanole mit 12 - 30 Kohlenstoffatomen, insbesondere mit 16 - 22 Kohlenstoffatomen, insbesondere Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol oder Gemische dieser Alkohole, wie sie bei der technischen Hydrierung von pflanzlichen und tierischen Fettsäuren erhältlich sind,
• - Ester und insbesondere Partialester aus einem Polyol mit 2 - 6 C-Atomen und linearen oder verzweigten, gesättigten oder ungesättigten Fettsäuren mit 12 - 30, insbesondere 14 - 22 C-Atomen, die hydroxyliert sein können. Solche Ester oder Partialester sind z. B. die Mono- und Diester von Glycerin oder Ethylenglycol oder die Monoester von Propylenglycol mit linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, insbesondere diejenigen mit Palmitin- und Stearinsäure, die Sorbitanmono-, -di- oder -triester von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, insbesondere diejenigen von Myristinsäure, Palmitinsäure, Stearinsäure oder von Mischungen dieser Fettsäuren, die Pentaerythritylmono-, -di-, -tri- und -tetraester und die Methylglucosemono- und -diester von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, wovon besonders bevorzugt sind die Mono-, Di-, Tri- und Tetraester von Pentaerythrit mit linearen gesättigten Fettsäuren mit 12 - 30, insbesondere 14 - 22 Kohlenstoffatomen, die hydroxyliert sein können, sowie Mischungen hiervon. Erfindungsgemäß besonders bevorzugt sind die Mono- und Diester. Erfindungsgemäß bevorzugte C₁₂-C₃₀-Fettsäurereste sind ausgewählt aus Laurinsäure-, Myristinsäure-, Palmitinsäure-, Stearinsäure-, Arachinsäure- und Behensäure-Resten; besonders bevorzugt ist der Stearinsäurerest. Weitere erfindungsgemäß besonders bevorzugte nichtionische Wasser-in-Öl-Emulgatoren, bevorzugt mit einem HLB-Wert größer 1,0 und kleiner/gleich 7,0, sind ausgewählt aus Pentaerythritylmonostearat, Pentaerythrityldistearat, Pentaerythrityltristearat, Pentaerythrityltetrastearat, Ethylenglycolmonostearat, Ethylenglycoldistearat und Mischungen hiervon;
• - Glycerinmonoether gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8 - 30, insbesondere 12 - 18 Kohlenstoffatomen,
• - Partialester von Polyglycerinen mit n = 2 bis 10 Glycerineinheiten und mit 1 bis 5 gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls hydroxylierten C₈ - C₃₀-Fettsäureresten verestert, sofern sie einen HLB-Wert von kleiner/gleich als 7 aufweisen,
• - sowie Mischungen der vorgenannten Substanzen.

Particularly preferred nonionic water-in-oil emulsifiers according to the invention, which preferably have an HLB value greater than 1.0 and less than or equal to 7.0, are:

• - linear, saturated alkanols with 12 - 30 carbon atoms, in particular with 16 - 22 carbon atoms, in particular myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol or mixtures of these alcohols, as are obtainable from the technical hydrogenation of vegetable and animal fatty acids,
• - Esters and in particular partial esters of a polyol with 2 - 6 C atoms and linear or branched, saturated or unsaturated fatty acids with 12 - 30, in particular 14 - 22 C atoms, which may be hydroxylated. Such esters or partial esters are, for example, the mono- and diesters of glycerol or ethylene glycol or the monoesters of propylene glycol with linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, in particular those with palmitic and stearic acid, the sorbitan mono-, di- or triesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, in particular those of myristic acid, palmitic acid, stearic acid or mixtures of these fatty acids, the pentaerythrityl mono-, di-, tri- and tetraesters and the methylglucose mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, of which particularly preferred are the mono-, di-, tri- and tetraesters of pentaerythritol with linear saturated fatty acids with 12 - 30, in particular 14 - 22 carbon atoms, which may be hydroxylated and mixtures thereof. Particularly preferred according to the invention are the mono- and diesters. C ₁₂ -C ₃₀ fatty acid residues preferred according to the invention are selected from lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid residues; the stearic acid residue is particularly preferred. Further nonionic water-in-oil emulsifiers particularly preferred according to the invention, preferably with an HLB value greater than 1.0 and less than or equal to 7.0, are selected from pentaerythrityl monostearate, pentaerythrityl distearate, pentaerythrityl tristearate, pentaerythrityl tetrastearate, ethylene glycol monostearate, ethylene glycol distearate and mixtures thereof;
• - Glycerol monoethers of saturated and/or unsaturated, branched and/or unbranched alcohols with a chain length of 8 - 30, in particular 12 - 18 carbon atoms,
• - Partial esters of polyglycerols with n = 2 to 10 glycerol units and esterified with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ - C ₃₀ fatty acid residues, provided they have an HLB value of less than or equal to 7,
• - as well as mixtures of the aforementioned substances.

worin R1, R2 und R3 unabhängig voneinander für ein Wasserstoffatom oder eine Gruppierung der Formel (III) stehen,

worin R4 für eine unverzweigte oder verzweigte, gesättigte oder ungesättigte C₁₁-C₂₇-Alkylgruppe oder C₁₁-C₂₇-Alkylengruppe steht,
mit der Maßgabe, dass mindestens einer und maximal zwei der Reste ausgewählt aus R1, R2 und R3 für eine Gruppierung der Formel (III) stehen,Preferred agents according to the invention are characterized in that they contain at least one non-ionic water-in-oil emulsifier selected from glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, which have the formula (II):

wherein R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III),

wherein R4 represents a straight or branched, saturated or unsaturated C ₁₁ -C ₂₇ alkyl group or C ₁₁ -C ₂₇ alkylene group,
with the proviso that at least one and a maximum of two of the radicals selected from R1, R2 and R3 represent a group of the formula (III),

The radical R4 in the formula (III) represents a straight or branched, saturated or unsaturated C ₁₁ -C ₂₇ alkyl group.
Preferably, R4 is an unbranched, saturated C ₁₁ -C ₂₇ alkyl group. More preferably, R4 is an unbranched, saturated C ₁₃ -C ₂₃ alkyl group. Particularly preferably, R4 is an unbranched, saturated C ₁₅ -C ₁₇ alkyl group.
Preferred agents according to the invention are characterized in that at least one compound from the group of formulas (IIa) to (IId) is contained as glyceryl fatty acid ester of general formula (II):

The compounds of formulas (IIa) to (IId) are also known under the names glyceryl monostearate and glyceryl monopalmitate.
Further preferred agents according to the invention are characterized in that at least one compound from the group of formulas (IIe) to (IIh) is contained as glyceryl fatty acid ester of general formula (II):

The compounds of formula (Ile) to (IIh) are also known under the names glyceryl distearate and glyceryl dipalmitate.
Further agents preferred according to the invention are characterized in that at least one compound from the group of formulas (IIa) to (IIh) is contained as glyceryl fatty acid ester of formula (II).
Further agents which are particularly preferred according to the invention are characterized in that at least one compound selected from glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate is contained as glyceryl fatty acid ester of the formula (II).
It is particularly preferred if the agent according to the invention contains, based on its weight, one or more glyceryl fatty acid esters of the formula (II) in a total amount of 0.1 - 15 wt.%, particularly preferably 0.5 to 10 wt.%, particularly preferably 1 - 5 wt.%.
In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains, as glyceryl fatty acid ester of the formula (II), at least one compound selected from glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate, in a total amount of 0.1 - 15 wt.%, particularly preferably 0.5 to 10 wt.%, particularly preferably 1 - 5 wt.%, based on the weight of the agent according to the invention.
According to the invention, it may be preferable to use only a single water-in-oil emulsifier. In another preferred embodiment, the agents according to the invention contain mixtures, in particular technical mixtures, of at least two water-in-oil emulsifiers. A technical mixture is understood to mean, for example, a commercial product such as Cutina ^® GMS, which is a mixture of glyceryl monostearate and glyceryl distearate. Here, the molar ratio of monoester to diester is approximately 1:1. Another technical emulsifier mixture preferred according to the invention is the commercial product Cutina ^® GMS SE, where "SE" stands for "self-emulsifying". The commercial product Cutina ^® GMS SE contains, based on its weight, 5 - 10% by weight, preferably 7 - 8% by weight, of potassium stearate.
Further agents which are particularly preferred according to the invention are characterized in that the at least one non-ionic water-in-oil emulsifier is selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol as well as mixtures of these alkanols. Further agents which are particularly preferred according to the invention are characterized in that the at least one non-ionic water-in-oil emulsifier, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol as well as mixtures of these alkanols, is contained in a total amount of 1-25% by weight, preferably 2-20% by weight, particularly preferably 5-15% by weight, extremely preferably 10-15% by weight, in each case based on the weight of the agent.
Further agents which are particularly preferred according to the invention are characterized in that the at least one non-ionic water-in-oil emulsifier is selected from mixtures of at least one linear, saturated C ₁₂ - C ₃₀ alkanol, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol, as well as mixtures of these alkanols, in combination with at least one glycerol mono- or diester of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated.
Further agents which are particularly preferred according to the invention are characterized in that the at least one non-ionic water-in-oil emulsifier is selected from mixtures of at least one linear, saturated C ₁₂ - C ₃₀ alkanol, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol, as well as mixtures of these alkanols, in combination with at least one glycerin mono- or diester of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, wherein the non-ionic water-in-oil emulsifiers mentioned are contained in a total amount of 1 - 30 wt.%, preferably 2 - 25 wt.%, particularly preferably 5 - 20 wt.%, extremely preferably 10 - 20 wt.%, based on the weight of the agent.

Water-in-oil emulsifiers that can be used particularly advantageously are stearyl alcohol, cetyl alcohol, glyceryl monostearate, in particular in the form of the commercial products Cutina ^® GMS, Cutina ^® MD and Cutina ^® GMS SE (ex BASF), glyceryl distearate, glyceryl monocaprinate, glyceryl monocaprylate, glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monohydroxystearate, glyceryl monooleate, glyceryl monolanolate, glyceryl dimyristate, glyceryl dipalmitate, glyceryl dioleate, propylene glycol monostearate, propylene glycol monolaurate, sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan sesquistearate, sorbitan distearate, sorbitan dioleate, sorbitan sesquioleate, sucrose distearate, arachidyl alcohol, behenyl alcohol, diglycerol monostearate, diglycerol monoisostearate, diglycerol monooleate, diglycerol dihydroxystearate, diglycerol distearate, diglycerol dioleate, triglycerol distearate, tetraglycerol monostearate, tetraglycerol distearate, tetraglycerol tristearate, decaglycerol pentastearate, decaglycerol pentahydroxystearate, decaglycerol pentaisostearate and decaglycerol pentaoleate.
Preferred agents according to the invention are characterized in that the nonionic water-in-oil emulsifier c), which preferably has an HLB value greater than 1.0 and less than/equal to 7.0, is selected from linear, saturated C ₁₂ - C ₃₀ alkanols, ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, propylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, methylglucose mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, glycerol monoethers of saturated or unsaturated, branched and/or unbranched alcohols with a chain length of 8 - 30, in particular 12 - 18 carbon atoms, partial esters of polyglycerols with n = 2 to 10 glycerol units and esterified with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ - C ₃₀ fatty acid residues, which preferably have an HLB value of less than or equal to 7, as well as mixtures of the aforementioned substances.
Particularly preferred agents according to the invention are characterized in that the nonionic water-in-oil emulsifier(s) c), preferably with an HLB value greater than 1.0 and less than or equal to 7.0, is selected from the mono-, di-, tri- and tetraesters of ethylene glycol or pentaerythritol with linear or branched, saturated or unsaturated fatty acids with 12-30, in particular 14-22 carbon atoms, which may be hydroxylated. The mono- and diesters are preferred according to the invention. C ₁₂ -C ₃₀ fatty acid residues preferred according to the invention are selected from lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid residues; the stearic acid residue is particularly preferred. Particularly preferred nonionic water-in-oil emulsifiers according to the invention, preferably with an HLB value greater than 1.0 and less than or equal to 7.0, are selected from ethylene glycol monostearate, ethylene glycol distearate and mixtures thereof. According to the invention, it may be preferable to use only a single water-in-oil emulsifier. In another preferred embodiment, the compositions according to the invention contain mixtures, in particular technical mixtures, of at least two water-in-oil emulsifiers. A technical mixture is understood to mean, for example, commercial products such as Cutina ^® GMS, Cutina ^® GMS SE or Cutina ^® PES.
The HLB values can be calculated according to Griffin, for example, as shown or tabulated in the RÖMPP Chemistry Lexicon, particularly in the online version from November 2003, and the handbooks by Fiedler, Kirk-Othmer and Janistyn cited there under the keyword “HLB system”. If there are different details in the literature on the HLB value of a substance, the HLB value that is closest to the value calculated according to Griffin should be used for the teaching according to the invention. If a clear HLB value cannot be determined in this way, the HLB value specified by the manufacturer of the emulsifier should be used for the teaching according to the invention. If this is not possible either, the HLB value should be determined experimentally.

Further agents preferred according to the invention are characterized in that they additionally contain at least one surfactant g) in a total amount of 0.1 - 10% by weight, based on the weight of the agent, which is different from the non-ionic water-in-oil emulsifiers c). 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 radical 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.

Particularly preferred agents according to the invention are characterized in that the at least one additional surfactant g) is selected from ionic surfactants, preferably selected from anionic, zwitterionic and amphoteric surfactants and mixtures thereof, with mixtures of at least one anionic surfactant and at least one zwitterionic surfactant being particularly preferred.

Further agents (M1) preferred 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 have 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 N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines with 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. 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-alkylamino propionic 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.
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, are suitable as anionic surfactants. The molecule can also 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 ethercarboxylic 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.

Preferably, the total amount of the at least one surfactant g), which is different from the nonionic water-in-oil emulsifiers c), in the agent (M1) preferred according to the invention is 0.1 - 5 wt.%, preferably 0.5 - 4 wt.%, particularly preferably 1 - 3 wt.% and extremely preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1). Further agents (M1) particularly preferred according to the invention are characterized in that they contain, in each case based on their weight, at least one surfactant g), which is selected from anionic surfactants, in a total amount of 0.1 - 5 wt.%, preferably 0.5 - 4 wt.%, particularly preferably 1 - 3 wt.% and extremely preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1).
Further agents (M1) which are particularly preferred according to the invention are characterized in that they contain, in each case based on their weight, at least one surfactant g) which is selected from zwitterionic surfactants, in a total amount of 0.1 - 5 wt.%, preferably 0.2 - 3 wt.%, particularly preferably 0.5 - 2 wt.% and extremely preferably 0.6 to 1 wt.%, in each case based on the weight of the agent (M1).
Further agents (M1) which are particularly preferred according to the invention are characterized in that they contain as surfactants g) a mixture of at least one anionic surfactant and at least one zwitterionic surfactant in a total amount of 0.1 - 5 wt.%, preferably 0.5 - 4 wt.%, particularly preferably 1 - 3 wt.% and extremely preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1).

Surprisingly, it was found that the rheological properties of the agents (M1) according to the invention can be improved by the addition of at least one further fat component which is different from the non-ionic water-in-oil emulsifiers c), which also has a positive effect on the thermal stability of the agents (M1).
Further agents (M1) preferred according to the invention are characterized in that they additionally contain at least one fatty component which is different from the non-ionic water-in-oil emulsifiers c) and which is selected from oils that are liquid at 25°C and fatty components with a melting point in the range from >25°C to 120°C, and mixtures thereof. Fatty components according to the invention are lipophilic organic substances which have a water solubility of a maximum of 0.001% by weight or less at 20°C. According to the invention, these fatty substances include oils, fats and waxes. Linear, saturated fatty alcohols are counted among the non-ionic water-in-oil emulsifiers according to the invention. Essential oils and perfume oils or fragrances are also not counted among the fatty substances in the sense of the present invention.
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 25°C and a pressure of 1013.25 mbar.

Agents (M1) which are particularly preferred according to the invention are characterized in that the at least one fat component which is different from the non-ionic water-in-oil emulsifiers c) is is selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, esters of 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, mineral oil, isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 -Fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ -alkanols, esters of 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, and mixtures thereof.

Among the oils preferred according to the invention which are liquid at 25°C and are selected from branched saturated or unsaturated fatty alcohols having 6-30 carbon atoms are 2-octyldodecanol, 2-hexyldecanol and 2-ethylhexyl alcohol, of which 2-octyldodecanol is particularly preferred.
Other oils preferred according to the invention are selected from the triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids. The use of natural oils, e.g. argan oil, moringa oil, macadamia oil, apricot kernel oil, marula oil, soybean oil, cottonseed oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, castor oil, corn oil, olive oil, rapeseed oil, sesame oil, safflower oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil and the like, as well as mixtures of these oils, can be particularly suitable. Synthetic triglyceride oils or triglyceride oils obtained by transesterification of natural oils are also suitable, in particular capric/caprylic triglycerides, e.g. the commercial product Myritol ^® 318 (BASF) with unbranched fatty acid residues and glyceryltriisostearin with branched fatty acid residues. Further oils which are particularly preferred according to the invention are selected from the dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, in particular diisopropyl adipate, di-n-butyl adipate, di-(2-ethylhexyl) adipate, dioctyl adipate, diethyl/di-n-butyl/dioctyl sebacate, diisopropyl sebacate, dioctyl malate, dioctyl maleate, dicaprylyl maleate, diisooctyl succinate, di-2-ethylhexyl succinate and di-(2-hexyldecyl) succinate.
Further oils which may be preferred according to the invention are selected from the 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, and which are preferably selected from 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, hexyldecyl stearate, hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl palmitate and 2-ethylhexyl stearate.
Other oils which may be preferred according to the invention are selected from the C ₈ -C ₂₂ fatty alcohol esters of monovalent or polyvalent C ₂ -C ₇ hydroxycarboxylic acids, in particular the esters of glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and salicylic acid. It may be preferred according to the invention to use mixtures of the aforementioned oils.
Further agents (M1) preferred according to the invention are characterized in that the at least one fat component, which is different from the non-ionic water-in-oil emulsifiers c), is selected from fat components with a melting point in the range from >25°C to 120°C, preferably selected from paraffin wax, saturated n-alkanes with at least 20 carbon atoms, preferably with 22 to 60 carbon atoms, for example docosan, butyrospermum parkii (shea butter), mango butter, cocoa butter and esters of saturated, monohydric C ₈ -C ₁₈ alcohols with saturated C ₁₂ -C ₁₈ monocarboxylic acids, in particular stearyl laurate, cetearyl stearate, cetyl palmitate and myristyl myristate, esters of a saturated, monohydric C ₁₆ -C ₆₀ alkanol and a saturated C ₈ -C ₃₆ -Monocarboxylic acid, in particular cetyl behenate, stearyl behenate, C ₂₀ -C ₄₀ alkyl stearate, candelilla wax, carnauba wax and beeswax, glycerol triesters of saturated linear C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, in particular castor wax, and mixtures of the aforementioned substances.
Further agents (M1) which are particularly preferred according to the invention are characterized in that they contain at least one fat component which is different from the non-ionic water-in-oil emulsifiers c) in a total amount of 0.1 - 5 wt.%, preferably 0.2 - 4 wt.%, particularly preferably 0.5 - 3 wt.% and extremely preferably 1 to 2 wt.%, in each case based on the weight of the agent (M1).

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. Whenever a cosmetic oil is mentioned in the present application, this always refers to a cosmetic oil that is not a fragrance or 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 customary in the art, as it is RÖMPP Chemistry Lexicon, as of December 2007 , can be taken. 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 that 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 stimulate the receptors of the hair cells of the olfactory system.
Particularly preferred agents according to the invention (M1) 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 agent according to the invention.

Furthermore, it was surprisingly found that the application properties of the agents according to the invention are further optimized, in particular the storage stability at higher temperatures, as well as the coloring properties, in particular with regard to color intensity and balancing power, if they additionally contain at least one polyol selected from polyols with 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain can be interrupted by one or more oxygen atoms, preferably in a total amount of 0.1 wt.% to 10 wt.%, preferably 0.5 to 5 wt.%, particularly preferably 1.0 to 3 wt.%, in each case based on the weight of the agent.
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 agents according to the invention (M1) are characterized in that at least one polyol 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 0.1 - 10 wt.%, preferably 0.5 - 5 wt.%, particularly preferably 1.0 - 3.0 wt.%, in each case based on the weight of the agent according to the invention.

Color-changing agents preferred according to the invention have a viscosity in the range of 5000 - 50000 mPas, preferably 5500 - 30000 mPas, particularly preferably 6000 - 25000 mPas, extremely preferably 6500 - 20000 mPas, in each case measured at 20°C.
The ready-to-use mixture of the color-changing agent according to the invention or preferred according to the invention and the hydrogen peroxide solution preferably has a viscosity in the range of 5000-20000 mPas, preferably 6000-1800 mPas, particularly preferably 6500-1500 mPas, extremely preferably 7000-12000 mPas, in each case measured at 20°C.
A Haake model MVII rheometer can be used for the measurement, for example at a shear rate of 7.2 revolutions per second.

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 contain no ammonia and no 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 extremely preferred according to the invention.
The alkanolamines which can be used as alkalizing agents preferably have 2 to 9 carbon atoms in the molecule and are particularly preferably selected from primary amines having a C ₂ -C ₆ alkyl parent structure which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group consisting of 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. According to the invention, particularly preferred alkanolamines 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. Particularly preferred agents 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 value to form a ready-to-use colorant immediately before application to the keratin fibers 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.

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 coloration on their own in the context of 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 as well as 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 or its salt is contained in a total amount of 0.01 to 5 wt. %, preferably 0.1 to 4 wt. %, particularly preferably 0.2 to 3.0 wt. %, extremely preferably 0.5 to 2.0 wt. %, in each case based on the weight of the agent according to the invention (M1).
Preferably, at least one coupler component or its salt is contained in a total amount of 0.001 to 4 wt. %, preferably 0.01 to 3 wt. %, particularly preferably 0.05 to 2 wt. %, extremely preferably 0.1 to 1 wt. %, in each case based on the weight of the agent according to the invention (M1).
The total amount of oxidation dye precursors or their salts in the agent (M1) according to the invention is preferably 0.011 to 9 wt. %, preferably 0.11 to 7 wt. %, particularly preferably 0.25 to 5 wt. %, extremely preferably 0.6 to 3.0 wt. %, in each case based on the weight of the agent (M1).

• - 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.
Particularly preferred additional coupler components according to the invention are selected from 3-amino phenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophen-oxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis-(2,4-diaminophenoxy)propane, 1-beta-hydroxyethyl-3,4-methylenedioxyaniline, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene (= 2-amino-4-hydroxyethylaminoanisole), 1,3-bis (2,4-diaminophenyl)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-methoxypyridine, 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. It may be preferable to avoid resorcinol and resorcinol derivatives.

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 onto 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 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 containing a heterocycle having at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic direct dyes sold under the trademark Arianor are also preferred cationic direct dyes according to the invention. Nonionic direct dyes that 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.

The agents (M1) according to the invention are further 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).

Oxidative color-changing agents with ammonia or ammonium hydroxide release ammonia during the color-changing process, so that non-volatile alkalizing agents, i.e. all alkalizing agents other than ammonia or ammonium hydroxide, can be preferred according to the invention. Therefore, for some applications according to the invention, it can be preferred that the agents according to the invention do not contain ammonia or ammonium hydroxide as an alkalizing agent.

1. i) mindestens einen Container (C1), enthaltend ein Mittel zur oxidativen Farbveränderung keratinischer Fasern, insbesondere menschlicher Haare, das in Form einer Öl-in-Wasser-Emulsion vorliegt und das, jeweils bezogen auf sein Gewicht, folgende Bestandteile enthält:
   1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
   2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide,
   3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator,
   4. d) mindestens ein Alkalisierungsmittel,
   5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
   6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
   wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist, und 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. ii) 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.

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

1. i) at least one container (C1) containing an agent for the oxidative colour change of keratin fibres, in particular human hair, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, the following components:
   1. a) 40 wt.% to 85 wt.% water,
   2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides,
   3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier,
   4. d) at least one alkalizing agent,
   5. e) zero to less than 0.1% by weight of peroxide compounds,
   6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
   wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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, and
2. ii) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, 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 wt.% data in each case refer 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 regarding the agents according to the invention for oxidative color change applies mutatis mutandis.

The present invention further relates to the use of an agent according to the invention or preferred according to the invention 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.

1. i) Bereitstellen eines kosmetischen Mittels (M1) zur oxidativen Farbveränderung keratinischer Fasern, insbesondere menschlicher Haare, das in Form einer Öl-in-Wasser-Emulsion vorliegt und das, jeweils bezogen auf sein Gewicht, folgende Bestandteile enthält:
   1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
   2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide,
   3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator,
   4. d) mindestens ein Alkalisierungsmittel,
   5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
   6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
   wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist, und 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. 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,
3. 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
4. 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,
5. v) Spülen der Haare mit Wasser und/oder einer reinigenden Zusammensetzung, und
6. 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:

1. i) Providing a cosmetic product (M1) for the oxidative colour change of keratin fibres, in particular human hair, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, the following components:
   1. a) 40 wt.% to 85 wt.% water,
   2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides,
   3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier,
   4. d) at least one alkalizing agent,
   5. e) zero to less than 0.1% by weight of peroxide compounds,
   6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
   wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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, and
2. ii) providing an oxidizing agent preparation (M2) containing 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, 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 refer in each case to the weight of the oxidizing agent preparation (M2), wherein optionally at least one surfactant and/or one oil are contained,
3. 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
4. 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,
5. v) rinsing the hair with water and/or a cleansing composition, and
6. 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 oxidizing agent composition (M2) 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 contains, in each case based on its weight, 40 - 96 wt.%, preferably 65 - 90 wt.%, particularly preferably 70 - 80 wt.%, water.
The oxidizing agent preparation (M2) used in the color change kits according to the invention and preferred according to the invention and in the 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.

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 according to the invention (M1) 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 have 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 N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines with 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. 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, glycol or polyglycols can be present in the molecule. 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, which has the general structural formula (III), in which 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 under the trademarks Stepantex, Dehyquart and Armocare.
In terms of optimal application properties and optimal color results, C10-C22 alkyltrimethylammonium chlorides have proven to be particularly suitable. 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.
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, 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; Preference is given to using 6 to 12 percent by weight solutions in water. Kits, uses and methods preferred according to the invention are characterized in that the composition (M2) used to prepare them contains - based on its weight - 1 to 24% by weight, preferably 4 to 10% by weight, particularly preferably 3 to 6% by weight of 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 equally 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 according to the invention (M1) 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 wt.%, particularly preferably in a total amount of 1 to 15 wt.%, 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.

1. 1. Mittel zur oxidativen Farbveränderung keratinischer Fasern, insbesondere menschlicher Haare, das in Form einer Öl-in-Wasser-Emulsion vorliegt und das, jeweils bezogen auf sein Gewicht, folgende Bestandteile enthält:
   1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
   2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide,
   3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator,
   4. d) mindestens ein Alkalisierungsmittel,
   5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
   6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
   wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist, und 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.
2. 2. Mittel nach Punkt 1, dadurch gekennzeichnet, dass das mindestens eine Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide, in einer Gesamtmenge von 0,05 bis 2,0 Gew.-%, bevorzugt 0,1 bis 1,5 Gew.-%, besonders bevorzugt 0,2 bis 1,2 Gew.-%, außerordentlich bevorzugt 0,5 bis 1,0 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten ist.
3. 3. Mittel nach Punkt 1 oder 2, dadurch gekennzeichnet, dass das Polysaccharid ausgewählt ist aus iota-Carrageen.
4. 4. Mittel nach einem der Punkte 1 - 3, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator einen HLB-Wert größer 1,0 und kleiner/gleich 7,0 aufweist.
5. 5. Mittel nach einem der Punkte 1 - 4, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator ausgewählt ist aus
   1. i. linearen, gesättigten C₁₂ - C₃₀-Alkanolen,
   2. ii. Ethylenglycolmono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   3. iii. Glycerinmono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   4. iv. Propylenglycolmono- und -diestern von linearen, gesättigten und ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   5. v. Sorbitanmono-, -di- und -triestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   6. vi. Pentaerythritylmono-, -di-, -tri- und -tetraestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   7. vii. Methylglucosemono- und -diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können,
   8. viii. Glycerinmonoethern gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8 - 30, insbesondere 12 - 18 Kohlenstoffatomen,
   9. ix. Partialestern von Polyglycerinen mit n = 2 bis 10 Glycerineinheiten und mit 1 bis 5 gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls hydroxylierten C₈ - C₃₀-Fettsäureresten verestert,
   10. x. sowie Mischungen der vorgenannten Substanzen.
6. 6. Mittel nach einem der Punkte 1 - 5, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator ausgewählt ist aus Glycerinmono- und diestern von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, die die Formel (II) aufweisen:
   
   worin R1, R2 und R3 unabhängig voneinander für ein Wasserstoffatom oder eine Gruppierung der Formel (III) stehen,
   
   worin R4 für eine lineare, gesättigte oder lineare, ungesättigte C₁₁-C₂₉-Alkylgruppe steht, mit der Maßgabe, dass mindestens einer und maximal zwei der Reste, ausgewählt aus R1, R2 und R3, für eine Gruppierung der Formel (III) stehen.
7. 7. Mittel nach einem der Punkte 1 - 6, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator ausgewählt ist aus Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol sowie Mischungen dieser Alkanole.
8. 8. Mittel nach einem der Punkte 1 - 7, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator ausgewählt ist aus Mischungen von mindestens einem linearen, gesättigten C₁₂ - C₃₀-Alkanol, ausgewählt aus Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol sowie Mischungen dieser Alkanole, in Kombination mit mindestens einem Glycerinmono- oder -diester von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können.
9. 9. Mittel nach einem der Punkte 1 - 8, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator, ausgewählt aus Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol sowie Mischungen dieser Alkanole, in einer Gesamtmenge von 1 - 25 Gew.-%, bevorzugt 2 - 20 Gew.-%, besonders bevorzugt 5 - 15 Gew.-%, außerordentlich bevorzugt 10 - 15 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten ist.
10. 10. Mittel nach einem der Punkte 1 - 9, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator ausgewählt ist aus Mischungen von mindestens einem linearen, gesättigten C₁₂ - C₃₀-Alkanol, ausgewählt aus Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol sowie Mischungen dieser Alkanole, in Kombination mit mindestens einem Glycerinmono- oder -diester von linearen oder verzweigten, gesättigten oder ungesättigten C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, wobei die genannten nichtionischen Wasser-in-Öl-Emulgatoren, bezogen auf das Gewicht des Mittels, in einer Gesamtmenge von 1 - 30 Gew.-%, bevorzugt 2 - 25 Gew.-%, besonders bevorzugt 5 - 20 Gew.-%, außerordentlich bevorzugt 10 - 20 Gew.-%, enthalten sind.
11. 11. Mittel nach einem der Punkte 1 - 10, dadurch gekennzeichnet, dass zusätzlich in einer Gesamtmenge von 0,1 - 10 Gew.-%, bezogen auf das Gewicht des Mittels, mindestens ein Tensid g) enthalten ist, das von den nichtionischen Wasser-in-Öl-Emulgatoren c) verschieden ist.
12. 12. Mittel nach Punkt 11, dadurch gekennzeichnet, dass das mindestens eine zusätzliche Tensid g) ausgewählt ist aus ionischen Tensiden, bevorzugt ausgewählt aus anionischen, zwitterionischen und amphoteren Tensiden sowie Mischungen hiervon, wobei Mischungen aus mindestens einem anionischen Tensid und mindestens einem zwitterionischen Tensid besonders bevorzugt sind.
13. 13. Mittel nach einem der Punkte 1 - 12, dadurch gekennzeichnet, dass zusätzlich mindestens eine Fettkomponente enthalten ist, die von den nichtionischen Wasser-in-Öl-Emulgatoren c) verschieden ist und die ausgewählt ist aus bei 25°C flüssigen Ölen und Fettkomponenten mit einem Schmelzpunkt im Bereich von >25°C bis 120°C, sowie Mischungen hiervon.
14. 14. Mittel nach Punkt 13, dadurch gekennzeichnet, dass die mindestens eine Fettkomponente, die von den nichtionischen Wasser-in-Öl-Emulgatoren c) verschieden ist, ausgewählt ist aus mindestens einem bei 25°C flüssigen Öl, das ausgewählt ist aus verzweigten und gesättigten oder ungesättigten Alkanolen mit 6 - 30 Kohlenstoffatomen, Glycerintriestern von linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten C_8-30-Fettsäuren, Dicarbonsäureestern von linearen oder verzweigten C₂-C₁₀-Alkanolen, Estern von verzweigten gesättigten oder ungesättigten Fettalkoholen mit 2 - 30 Kohlenstoffatomen mit linearen oder verzweigten gesättigten oder ungesättigten Fettsäuren mit 2 - 30 Kohlenstoffatomen, die hydroxyliert sein können, Mineralöl, Isoparaffinen, Polydecenen, Siliconölen und Mischungen hiervon, bevorzugt ausgewählt aus verzweigten und gesättigten oder ungesättigten Alkanolen mit 6 - 30 Kohlenstoffatomen, Glycerintriestern von linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten C_8-30-Fettsäuren, Dicarbonsäureestern von linearen oder verzweigten C₂-C₁₀-Alkanolen, Estern von verzweigten gesättigten oder ungesättigten Fettalkoholen mit 2 - 30 Kohlenstoffatomen mit linearen oder verzweigten gesättigten oder ungesättigten Fettsäuren mit 2 - 30 Kohlenstoffatomen, die hydroxyliert sein können, und Mischungen hiervon.
15. 15. Mittel nach einem der Punkte 1 - 14, dadurch gekennzeichnet, dass die mindestens eine Fettkomponente, die von den nichtionischen Wasser-in-Öl-Emulgatoren c) verschieden ist, ausgewählt ist aus mindestens einer Fettkomponente mit einem Schmelzpunkt im Bereich von >25°C bis 120°C, die ausgewählt ist aus Paraffinwachs, gesättigten n-Alkanen mit mindestens 20 Kohlenstoff-Atomen, bevorzugt mit 22 bis 60 Kohlenstoff-Atomen, beispielsweise Docosan, Butyrospermum Parkii (Shea Butter), Mangobutter, Kakaobutter und Estern von gesättigten, einwertigen C₈-C₁₈-Alkoholen mit gesättigten C₁₂-C₁₈-Monocarbonsäuren insbesondere Stearyllaurat, Cetearylstearat, Cetylpalmitat und Myristylmyristat, Estern aus einem gesättigten, einwertigen C₁₆-C₆₀-Alkanol und einer gesättigten C₈-C₃₆-Monocarbonsäure, insbesondere Cetylbehenat, Stearylbehenat C₂₀-C₄₀-Alkylstearat, Candelillawachs, Carnaubawachs und Bienenwachs, Glycerintriestern von gesättigten linearen C₁₂ - C₃₀-Carbonsäuren, die hydroxyliert sein können, insbesondere Castor-Wachs, sowie Mischungen der vorgenannten Substanzen.
16. 16. Mittel nach einem der Punkte 1 - 15, dadurch gekennzeichnet, dass die mindestens eine Fettkomponente, die von den nichtionischen Wasser-in-Öl-Emulgatoren c) verschieden ist, in einer Gesamtmenge von 0,1 - 5 Gew.-%, bevorzugt 0,2 - 4 Gew.-%, besonders bevorzugt 0,5 - 3 Gew.-% und außerordentlich bevorzugt 1 bis 2 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten ist.
17. 17. Mittel nach einem der Punkte 1 - 16, dadurch gekennzeichnet, dass zusätzlich mindestens ein Polyol, ausgewählt aus Polyolen mit 2 bis 20 Kohlenstoffatomen und 2 bis 15 Hydroxygruppen, deren Kohlenstoffatom-Kette durch ein oder mehrere Sauerstoffatome unterbrochen sein kann, enthalten ist, bevorzugt in einer Gesamtmenge von 0,1 Gew.-% bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, besonders bevorzugt 1,0 bis 3 Gew.-%, jeweils bezogen auf das Gewicht des Mittels.
18. 18. Mittel nach einem der Punkte 1 - 17, dadurch gekennzeichnet, dass das mindestens eine Alkalisierungsmittel ausgewählt ist aus Alkanolaminen, Alkalihydroxiden, basischen Aminosäuren, Alkalimetallmetasilikaten, Alkalimetalldisilikaten, Alkaliphosphaten und Dialkalimonohydrogenphosphaten sowie Mischungen dieser Substanzen.
19. 19. Mittel nach einem der Punkte 1 bis 18, dadurch gekennzeichnet, dass kein Ammoniak und kein Ammoniumhydroxid enthalten sind.
20. 20. Mittel nach einem der Punkte 1 bis 19, dadurch gekennzeichnet, dass die Gesamtmenge an Oxidationsfarbstoffvorprodukten oder deren Salzen 0,011 bis 9 Gew.-%, bevorzugt 0,11 bis 7 Gew.-%, besonders bevorzugt 0,25 bis 5 Gew.-%, außerordentlich bevorzugt 0,6 bis 3,0 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, beträgt.
21. 21. Mittel nach einem der Punkte 1 bis 20, dadurch gekennzeichnet, dass der mindestens eine nichtionische Wasser-in-Öl-Emulgator in einer Gesamtmenge von 2 - 25 Gew.-%, bevorzugt 5 - 20 Gew.-%, besonders bevorzugt 10 - 20 Gew.-%, jeweils bezogen auf das Gewicht des Mittels., enthalten ist.
22. 22. Mittel nach einem der Punkte 1 bis 21, dadurch gekennzeichnet, dass mindestens ein Kaliumsalz, bevorzugt in einer Gesamtmenge von 0,05 bis 0,5 Gew.-%, bevorzugt 0,1 bis 0,4 Gew.-%, weiter bevorzugt 0,15 bis 0,35 Gew.-%, besonders bevorzugt 0,2 bis 0,3 Gew.-%, außerordentlich bevorzugt 0,21 bis 0,25 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten ist.
23. 23. Mittel nach Punkt 22, dadurch gekennzeichnet, dass das mindestens eine Kaliumsalz ausgewählt ist aus Kaliumstearat, Kaliumchlorid, Kaliumhydrogensulfat, Dikaliumsulfat, Dikaliumhydrogenphosphat, Kaliumdihydrogenphosphat, Trikaliumphosphat, Kaliumhydroxid, Kaliumtartrat, Kaliumlactat, Kaliumsuccinat sowie Mischungen dieser Salze, bevorzugt ausgewählt aus den anorganischen Salzen Kaliumchlorid, Kaliumhydrogensulfat, Dikaliumsulfat, Dikaliumhydrogenphosphat, Kaliumdihydrogenphosphat, Trikaliumphosphat und Kaliumhydroxid sowie Mischungen dieser Salze.
24. 24. Mittel nach einem der Punkte 1 bis 23, dadurch gekennzeichnet, dass mindestens ein Salz, ausgewählt aus Calciumchlorid, Calciumchlorid, Calciumlactat, Calciumgluconat und Calciumgluconatlactat sowie Mischungen hiervon in einer Gesamtmenge von 0,1 - 5 Gew.-%, besonders bevorzugt 0,2 - 3 Gew.-%, außerordentlich bevorzugt 0,5 - 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Mittels (M1), enthalten ist.
25. 25. Verwendung eines Mittels nach einem der Punkte 1 bis 24 zur oxidativen Farbveränderung keratinischer Fasern, insbesondere menschlicher Haare.
26. 26. Verfahren zur oxidativen Farbveränderung, das die folgenden Verfahrensschritte umfasst:
    1. i) Bereitstellen eines kosmetischen Mittels (M1) zur oxidativen Farbveränderung keratinischer Fasern gemäß einem der Punkte 1 bis 24, enthaltend
       1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
       2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen der vorgenannten Substanzen,
       3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator,
       4. d) mindestens ein Alkalisierungsmittel,
       5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
       6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
       wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist, und 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. 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 Öl und/oder mindestens ein Tensid enthalten sind,
    3. 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
    4. 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,
    5. v) Spülen der Haare mit Wasser und/oder einer reinigenden Zusammensetzung, und
    6. vi) gegebenenfalls Applizieren eines Nachbehandlungsmittels auf die Haare und gegebenenfalls Ausspülen, anschließend Trocknen.
27. 27. Verpackungseinheit (Kit-of-Parts), die - getrennt voneinander verpackt - folgendes umfasst:
    1. i) mindestens einen Container (C1), enthaltend ein Mittel zur oxidativen Farbveränderung keratinischer Fasern gemäß einem der Punkte 1 bis 24, enthaltend:
       1. a) 40 Gew.-% bis 85 Gew.-% Wasser,
       2. b) mindestens ein Polysaccharid, ausgewählt aus iota-Carrageen und Alginsäure sowie Mischungen dieser Polysaccharide u,
       3. c) in einer Gesamtmenge von 1 - 30 Gew.-% mindestens einen nichtionischen Wasser-in-Öl-Emulgator, bevorzugt mit einem HLB-Wert größer 1,0 und kleiner/gleich 7,0,
       4. d) mindestens ein Alkalisierungsmittel,
       5. e) null bis weniger als 0,1 Gew.-% an Peroxidverbindungen,
       6. f) optional mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp und mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp,
       wobei kein Polymer oder Copolymer mit Acrylat-, Methacrylat- oder Vinyl-haltigen Monomeren und kein Polyurethan enthalten ist, und 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. ii) 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.

The subject matter of the present invention is summarized by the following points:

1. 1. Agent for the oxidative colour change of keratin fibres, in particular human hair, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, the following components:
   1. a) 40 wt.% to 85 wt.% water,
   2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides,
   3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier,
   4. d) at least one alkalizing agent,
   5. e) zero to less than 0.1% by weight of peroxide compounds,
   6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
   wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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.
2. 2. Agent according to item 1, characterized in that the at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides is contained in a total amount of 0.05 to 2.0 wt.%, preferably 0.1 to 1.5 wt.%, particularly preferably 0.2 to 1.2 wt.%, extremely preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent.
3. 3. Agent according to point 1 or 2, characterized in that the polysaccharide is selected from iota-carrageenan.
4. 4. Agent according to one of items 1 - 3, characterized in that the at least one non-ionic water-in-oil emulsifier has an HLB value greater than 1.0 and less than/equal to 7.0.
5. 5. Agent according to one of items 1 - 4, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from
   1. i. linear, saturated C ₁₂ - C ₃₀ alkanols,
   2. ii. Ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   3. iii. Glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   4. iv. Propylene glycol mono- and diesters of linear, saturated and unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   5. v. Sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   6. vi. Pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   7. vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated,
   8. viii. Glycerol monoethers of saturated and/or unsaturated, branched and/or unbranched alcohols with a chain length of 8 - 30, in particular 12 - 18 carbon atoms,
   9. ix. Partial esters of polyglycerols with n = 2 to 10 glycerol units and esterified with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ - C ₃₀ fatty acid residues,
   10. x. and mixtures of the aforementioned substances.
6. 6. Agent according to one of points 1 - 5, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, which have the formula (II):
   
   wherein R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III),
   
   wherein R4 represents a linear, saturated or linear, unsaturated C ₁₁ -C ₂₉ alkyl group, with the proviso that at least one and a maximum of two of the radicals selected from R1, R2 and R3 represent a grouping of the formula (III).
7. 7. Agent according to one of points 1 - 6, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol as well as mixtures of these alkanols.
8. 8. Agent according to one of points 1 - 7, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from mixtures of at least one linear, saturated C ₁₂ - C ₃₀ alkanol, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols, in combination with at least one glycerol mono- or diester of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated.
9. 9. Agent according to one of points 1 - 8, characterized in that the at least one non-ionic water-in-oil emulsifier, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols, is contained in a total amount of 1 - 25 wt.%, preferably 2 - 20 wt.%, particularly preferably 5 - 15 wt.%, extremely preferably 10 - 15 wt.%, in each case based on the weight of the agent.
10. 10. Agent according to one of points 1 - 9, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from mixtures of at least one linear, saturated C ₁₂ - C ₃₀ alkanol, selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols, in combination with at least one glycerol mono- or diester of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, wherein the said non-ionic water-in-oil emulsifiers, based on the weight of the agent, are contained in a total amount of 1 - 30 wt.%, preferably 2 - 25 wt.%, particularly preferably 5 - 20 wt.%, extremely preferably 10 - 20 wt.%.
11. 11. Agent according to one of items 1 - 10, characterized in that in addition, in a total amount of 0.1 - 10 wt. %, based on the weight of the agent, at least one surfactant g) is contained which is different from the non-ionic water-in-oil emulsifiers c).
12. 12. Agent according to item 11, characterized in that the at least one additional surfactant g) is selected from ionic surfactants, preferably selected from anionic, zwitterionic and amphoteric surfactants and mixtures thereof, with mixtures of at least one anionic surfactant and at least one zwitterionic surfactant being particularly preferred.
13. 13. Agent according to one of items 1 - 12, characterized in that it additionally contains at least one fat component which is different from the non-ionic water-in-oil emulsifiers c) and which is selected from oils which are liquid at 25°C and fat components with a melting point in the range from >25°C to 120°C, and mixtures thereof.
14. 14. Agent according to item 13, characterized in that the at least one fat component, which is different from the non-ionic water-in-oil emulsifiers c), is selected from at least one oil which is liquid at 25°C and which is selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, esters of 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, mineral oil, isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, esters of 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, and mixtures thereof.
15. 15. Agent according to one of points 1 - 14, characterized in that the at least one fat component, which is different from the non-ionic water-in-oil emulsifiers c), is selected from at least one fat component with a melting point in the range of >25°C to 120°C, which is selected from paraffin wax, saturated n-alkanes with at least 20 carbon atoms, preferably with 22 to 60 carbon atoms, for example docosan, butyrospermum parkii (shea butter), mango butter, cocoa butter and esters of saturated, monohydric C ₈ -C ₁₈ alcohols with saturated C ₁₂ -C ₁₈ monocarboxylic acids, in particular stearyl laurate, cetearyl stearate, cetyl palmitate and myristyl myristate, esters of a saturated, monohydric C ₁₆ -C ₆₀ alkanol and a saturated C ₈ -C ₃₆ -monocarboxylic acid, in particular cetyl behenate, stearyl behenate, C ₂₀ -C ₄₀ -alkyl stearate, candelilla wax, carnauba wax and beeswax, glycerol triesters of saturated linear C ₁₂ - C ₃₀ -carboxylic acids, which may be hydroxylated, in particular castor wax, and mixtures of the aforementioned substances.
16. 16. Agent according to one of items 1 - 15, characterized in that the at least one fat component which is different from the non-ionic water-in-oil emulsifiers c) is contained in a total amount of 0.1 - 5 wt.%, preferably 0.2 - 4 wt.%, particularly preferably 0.5 - 3 wt.% and extremely preferably 1 to 2 wt.%, in each case based on the weight of the agent.
17. 17. Agent according to one of items 1 - 16, characterized in that it additionally contains at least one polyol 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, preferably in a total amount of 0.1 wt.% to 10 wt.%, preferably 0.5 to 5 wt.%, particularly preferably 1.0 to 3 wt.%, in each case based on the weight of the agent.
18. 18. Agent according to one of items 1 - 17, 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.
19. 19. Agent according to one of items 1 to 18, characterized in that it contains no ammonia and no ammonium hydroxide.
20. 20. Agent according to one of items 1 to 19, characterized in that the total amount of oxidation dye precursors or salts thereof is 0.011 to 9 wt.%, preferably 0.11 to 7 wt.%, particularly preferably 0.25 to 5 wt.%, extremely preferably 0.6 to 3.0 wt.%, in each case based on the weight of the agent.
21. 21. Agent according to one of items 1 to 20, characterized in that the at least one non-ionic water-in-oil emulsifier is contained in a total amount of 2 - 25 wt.%, preferably 5 - 20 wt.%, particularly preferably 10 - 20 wt.%, in each case based on the weight of the agent.
22. 22. Agent according to one of items 1 to 21, characterized in that at least one potassium salt is contained, preferably in a total amount of 0.05 to 0.5 wt.%, preferably 0.1 to 0.4 wt.%, more preferably 0.15 to 0.35 wt.%, particularly preferably 0.2 to 0.3 wt.%, extremely preferably 0.21 to 0.25 wt.%, in each case based on the weight of the agent.
23. 23. Agent according to item 22, characterized in that the at least one potassium salt is selected from potassium stearate, 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, preferably 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.
24. 24. Agent according to one of items 1 to 23, characterized in that at least one salt selected from calcium chloride, calcium chloride, calcium lactate, calcium gluconate and calcium gluconate lactate and mixtures thereof is contained in a total amount of 0.1 - 5 wt.%, particularly preferably 0.2 - 3 wt.%, extremely preferably 0.5 - 2.5 wt.%, in each case based on the weight of the agent (M1).
25. 25. Use of an agent according to one of items 1 to 24 for the oxidative colour change of keratin fibres, in particular human hair.
26. 26. Process for oxidative colour change, which comprises the following process steps:
    1. i) Providing a cosmetic agent (M1) for the oxidative color change of keratin fibers according to one of items 1 to 24, containing
       1. a) 40 wt.% to 85 wt.% water,
       2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of the aforementioned substances,
       3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier,
       4. d) at least one alkalizing agent,
       5. e) zero to less than 0.1% by weight of peroxide compounds,
       6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
       wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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, and
    2. 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 refer in each case to the weight of the oxidizing agent preparation (M2), wherein optionally at least one oil and/or at least one surfactant are contained,
    3. 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
    4. 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,
    5. v) rinsing the hair with water and/or a cleansing composition, and
    6. vi) if necessary, apply a post-treatment product to the hair and, if necessary, rinse and then dry.
27. 27. Packaging unit (kit of parts) which, when packed separately, comprises:
    1. i) at least one container (C1) containing an agent for the oxidative colour change of keratin fibres according to one of items 1 to 24, containing:
       1. a) 40 wt.% to 85 wt.% water,
       2. b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides u,
       3. c) in a total amount of 1 - 30 wt.% of at least one non-ionic water-in-oil emulsifier, preferably with an HLB value greater than 1.0 and less than or equal to 7.0,
       4. d) at least one alkalizing agent,
       5. e) zero to less than 0.1% by weight of peroxide compounds,
       6. f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type,
       which does not contain any polymer or copolymer with acrylate, methacrylate or vinyl-containing monomers and no polyurethane, and 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. ii) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, 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 wt.% data in each case refer to the weight of the oxidizing agent preparation (M2), optionally containing at least one oil and/or at least one surfactant.

The following examples are intended to illustrate the subject matter of the invention without limiting it thereto.

examples

The temperature stability of the emulsions (M1) for oxidative color change is determined using the test for determining the phase separation temperature described below.

Determination of the phase separation temperature of the emulsion

A standardized sample of the emulsion to be tested was filled into a test tube and slowly heated to 50°C. After the temperature of the samples was kept at 50°C for 5 minutes, the temperature was slowly increased (approx. 2°C in 3-5 minutes). Trained test persons visually observed at which temperature the emulsion began to show separation phenomena. This temperature was noted as the "phase separation temperature".
A phase separation temperature determined in this way should be at least 63°C in order to characterize the emulsion product as sufficiently stable for storage. Phase separation temperatures below 63°C indicate that the temperature stability is not sufficient when exposed to higher temperatures for longer periods (for example > 50°C, preferably > 60°C).

The table below shows nine different oil-in-water emulsions which represent the alkalizing component (M1) of a two-part oxidative dye and their phase separation temperatures determined according to the method described above. The samples marked with (E) are in accordance with the invention, while (V) are comparative formulations. No. 1 (V) No. 2 (V) No. 3 (V) No. 4 (E) No. 5 (E) No. 6 (E) No. 7 (V) No. 8 (V) No. 9 (V) 2-octyldodecanol 2.200000 2.200000 2.200000 2.200000 2.200000 2.200000 2.200000 2.200000 2.200000 cetearyl alcohol 11,000000 11,000000 11,000000 11,000000 11,000000 11,000000 11,000000 11,000000 11,000000 Docosan 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000 0.000000 Ceteareth-12 0.200000 0.350000 0.500000 0.050000 0.050000 0.050000 0.050000 0.050000 0.050000 Ceteareth-50 4.000000 3.700000 3.700000 3.700000 3.700000 3.700000 3.700000 3.700000 3.700000 Cutina GMS 0.500000 0.500000 0.500000 0.500000 0.500000 0.500000 0.500000 0.500000 0.500000 Water 49.900000 50.050000 50.35000 49.35000 49.35000 49.25000 49.850000 50.15000 51.35000 Acrylates Copolymer 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.500000 0.000000 0.000000 calcium chloride 0.000000 0.000000 0.000000 0.000000 0.000000 0.100000 0.000000 0.000000 0.000000 alginic acid 0.000000 0.000000 0.000000 1.000000 0.000000 1.000000 0.000000 0.000000 0.000000 iota-carrageenan 0.000000 0.000000 0.000000 0.000000 1.000000 0.000000 0.000000 0.000000 0.000000 Carbomer 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.200000 0.000000 monoethanolamine 1.100000 1.100000 1.100000 1.100000 1.100000 1.100000 1.100000 1.100000 1.100000 sodium sulfite 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 Water 17.440000 17.640000 17.190000 17.640000 17.640000 17.640000 17.640000 17.640000 17.640000 HEDP 60% (etidronic acid) 0.200000 0.200000 0.200000 0.200000 0.200000 0.200000 0.200000 0.200000 0.200000 ammonia (25%) 6,000000 6,000000 6,000000 6,000000 6,000000 6,000000 6,000000 6,000000 6,000000 vitamin C 0.100000 0.100000 0.100000 0.100000 0.100000 0.100000 0.100000 0.100000 0.100000 Perfume 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 0.400000 p-toluenediamine sulfate 3.240000 3.240000 3.240000 3.240000 3.240000 3.240000 3.240000 3.240000 3.240000 resorcinol 0.810000 0.810000 0.810000 0.810000 0.810000 0.810000 0.810000 0.810000 0.810000 m-aminophenol 0.160000 0.160000 0.160000 0.160000 0.160000 0.160000 0.160000 0.160000 0.160000 4-chlororesorcinol 0.570000 0.570000 0.570000 0.570000 0.570000 0.570000 0.570000 0.570000 0.570000 2,4-diaminophenoxyethanol 2HCl 0.580000 0.580000 0.580000 0.580000 0.580000 0.580000 0.580000 0.580000 0.580000 total content [wt.%] 105.36 105.36 105.36 105.36 105.36 105.36 105.36 105.36 105.36 phase separation temperature [°C] 57 57 57 74 74 63 54 56 57

examples

• erfindungsgemäße Färbekomponente in Form einer Öl-in-Wasser-Emulsion (M1-1)

Cetearylalkohol 15,000 Monoethanolamin 6,000 Glyceryl Stearate SE (Glycerylmono-, -distearat, 1:1, selbstemulgierend) 5,000 Aprikosenkernöl 3,500 Glycerin 2,500 2-Octyldodecanol 2,000 Natriumcetearylsulfat 1,200 Cocamidopropylbetain 0,700 iota-Carrageen (Chondrus Crispus Powder, INCI: Carrageenan) 0,500 Natriumsulfit 0,200 2-Methoxymethyl-p-phenylendiamin 0,150 Natriumchlorid 0,140 2,7-Naphthalindiol 0,067 Natriumsulfat 0,050 Resorcin 0,050 2,4-Diaminophenoxyethanol HCl 0,021 3-Amino-2-chlor-6-methylphenol (5-Amino-6-chloro-o-cresol) 0,003 Wasser ad 100,000 The following dye or composition (M1) was prepared (oil-in-water emulsion, all amounts in wt.%):

• coloring component according to the invention in the form of an oil-in-water emulsion (M1-1)

cetearyl alcohol 15,000 monoethanolamine 6,000 Glyceryl Stearate SE (glyceryl mono- and distearate, 1:1, self-emulsifying) 5,000 apricot kernel oil 3,500 glycerin 2,500 2-octyldodecanol 2,000 sodium cetearyl sulfate 1,200 cocamidopropyl betaine 0.700 iota-carrageenan (Chondrus Crispus Powder, INCI: carrageenan) 0.500 sodium sulfite 0.200 2-Methoxymethyl-p-phenylenediamine 0.150 sodium chloride 0.140 2,7-naphthalenediol 0.067 sodium sulfate 0.050 resorcinol 0.050 2,4-Diaminophenoxyethanol HCl 0.021 3-Amino-2-chloro-6-methylphenol (5-amino-6-chloro-o-cresol) 0.003 Water ad 100,000

• Entwickleremulsion (M2-1) (9 Gew.-% H₂O₂)

Mineralöl 17,00 Wasserstoffperoxid 9,00 Cetearylalkohol 3,50 PEG-40 Castor Oil 0,70 Natriumcetearylsulfat 0,40 Etidronsäure 0,20 Kaliumhydroxid 0,12 Dinatriumpyrophosphat 0,10 2,6-Dicarboxypyridin 0,10 Natriumbenzoat 0,04 Natriumsulfat 0,01 Natriumchlorid 0,01 Wasser 68,82 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) (6 wt.% H ₂ O ₂ ) Developer 6% sodium benzoate 0.04 2,6-dicarboxypyridine 0.10 disodium pyrophosphate 0.10 potassium hydroxide 0.09 propanediol-1,2 0.50 etidronic acid 0.15 Paraffinum Liquidum 2.00 Ceteareth-20 1.20 Cetearyl Alcohol 3.60 hydrogen peroxide 6.00 water, demineralized 86.22

developer emulsion (M2-4) (3 wt.% H ₂ O ₂ ) Developer 6% sodium benzoate 0.04 2,6-dicarboxypyridine 0.10 disodium pyrophosphate 0.10 potassium hydroxide 0.09 propanediol-1,2 0.50 etidronic acid 0.15 Paraffinum Liquidum 2.00 Ceteareth-20 1.20 Cetearyl Alcohol 3.60 hydrogen peroxide 3.00 water, demineralized 89.22

coloring

To produce ready-to-use oxidative dyes, the agent according to the invention (M1-1) 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 of oxidative dye per 1 g of 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 were easily prepared homogeneously 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.

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

• WO 2017108364A1 [0004]
• WO 2020234196A1 [0004]

Cited non-patent literature

• RÖMPP Chemistry Lexicon, as of December 2007 [0026]

Claims (15)

Agent for the oxidative color change of keratin fibers, in particular human hair, which is in the form of an oil-in-water emulsion and which, based on its weight, contains the following components: a) 40% by weight to 85% by weight of water, b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides, c) in a total amount of 1 - 30% by weight of at least one non-ionic water-in-oil emulsifier, d) at least one alkalizing agent, e) zero to less than 0.1% by weight of peroxide compounds, f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane are contained, and wherein the agent has a pH value in the range from 7 to 11, preferably in the range from 7.5 to 10.7, particularly preferably in the range of 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C. means after claim 1 , characterized in that the at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides is contained in a total amount of 0.05 to 2.0 wt.%, preferably 0.1 to 1.5 wt.%, particularly preferably 0.2 to 1.2 wt.%, extremely preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent. means after claim 1 or 2 , characterized in that the polysaccharide is selected from iota-carrageenan. Remedy according to one of the Claims 1 - 3 , characterized in that the at least one non-ionic water-in-oil emulsifier has an HLB value greater than 1.0 and less than or equal to 7.0. Remedy according to one of the Claims 1 - 4 , characterized in that the at least one non-ionic water-in-oil emulsifier is selected from i. linear, saturated C ₁₂ - C ₃₀ alkanols, ii. ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, iii. glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, iv. propylene glycol mono- and diesters of linear, saturated and unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, v. Sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, vi. Pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, viii. Glycerol monoethers of saturated and/or unsaturated, branched or unbranched alcohols with a chain length of 8 - 30, in particular 12 - 18 carbon atoms, ix. Partial esters of polyglycerols with n = 2 to 10 glycerol units and esterified with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ - C ₃₀ fatty acid residues, x. and mixtures of the aforementioned substances. Remedy according to one of the Claims 1 - 5 , characterized in that the at least one non-ionic water-in-oil emulsifier is selected from glycerol mono- and diesters of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated, having the formula (II):

wherein R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III),

wherein R4 represents a linear, saturated or linear, unsaturated C ₁₁ -C ₂₉ alkyl group, with the proviso that at least one and a maximum of two of the radicals selected from R1, R2 and R3 represent a grouping of the formula (III). Remedy according to one of the Claims 1 - 6 , characterized in that the at least one non-ionic water-in-oil emulsifier is selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols. Remedy according to one of the Claims 1 - 7 , characterized in that the at least one non-ionic water-in-oil emulsifier is selected from mixtures of at least one linear, saturated C ₁₂ - C ₃₀ alkanol selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols, in combination with at least one glycerol mono- or diester of linear or branched, saturated or unsaturated C ₁₂ - C ₃₀ carboxylic acids, which may be hydroxylated. Remedy according to one of the Claims 1 - 8 , characterized in that in addition, in a total amount of 0.1 - 10 wt. %, based on the weight of the agent, at least one surfactant g) is contained which is different from the non-ionic water-in-oil emulsifiers c), wherein the at least one additional surfactant g) is preferably selected from ionic surfactants, particularly preferably selected from anionic, zwitterionic and amphoteric surfactants and mixtures thereof, wherein mixtures of at least one anionic surfactant and at least one zwitterionic surfactant are extremely preferred. Remedy according to one of the Claims 1 - 9 , characterized in that at least one fat component is additionally contained which is different from the non-ionic water-in-oil emulsifiers c) and which is selected from oils liquid at 25°C and fat components with a melting point in the range from >25°C to 120°C, and mixtures thereof. means after claim 10 , characterized in that the at least one fat component which is different from the non-ionic water-in-oil emulsifiers c) is selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, esters of 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, mineral oil, isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols with 6 - 30 carbon atoms, Glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C _8-30 fatty acids, dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ alkanols, esters of 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, and mixtures thereof. Remedy according to one of the Claims 1 - 11 , characterized in that at least one polyol selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain may be interrupted by one or more oxygen atoms, is additionally contained before preferably in a total amount of 0.1 wt.% to 10 wt.%, preferably 0.5 to 5 wt.%, particularly preferably 1.0 to 3 wt.%, in each case based on the weight of the agent. 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 colour change, comprising the following method steps: i) providing a cosmetic agent (M1) for oxidative colour change of keratin fibres, in particular human hair, according to one of the Claims 1 until 12 , which is in the form of an oil-in-water emulsion and which, in each case based on its weight, contains the following components: a) 40% by weight to 85% by weight of water, b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of the aforementioned substances, c) in a total amount of 1 - 30% by weight of at least one non-ionic water-in-oil emulsifier, d) at least one alkalizing agent, e) zero to less than 0.1% by weight of peroxide compounds, f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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 of 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 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: i) at least one container (C1) containing an agent for the oxidative colour change of keratin fibres, in particular human hair, according to one of the Claims 1 until 12 , which is in the form of an oil-in-water emulsion and which, in each case based on its weight, contains the following components: a) 40% by weight to 85% by weight of water, b) at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides u, c) in a total amount of 1 - 30% by weight of at least one non-ionic water-in-oil emulsifier, preferably with an HLB value greater than 1.0 and less than or equal to 7.0, d) at least one alkalizing agent, e) zero to less than 0.1% by weight of peroxide compounds, f) optionally at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type, wherein no polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane is contained, and 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 of 8 to 10, extremely preferably 8.5 to 9.5, each measured at a temperature of 22 °C, and ii) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, 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 wt.% data in each case refer to the weight of the oxidizing agent preparation (M2), optionally containing at least one oil and/or at least one surfactant.