Oil-in-water emulsion having improved temperature stability, for oxidatively changing the color of keratin fibers

Abstract

The invention relates to a product for oxidatively changing the color of keratin fibers, which is present in the form of an oil-in-water emulsion and has improved stability, in particular improved temperature stability with respect to higher temperatures, and which also has optimized properties of use and / or improved coloring power, and to a method for oxidatively changing the color, using the aforementioned oxidative color changing product in the form of an emulsion.

Description

[0001] "Oil-in-water emulsion for oxidative color change of keratin fibers with improved

[0002] Temperature stability"

[0003] 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 to a method for oxidative color change using the aforementioned oxidative color change agent in emulsion form.

[0004] So-called oxidation dyes are used for permanent, intensive colorings with corresponding fastness properties. Oxidative dyes typically 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, particularly hydrogen peroxide, which are added to the first component shortly before application to the hair, or of atmospheric oxygen, either with each other or by coupling with one or more coupler components. Typically, primary aromatic amines with an additional free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraaminopyrimidine and its derivatives are used as developer components.Typically, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols, and substituted pyridine derivatives are used as coupler components. These oxidation dyes are characterized by excellent, long-lasting color results.

[0005] Conventional oxidative colorants have a more alkaline pH value, significantly above 9.0, to stabilize the dye precursors during storage and to accelerate the reaction during oxidative application. Ammonia, in particular, enables good color results, but also presents disadvantages for the user due to its odor and potential irritation to skin and mucous membranes. The alkalizing agent causes the keratin fibers to swell, allowing the dye precursors to penetrate the hair easily. However, the alkaline pH also intensifies 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, the outer layer of the keratin fiber.This manifests itself in increased roughness, poorer feel, reduced shine, and poorer stability of the fiber. The roughened cuticle structure allows small molecules, such as water, to escape more quickly. As a result, damaged hair further loses its suppleness and elasticity. The roughened fiber surface also impairs the colorfastness properties.

[0006] To reduce hair damage caused by alkaline oxidative color-changing agents, these products often contain fats or oils. 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 power of the hair colorant can also be improved by the content of oil and / or fat components, so that the resulting color is less selective, absorbing roughly equally into both the damaged and undamaged sections of the keratin fibers.

[0007] Many oxidation dye precursors are aromatic amines. Some of these aromatic amines are preferably used in the form of their salts, particularly 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 contribute a higher salt load to the dyeing component. This is particularly true for darker shades, which contain a higher overall concentration of oxidation dye precursors. Dyeing components in emulsion form are often less stable due to this high salt concentration and tend to separate into the oil and water phases over time. This phase separation is accelerated by increasing the storage temperature.However, thermal stability is essential for a mass-produced emulsion, as the product can be exposed to significant temperature fluctuations during transport from production through various intermediate storage facilities to the point of sale in online or brick-and-mortar retail stores. Both high and very low temperatures can be detrimental to emulsion stability. Particularly problematic, however, are high temperatures of 50°C and above, which typically occur during ocean transport on container ships.

[0008] In the prior art, this problem was often addressed by adding a polymeric gelling agent, such as 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 recommended to avoid polyacrylates and other polymeric thickeners that are synthesized from petrochemical raw materials and / or that can be considered microplastics.

[0009] Replacing petrochemically based synthetic polymers with natural or biogenic gel formers, which may be chemically or physically modified, is not trivial, however. For example, the naturally based gel former sodium carboxymethylcellulose, also known as cellulose gum, provides insufficient emulsion stability in the alkaline pH ranges required for hair coloring and bleaching products, particularly under prolonged thermal stress. The polymer sodium carboxymethylcellulose itself also degrades in aqueous alkaline media upon prolonged exposure to temperatures above 50°C. This is unproblematic for the formulation of anhydrous bleaching powders and bleaching pastes, which is why sodium carboxymethylcellulose is used in many such products. However, sodium carboxymethylcellulose is unsuitable for the highly water-containing, alkaline emulsions present.

[0010] Therefore, special efforts are being made to develop efficient oxidative color-changing agents, in particular agents for lightening and / or coloring keratin fibers, which achieve good coloring and lightening results and have high emulsion stability, especially against thermal stress.

[0011] 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 application behavior and viscosity during the exposure time on the keratin fibers.

[0012] During oxidative coloring, the oxidizing agent destroys the fiber's natural pigment, melanin. This lightens or bleaches the keratin fibers. By adding oxidative dye precursors and / or direct dyes to the oxidative color-change agent, even darker hair can be dyed in many fashionable shades, which are often lighter than the fiber's original color.

[0013] Oxidative color-changing agents that are adjusted to a weakly alkaline or even weakly acidic pH value are not preferred by consumers because of the often less satisfactory color result.

[0014] 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 further 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 petrochemically based thickeners. The stabilizers should not impair the coloring properties, in particular with regard to color intensity and balancing power.

[0015] State of the art

[0016] The use of iota-carrageenan or alginic acid in the form of their salts with polyvalent ions in oxidative hair color modification was known from WO2017108364A1. This published application teaches the use of iota-carrageenan or alginic acid in the form of calcium salts as a release film, for example, in the form of a hair highlighting film. WO 2020234196A1 teaches oil-in-water macroemulsions containing a hydrophobic active ingredient in the oil phase and stabilized with a polymeric stabilizer. The list of polymeric stabilizers non-specifically includes 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 are documented only 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 achieving the object of the invention due to its lack of thermal stability in alkaline media.

[0017] 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, thus eliminating the need for petrochemical-based thickeners and microplastics.

[0018] The present invention relates, in a first embodiment, to an agent for the oxidative color change of keratinic fibers, in particular human hair, which agent is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, 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-% 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 present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C.

[0019] 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.%, extraordinarily preferably 55 - 65 wt.% water.

[0020] The agent according to the invention is an oil-in-water emulsion thickened and stabilized with at least one polysaccharide selected from iota-carrageenan and alginic acid, as well as 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.

[0021] Surprisingly, it was found that an oil-in-water emulsion thickened with iota-carrageenan or alginic acid, intended as an alkalizing component for an oxidative dye or brightening agent, exhibits excellent thermal stability, particularly 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 compromising viscosity stability.

[0022] 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 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.%, extraordinarily preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent.

[0023] 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.

[0024] It is particularly advantageous that iota-carrageenan is introduced via the molten oil phase or via the hot aqueous phase during emulsion preparation for the preparation of the emulsions according to the invention. The temperatures of the oil phase and the aqueous phase before mixing and emulsification are in the range of 50-95°C, preferably in the range of 65-85°C.

[0025] The thickening of iota-carrageenan or alginic acid can be enhanced in the presence of at least one salt selected from potassium and calcium salts with a water solubility of at least 500 mg / l at 20°C. However, no consistent results could be obtained for the temperature stabilization effect according to the invention for the addition of a potassium or calcium salt.

[0026] 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 wt.%. Further agents preferred according to the invention contain at least one potassium salt in a total amount of 0.1 to 0.4 wt.%, 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.

[0027] 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, as well as mixtures of these salts.

[0028] 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 particularly preferred according to the invention are selected from calcium acetate (water solubility 374 g / l), calcium lactate, calcium gluconate, and calcium gluconate lactate.

[0029] The agent particularly preferably 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.%, extraordinarily preferably 0.5 - 2.5 wt.%, in each case based on the weight of the agent (M1).

[0030] A further 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 wt. %, preferably 2-25 wt. %, particularly preferably 5-20 wt. %, extraordinarily preferably 10-20 wt. %, 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. Further 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.

[0031] Nonionic water-in-oil emulsifiers preferred according to the invention, which preferably have an HLB value greater than 1.0 and less than / equal to 7.0, are selected from i. linear, saturated C12-C10-alkanols, ii. ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated,

[0032] Hi. Glycerol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, iv. Propylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, v. Sorbitan mono-, di-, and triesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vi. Pentaerythrityl mono-, di-, tri-, and tetraesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C12-C50 carboxylic acids, which may be hydroxylated, 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, 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 Ca - Cao fatty acid residues, which preferably have an HLB value of less than or equal to 7, x. as well as mixtures of the aforementioned substances.

[0033] Particularly preferred non-ionic 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 having 12 - 30 carbon atoms, in particular having 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,

[0034] Esters and in particular partial esters of a polyol with 2-6 carbon atoms and linear or branched, saturated or unsaturated fatty acids with 12-30, in particular 14-22 carbon 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 C12 - CaO-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 C12 - CaO-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 C12 - CaO-carboxylic acids, which may be hydroxylated, of which 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.Mono- and diesters are particularly preferred according to the invention. Preferred C12-C10 fatty acid residues 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.

[0035] 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 Ca - Cao fatty acid residues, provided they have an HLB value of less than or equal to 7, as well as mixtures of the aforementioned substances.

[0036] 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 C12 - CaO carboxylic acids, which may be hydroxylated, having the formula (II): (II), wherein

[0037] R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III), (III), wherein

[0038] R4 represents an unbranched or branched, saturated or unsaturated Cn-C27 alkyl group or Cn-C27 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),

[0039] The radical R4 in formula (III) represents an unbranched or branched, saturated or unsaturated Cn-C27 alkyl group.

[0040] R4 is preferably an unbranched, saturated Cn-C27 alkyl group. More preferably, R4 is an unbranched, saturated C1a-C1a alkyl group. R4 is particularly preferably an unbranched, saturated C18-C16 alkyl group.

[0041] Preferred agents according to the invention are characterized in that at least one compound from the group of formulas (I la) to (I Id) is contained as glyceryl fatty acid esters of the general formula (II): (lid)

[0042] The compounds of formulas (Ila) to (Id) are also known under the names glyceryl monostearate and glyceryl monopalmitate.

[0043] Further agents preferred 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 esters of the general formula (II):

[0044] The compounds of formula (Ile) to (IIIh) are also known under the names glyceryl distearate and glyceryl dipalmitate.

[0045] 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).

[0046] 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 formula (II).

[0047] 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.%.

[0048] In a further particularly preferred embodiment, an agent according to the invention is characterized in that it contains, as glyceryl fatty acid ester of 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.

[0049] 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, for example, to be 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.

[0050] Further particularly preferred agents 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 particularly preferred agents 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 present in a total amount of 1-25 wt.%, preferably 2-20 wt.%, particularly preferably 5-15 wt.%, extraordinarily preferably 10-15 wt.%, in each case based on the weight of the agent.

[0051] 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 C12-C10-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 C12-C10-carboxylic acids, which may be hydroxylated.

[0052] Further particularly preferred agents 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 C12-C10-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 C12-C10-carboxylic acids, which may be hydroxylated, wherein the said non-ionic water-in-oil emulsifiers are present in a total amount of 1-30 wt.%, preferably 2-25 wt.%, particularly preferably 5-20 wt.%, extraordinarily preferably 10-20 wt.%, based on the weight of the agent.

[0053] Particularly advantageous water-in-oil emulsifiers are stearyl alcohol, cetyl alcohol, glyceryl monostearate, especially 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.

[0054] Preferred agents according to the invention are characterized in that the non-ionic 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 C12-C10-alkanols, ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, glycerol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, propylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C12- Cso-carboxylic acids, which may be hydroxylated, pentaerythritol mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C12 - Cso-carboxylic acids,which may be hydroxylated, methyl glucose mono- and diesters of linear or branched, saturated or unsaturated C12-C9-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 Ca-C9-fatty acid residues, which preferably have an HLB value of less than or equal to 7, as well as mixtures of the aforementioned substances.

[0055] Particularly preferred agents according to the invention are characterized in that the non-ionic water-in-oil emulsifier(s) c), preferably with an HLB value greater than 1.0 and less than or equal to 7.0, is / are selected from the mono-, di-, tri-, and tetraesters of ethylene glycol or pentaerythritol with linear or branched, saturated or unsaturated fatty acids having 12-30, in particular 14-22, carbon atoms, which may be hydroxylated. Mono- and diesters are preferred according to the invention. Preferred C12-C30 fatty acid residues 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 non-ionic 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.

[0056] The HLB values ​​can be calculated, for example, according to Griffin, as presented or tabulated in the RÖMPP Chemistry Encyclopedia, 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 the literature contains differing information 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 of the invention. If a clear HLB value cannot be determined in this way, the HLB value specified by the emulsifier manufacturer should be used for the teaching of the invention. If this is also not possible, the HLB value must be determined experimentally.

[0057] Further agents preferred according to the invention are characterized in that they additionally contain, in a total amount of 0.1 - 10 wt.%, based on the weight of the agent, at least one surfactant g) which is different from the non-ionic water-in-oil emulsifiers c).

[0058] Surfactants and emulsifiers within the meaning of the present application are amphiphilic (bifunctional) compounds consisting of at least one hydrophobic and at least one hydrophilic moiety. The hydrophobic moiety is preferably a hydrocarbon group with 8-28 carbon atoms, which can be saturated or unsaturated, linear or branched. This C8-C28 alkyl group is particularly preferably linear. Basic properties of surfactants and emulsifiers are oriented absorption at interfaces, aggregation into micelles, and the formation of lyotropic phases.

[0059] 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.

[0060] 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, as well as 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.

[0061] Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate, sulfonate, or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as 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, each containing 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

[0062] Amphoteric surfactants are surface-active compounds that, in addition to a C5-C24 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO5H group in the molecule 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 containing approximately 8 to 24 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate, and C12-C18-acylsarcosine.

[0063] Suitable anionic surfactants are all anionic surface-active substances suitable for use on the human body that contain a water-solubilizing anionic group, for example a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms, preferably 8 to 24 carbon atoms, in the molecule. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Examples of suitable anionic surfactants are, 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, acylsarcosides, acyltaurides, 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-olefin sulfonates, sulfonates of unsaturated fatty acids with up to 6 double bonds, alpha-sulfofatty acid methyl esters of fatty acids, C8-C2o-alkyl sulfates and C8-C2o-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, C8-C2o-alkyl sulfates, C8-C2o-alkyl ether sulfates, and Cs-C2o-ether carboxylic acids with 8 to 20 carbon 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 the at least one surfactant is preferably g).which is different from the non-ionic water-in-oil emulsifiers c), in the agent (M1) preferred according to the invention 0.1 - 5 wt.%, preferably 0.5 - 4 wt.%, particularly preferably 1 - 3 wt.% and extraordinarily preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1).

[0064] 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 anionic surfactants, in a total amount of 0.1 - 5 wt.%, preferably 0.5 - 4 wt.%, particularly preferably 1 - 3 wt.% and extraordinarily preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1).

[0065] 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 extraordinarily preferably 0.6 to 1 wt.%, in each case based on the weight of the agent (M1).

[0066] 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 extraordinarily preferably 1.5 to 2.5 wt.%, in each case based on the weight of the agent (M1).

[0067] 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).

[0068] Further agents (M1) preferred according to the invention are characterized in that they additionally contain 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 having a melting point in the range from >25°C to 120°C, and mixtures thereof.

[0069] Fat components according to the invention are lipophilic organic substances that have a water solubility of a maximum of 0.001 wt.% or less at 20°C. These fatty substances include oils, fats, and waxes. Linear, saturated fatty alcohols are considered nonionic water-in-oil emulsifiers. Essential oils and perfume oils or fragrances are also not considered fatty substances for the purposes of the present invention.

[0070] All information on the physical states of substances (solid, liquid, gaseous) in this application refers to standard conditions. "Standard conditions" for the purposes of this application are a temperature of 25°C and a pressure of 1013.25 mbar. Particularly preferred agents (M1) 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 branched and saturated or unsaturated alkanols having 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C 8 - 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, mineral oil,Isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols having 6-30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated Cs-C fatty acids, dicarboxylic acid esters of linear or branched C2-C10 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.

[0071] Among the oils preferred according to the invention which are liquid at 25°C and which 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.

[0072] Further oils preferred according to the invention are selected from the triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated Ca ao 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 components of coconut oil and the like, as well as mixtures of these oils, can be particularly suitable. Also suitable, however, are synthetic triglyceride oils or those obtained by transesterification of natural oils, in particular capric / caprylic triglycerides, e.g., the commercial product Myritol® 318 (BASF) with unbranched fatty acid residues, and glyceryl triisostearin with branched fatty acid residues.

[0073] Further oils which are particularly preferred according to the invention are selected from the dicarboxylic acid esters of linear or branched O2-C10-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.

[0074] 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.

[0075] Further oils that may be preferred according to the invention are selected from the C5-C22 fatty alcohol esters of monobasic or polybasic C2-C7 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.

[0076] Further agents (M1) preferred according to the invention are characterized in that the at least one fatty component which is different from the non-ionic water-in-oil emulsifiers c) is selected from fatty components with a melting point in the range of >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 Cs-Cs alcohols with saturated Cs-Cs monocarboxylic acids, in particular stearyl laurate, cetearyl stearate, cetyl palmitate and myristyl myristate, esters of a saturated, monohydric Cs-Cs alkanol and a saturated Cs-Cs monocarboxylic acid, in particular cetyl behenate, Stearyl behenate C20-C40 alkyl stearate, candelilla wax, carnauba wax and beeswax, glycerol triesters of saturated linear C12 - Cso-carboxylic acids,which may be hydroxylated, in particular castor wax, as well as mixtures of the aforementioned substances.

[0077] 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 extraordinarily preferably 1 to 2 wt.%, in each case based on the weight of the agent (M1).

[0078] Essential oils and perfume oils or fragrances are not considered fatty substances for the purposes of the present invention. Essential oils are understood, according to the invention, to be mixtures of volatile components produced by steam distillation from plant-based raw materials, such as citrus oils. Wherever reference is made to a cosmetic oil in this application, this always refers to a cosmetic oil that is neither a fragrance nor an essential oil, is liquid under normal conditions, and is immiscible with water.

[0079] The definition of a fragrance substance within the meaning of this application corresponds to the definition commonly used by those skilled in the art, as found in the RÖMPP Chemical Dictionary, as of December 2007. According to this definition, a fragrance substance 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 necessary physical and chemical properties are a low molecular weight of a maximum of 300 g / mol, a high vapor pressure, minimal water solubility and high lipid solubility, weak polarity, and the presence of at least one osmophoric group in the molecule.In order to distinguish volatile, low-molecular substances, which are usually and also in the sense of the present application not regarded and used as fragrances but primarily as solvents, such as ethanol, propanol, isopropanol and acetone, from fragrances according to the invention, fragrances according to the invention have a molecular mass of 74 to 300 g / mol, contain at least one osmophoric group in the molecule and have an odor and / or taste, i.e. they excite the receptors of the hair cells of the olfactory system.

[0080] Particularly preferred agents (M1) according to the invention are characterized in that at least one essential oil, perfume oil or fragrance is contained, preferably in a total amount of 0.1 - 3 wt.%, particularly preferably 0.2 - 1 wt.%, extraordinarily preferably 0.5 - 0.8 wt.%, in each case based on the weight of the agent according to the invention.

[0081] 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 having 2 to 20 carbon atoms and 2 to 15 hydroxyl 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.

[0082] Preferred polyols of this type according to the invention are selected from glycerol, 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, hexanetriols such as 1,2,6-hexanetriol, 1,2-octanediol, 1,8-octanediol, dipropylene glycol, tripropylene glycol, diglycerol, triglycerol, 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, as well as mixtures thereof, with glycerin, 1,2-propylene glycol, PEG-8, 1,3-butylene glycol, 1,6-hexanediol, dipropylene glycol, and xylitol, as well as 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.

[0083] Particularly preferred agents (M1) according to the invention 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 may be interrupted by one or more oxygen atoms, is present 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.

[0084] 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, extraordinarily preferably 7000-12000 mPas, in each case measured at 20°C.

[0085] A Haake model MVII rheometer can be used for the measurement, for example at a shear rate of 7.2 revolutions per second.

[0086] Oxidative color change processes on keratin fibers typically occur in a neutral to alkaline environment. Therefore, the pH of the agent according to the invention is in the range of 7 to 11, preferably in the range of 7.5 to 10.7, particularly preferably in the range of 8 to 10, and extremely preferably 8.5 to 9.5, each measured at a temperature of 22°C.

[0087] As a further mandatory ingredient, the agent according to the invention therefore contains at least one alkalizing agent.

[0088] The alkalizing agents preferably suitable for adjusting the pH 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.

[0089] Color-changing agents preferred according to the invention are characterized in that they do not contain ammonia or ammonium hydroxide.

[0090] Particularly preferred alkalizing agents are selected from alkanolamines, alkali metal hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali metal phosphates, and dialkali monohydrogen phosphates, as well as mixtures of these substances. The alkali metal ions in the aforementioned alkalizing salts are preferably lithium, sodium, or potassium, especially sodium or potassium.

[0091] The basic amino acids that can be used as alkalizing agents are preferably selected from the group consisting of 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.

[0092] The alkali hydroxides usable as alkalizing agents are preferably selected from sodium hydroxide and potassium hydroxide, as well as mixtures thereof. Potassium hydroxide is particularly preferred according to the invention.

[0093] 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 C2-C6 alkyl parent structure which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group consisting of 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, and 2-amino-2-methylpropan-1,3-diol and mixtures thereof. Alkanolamines which are particularly preferred according to the invention are selected from the group consisting of 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropan-1,3-diol; 2-aminoethan-1-ol is extremely preferred.However, secondary amines such as diisopropanolamine (1,1'-iminodipropan-2-ol) are also suitable alkalizing agents according to the invention. Particularly preferred alkalizing agents according to the invention contain 2-aminoethane-1-ol, potassium hydroxide, L-arginine, L-lysine, and mixtures thereof. Extremely preferred color-changing agents according to the invention contain a mixture of 2-aminoethane-1-ol, potassium hydroxide, L-arginine, and L-lysine.

[0094] 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.%, extraordinarily preferably 1.2 - 3 wt.%, in each case based on the weight of the color-changing agent.

[0095] 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) having an acidic pH immediately before application to the keratin fibers to form a ready-to-use colorant. The agent 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 degrades the melanin in the keratin fibers.If the agent (M1) according to the invention contains oxidation dye precursors, the hydrogen peroxide causes them to react with each other and form permanent dyes. To prevent this dye formation from occurring during storage of the agent, the agents according to the invention contain zero to less than 0.1 wt.% of peroxide compounds, based on their weight.

[0096] 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.

[0097] Oxidation dye precursors can be divided into two categories based on their reactivity, so-called developer components and coupler components.

[0098] Coupler components do not produce significant coloration on their own during oxidative dyeing, but always require the presence of developer components. Developer components can form the actual dye on their own. The developer and coupler components are usually used in free form. However, for substances containing amino groups, it may be preferable to use them in salt form, particularly in the form of hydrochlorides, hydrobromides, or sulfates.

[0099] 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-diaminopropan-2-ol, bis-(2-hydroxy-5-aminophenyl)methane, 1,3-bis-(2,5-diaminophenoxy)propan-2-ol, N,N'-Bis-(4-amino-phenyl)-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.

[0100] Very particularly preferred developer components are selected from 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-tolylenediamine, 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, as well as their physiologically acceptable salts. Exceptionally preferred are 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-tolylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, and mixtures of these compounds, as well as their physiologically acceptable salts.

[0101] 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.%, extraordinarily preferably 0.5 to 2.0 wt.%, in each case based on the weight of the agent (M1) according to the invention.

[0102] Preferably, at least one coupler component or its salt is present in a total amount of 0.001 to 4 wt.%, preferably 0.01 to 3 wt.%, particularly preferably 0.05 to 2 wt.%, extraordinarily preferably 0.1 to 1 wt.%, in each case based on the weight of the agent (M1) according to the invention.

[0103] The total amount of oxidation dye precursors or salts thereof 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.%, extraordinarily preferably 0.6 to 3.0 wt.%, in each case based on the weight of the agent (M1).

[0104] Coupler components within the meaning of the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This results in a covalent bond 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), said groups are preferably located in the ortho or meta position to one another.

[0105] 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:

[0106] - 3-aminophenol (m-aminophenol) and / or its derivatives,

[0107] - 3-aminoaniline (m-diaminobenzene) and / or its derivatives,

[0108] - 2-aminoaniline (1,2-diaminobenzene; o-diaminobenzene) and / or its derivatives,

[0109] - 2-aminophenol (o-aminophenol) and / or its derivatives,

[0110] - naphthalene derivatives containing at least one hydroxy group,

[0111] - Di- or trihydroxybenzene and / or their derivatives,

[0112] - pyridine derivatives,

[0113] - pyrimidine derivatives,

[0114] - monohydroxyindole derivatives and / or monoaminoindole derivatives,

[0115] - monohydroxyindoline derivatives and / or monoaminoindoline derivatives,

[0116] - Pyrazolone derivatives, such as 1-phenyl-3-methylpyrazol-5-one,

[0117] - Morpholine derivatives, such as 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,

[0118] - Quinoxaline derivatives, such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

[0119] Mixtures of two or more compounds from one or more of these classes are also preferred according to the invention in this embodiment.

[0120] Erfindungsgemäß besonders bevorzugte zusätzliche Kupplerkomponenten sind ausgewählt aus 3- Aminophenol, 5-Amino-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophen- oxyethanol, 5-Amino-4-chlor-2-methylphenol, 5-(2-Hydroxyethyl)amino-2-methylphenol, 2,4-Di- chlor-3-aminophenol, 2-Aminophenol, 3-Phenylendiamin, 2-(2,4-Diaminophenoxy)ethanol, 1 ,3-Bis- (2,4-diaminophenoxy)propan, 1-beta-Hydroxyethyl-3,4-methylendioxyanilin, 1-Methoxy-2-amino-4- (2’-hydroxyethylamino)benzol (= 2-Amino-4-Hydroxyethylaminoanisol), 1 ,3-Bis (2,4-diaminophe- nyl)propan, 2, 6-Bis(2'-hydroxyethylamino)-1 -methylbenzol, 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-methylphenylamin, 1-Amino-3-bis-(2- hydroxyethyl)aminobenzol, Resorcin, 2-Methylresorcin,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.

[0121] 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 aforementioned components. It may be preferable to avoid resorcinol and resorcinol derivatives.

[0122] 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.

[0123] 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 develop the color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, or indophenols.

[0124] Direct dyes can be anionic, cationic, or non-ionic. The direct dyes are preferably present in an amount of 0.001 to 2% by weight, based on the weight of the oxidative color-change agent.

[0125] 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 marketed under the trademark Arianor are also preferred cationic direct dyes according to the invention. Particularly suitable nonionic direct dyes are nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic direct dyes are those known under the international designations "Arianor" and "Arianor" respectively.Handelsnamen 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 bekannten Verbindungen, sowie 1 ,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(2-hydroxyethyl)- amino-2-nitrobenzol, 3-Nitro-4-(2-hydroxyethyl)aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitro- phenol, 4-[(2-Hydroxyethyl)amino]-3-nitro-1 -methylbenzol, 1-Amino-4-(2-hydroxyethyl)amino-5- chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2'-Ureidoethyl)amino-4-nitrobenzol, 2-[(4-Amino-2- nitrophenyl)amino]-benzoesäure, 6-Nitro-1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1 ,4-naphthochi- non, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoe- säure und 2-Chlor-6-ethylamino-4-nitrophenol.According to the invention, 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 is very particularly preferably contained.

[0126] The agents (M1) according to the invention are further characterized in that they do not contain any polymer or copolymer with acrylate-, methacrylate- or vinyl-containing monomers and no polyurethane, i.e., based on their weight, 0.0 wt.% of the aforementioned (co)polymers are contained in (M1).

[0127] Oxidative color-changing agents containing ammonia or ammonium hydroxide release ammonia during the color-changing process, so non-volatile alkalizing agents, i.e., all alkalizing agents other than ammonia or ammonium hydroxide, may be preferred according to the invention. Therefore, for some applications according to the invention, it may be preferred for the agents according to the invention not to contain ammonia or ammonium hydroxide as an alkalizing agent.

[0128] A further subject of the present invention is a packaging unit (kit of parts) which - packaged separately - comprises the following: i) at least one container (C1) containing an agent for the oxidative color change of keratin fibers, in particular human hair, which agent is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, 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-% 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 present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C, and ii) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40-96 wt.%, preferably 65-90 wt.%, particularly preferably 70-80 wt.%, water, furthermore hydrogen peroxide in a total amount of 0.5 to 23 wt.%, further preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, very particularly preferably 5 to 18 wt.% and most preferably 6 to 12 wt.%.-%, and has a pH in the range from 2.0 to 6.5, preferably 2.5 - 5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C, wherein the wt. % data relate in each case to the weight of the oxidizing agent preparation (M2), optionally containing at least one oil and / or at least one surfactant.

[0129] 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.

[0130] 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. Regarding further preferred embodiments of the use according to the invention, the statements regarding the agents according to the invention for oxidative color change apply mutatis mutandis.

[0131] The present invention further relates to a process for oxidative hair coloring, which comprises the following process steps: i) providing a cosmetic agent (M1) for the oxidative color change of keratinic 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: 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 is present, 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, extraordinarily preferably 8.5 to 9.5, in each case 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.%, further preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, most particularly preferably 5 to 18 % by weight and most preferably 6 to 12 % by weight.-%, and 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 relate in each case to the weight of the oxidizing agent preparation (M2), optionally containing at least one surfactant and / or an oil, iii) mixing the cosmetic agent (M1) with the oxidizing agent preparation (M2), preferably in a weight ratio (M1):(M2) in the range of 1:0.8 to 1:2.5, preferably 1:1 to 1:2, directly thereafter iv) applying the mixture obtained in step iii) to the hair and leaving this mixture 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 on the hair, v) rinsing the hair with water and / or a cleansing composition, and vi) if appropriate, applying a post-treatment product to the hair and, if appropriate, rinsing, followed by drying.

[0132] For oxidative hair coloring 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 coloring agent immediately before application to the hair and then applied to the hair. The agent according to the invention (M1) and the oxidizing agent-containing composition (M2) are usually matched to one another such that, at a mixing ratio of 1:1, based on parts by weight, the finished application mixture contains an initial hydrogen peroxide concentration of 0.5-12% by weight, preferably 2-10% by weight, particularly preferably 3-6% by weight of hydrogen peroxide (calculated as 100% H2O2), 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.

[0133] 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.

[0134] For the purposes of the invention, the term “room temperature” refers to the temperature in the room in which a person usually applies a hair coloring or lightening product, i.e. usually a bathroom or a hairdressing salon, where the temperature is in the range of 10 - 29 °C.

[0135] Leaving the coloring or lightening application mixture in process step iv) in the hair coloring 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.

[0136] 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.%, of water.

[0137] The oxidizing agent preparation (M2) used in the color-change kits according to the invention and those preferred according to the invention, as well as in the color-change processes according to the invention and those preferred according to the invention, further contains, 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 extraordinarily 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 from 2.0 to 6.5, preferably 2.5 to 5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C.

[0138] Oxidative color change processes on keratin fibers typically occur in a neutral to alkaline environment; even a slightly acidic pH value produces acceptable color results. Therefore, the pH value of the agent (M1) according to the invention is in the range of 7 to 11, preferably in the range of 7.5 to 10.7, particularly preferably in the range of 8 to 10, and extremely preferably 8.5 to 9.5, each measured at a temperature of 22°C.

[0139] The ready-to-use color-changing agent obtained by mixing the agent (M1) according to the invention with the oxidizing agent preparation (M2) has a pH in the range of 6.5-10, preferably 7-9.5, particularly preferably 7.5-9, extraordinarily preferably 7.5-8.5, further extraordinarily preferably 7.5-8, in each case measured at a temperature of 22 °C.

[0140] Surprisingly, it has been found that an application mixture with a viscosity suitable for application and drip-free retention on the hair is obtained by mixing the agent (M1) according to the invention or preferred according to the invention with an oxidizing agent preparation (M2) containing xanthan gum, preferably 1 to 5% by weight, particularly preferably 1.5 to 4% by weight, extraordinarily preferably 2-3% by weight of xanthan gum, based in each case on the weight of the oxidizing agent preparation (M2). The resulting consistency of the application mixture leads to optimal application properties, for example, for brush application.The resulting application mixtures, particularly with weight-based 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 to 8000 mPas, preferably 4000 to 7000 mPas, particularly preferably 4500 to 6500 mPas, and extraordinarily preferably 5000 to 6000 mPas, measured in each case at 20°C using 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.

[0141] 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.

[0142] Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate, sulfonate, or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as 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, each containing 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

[0143] Amphoteric surfactants are surface-active compounds that, in addition to a C5-C24 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO5H group in the molecule 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 containing approximately 8 to 24 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate, and C12-C18-acylsarcosine.

[0144] Suitable anionic surfactants are all anionic surface-active substances suitable for use on the human body that contain a water-solubilizing anionic group, for example a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms, preferably 8 to 24 carbon atoms, in the molecule. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Examples of suitable anionic surfactants are, 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, acylsarcosides, acyltaurides, 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-olefin sulfonates, sulfonates of unsaturated fatty acids with up to 6 double bonds, alpha-sulfofatty acid methyl esters of fatty acids, C8-C2o-alkyl sulfates and C8-C2o-alkyl ether sulfates with up to 15 oxyethyl groups, mixtures of surface-active hydroxysulfonates, sulfated hydroxyalkyl polyethylene and / or hydroxyalkyl 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, C8-C2o alkyl sulfates, C8-C2o alkyl ether sulfates, and C8-C2o ether carboxylic acids with 8 to 20 carbon atoms in the alkyl group and up to 12 ethylene oxide groups in the molecule. Sodium cetearyl sulfate is particularly preferred.

[0145] 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). Further particularly preferred 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.%.

[0146] 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 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). 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 composed of a hydrophobic part and a hydrophilic head group, whereby the hydrophobic part generally consists of a hydrocarbon backbone (e.g. consisting of one or two linear or branched alkyl groups), and the positive charge(s) are localized in the hydrophilic head group.Cationic surfactants adsorb at interfaces and aggregate in aqueous solution above the critical micelle concentration to form positively charged micelles.

[0147] Preferred according to the invention are cationic surfactants of the quaternary ammonium compound, esterquat, and alkylamidoamine type. 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), where x + y + z = 10. The long alkyl groups of the above-mentioned surfactants preferably have 10 to 22, particularly preferably 12 to 18 carbon atoms. Behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride are particularly preferred, with stearyltrimethylammonium chloride being extremely preferred. Further 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 marketed under the trademarks Stepantex, Dehyquart, and Armocare.

[0148] C10-C22-alkyltrimethylammonium chlorides have proven to be particularly suitable with regard to optimum application properties and optimum color results. Particularly preferred oxidizing agent preparations (M2) used according to the invention are therefore characterized in that they contain at least one cationic surfactant in a total amount of 0.05-3 wt. %, particularly preferably 0.1-1.5 wt. %, extraordinarily preferably 0.3-0.9 wt. %, based in each case 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, as well as mixtures of these surfactants, is present. 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 from 0.1 to 1.5 wt.%, extraordinarily preferably from 0.3 to 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

[0149] A further 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.%, extraordinarily preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

[0150] A further 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.%, extraordinarily preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

[0151] 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.%, extraordinarily preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

[0152] A further 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.%, extraordinarily preferably 0.3 - 0.9 wt.%, in each case based on the weight of the oxidizing agent preparation (M2).

[0153] Surprisingly, it has been found that an application mixture with a viscosity suitable for application and drip-free retention on the hair is obtained by mixing the agent (M1) according to the invention or preferred according to the invention with an oxidizing agent preparation (M2) containing at least one oil, preferably at least one oil in a total amount of 0.5-40 wt. %, preferably 1-25 wt. %, particularly preferably 3-20 wt. %, extraordinarily preferably 5-17 wt. %, in each case based on the weight of the oxidizing agent preparation (M2). The resulting consistency of the application mixture 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, extraordinarily 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.

[0154] Further oxidizing agent preparations (M2) preferably used according to the invention contain at least one oil. The at least one oil is preferably selected from mineral oils, branched fatty alcohols having 8-24 carbon atoms, dialkyl ethers having 6 to 18 carbon atoms in the alkyl groups, 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 mixtures of the aforementioned substances. Mineral oil is particularly preferred.

[0155] 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.%, extraordinarily preferably 5 - 17 wt.%.

[0156] 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.%, extraordinarily preferably 5-17 wt.%, mineral oil.

[0157] 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 containing 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 H2O2 (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), as well as mixtures of these oxidizing agents. Oxidizing agents used with particular preference according to the invention are aqueous hydrogen peroxide solutions.The concentration of a hydrogen peroxide solution is determined, on the one hand, by legal requirements and, on the other hand, by the desired effect; 6 to 12 percent by weight solutions in water are 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, 1 to 24 percent by weight, preferably 4 to 10 percent by weight, particularly preferably 3 to 6 percent by weight of hydrogen peroxide (calculated as 100% H2O2).

[0158] 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 (M1) according to the invention and the oxidizing agent-containing composition (M2) are usually matched to one another such that, at a mixing ratio of 1 to 1, based on parts by weight, the ready-to-use agent has an initial hydrogen peroxide concentration of 0.5-12% by weight, preferably 2-10% by weight, particularly preferably 3-6% by weight of hydrogen peroxide (calculated as 100% H2O2), 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-based mixing ratio of 1:2 or 1:3 or even 2:3. Preferred weight-based mixing ratios (M1):(M2) 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.

[0159] The ready-to-use color-changing agent obtained by mixing the agent (M1) according to the invention with the oxidizing agent preparation (M2) preferably has a pH in the range of 6.5-10, more preferably 7-9.5, particularly preferably 7.5-9, extraordinarily preferably 7.5-8.5, further extraordinarily preferably 7.5-8, in each case measured at a temperature of 22 °C.

[0160] For coloring that requires a significant lightening of very dark hair, the use of hydrogen peroxide or its adducts with organic or inorganic compounds is often insufficient. 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.

[0161] 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.

[0162] 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.

[0163] The subject matter of the present invention is summarized by the following points:

[0164] 1. 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: 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 is present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C.

[0165] 2. Agent according to point 1, characterized in that the at least one polysaccharide selected from iota-carrageenan and alginic acid and mixtures of these polysaccharides is present 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.%, extraordinarily preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent. Agent according to point 1 or 2, characterized in that the polysaccharide is selected from iota-carrageenan. Agent according to one of points 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. Agent according to one of points 1 - 4, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from i. linear, saturated C12 - C50 alkanols, ii.Ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12 - C50 carboxylic acids, which may be hydroxylated.

[0166] Hi. Glycerol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, iv. Propylene glycol mono- and diesters of linear, saturated and unsaturated C12-C10-carboxylic acids, which may be hydroxylated, v. Sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vi. Pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C12-C50 carboxylic acids, which may be hydroxylated, 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, 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 C8-C10 fatty acid residues, x. as well as mixtures of the aforementioned substances. Agents according to any one of items 1-5, characterized in that the at least one nonionic water-in-oil emulsifier is selected from glycerol mono- and diesters of linear or branched, saturated or unsaturated C12-C10 carboxylic acids, which may be hydroxylated, which have the formula (II):. (II), wherein

[0167] R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III), (III), wherein

[0168] R4 represents a linear, saturated or linear, unsaturated Cn-C29 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 group of formula (III). Agent according to any one of items 1-6, characterized in that the at least one nonionic 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. 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 C12 - C50 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 C12-C10-carboxylic acids, which may be hydroxylated. Agent according to any one of items 1-8, characterized in that the at least one nonionic 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 present in a total amount of 1-25 wt.%, preferably 2-20 wt.%, particularly preferably 5-15 wt.%, extraordinarily preferably 10-15 wt.%, in each case based on the weight of the agent. 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 C12 - C50 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 C12-C50 carboxylic acids, which may be hydroxylated, wherein the nonionic water-in-oil emulsifiers mentioned are present in a total amount of 1-30 wt.%, preferably 2-25 wt.%, particularly preferably 5-20 wt.%, extraordinarily preferably 10-20 wt.%, based on the weight of the agent. Agent according to any one of points 1-10, characterized in that at least one surfactant g) which is different from the nonionic water-in-oil emulsifiers c) is additionally present in a total amount of 0.1-10 wt.%, based on the weight of the agent. 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,Mixtures of at least one anionic surfactant and at least one zwitterionic surfactant are particularly preferred. Agents according to any one of items 1-12, characterized in that they additionally contain at least one fatty component that differs from the nonionic water-in-oil emulsifiers c) and 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, as well as mixtures thereof. 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 having 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated Ca ao fatty acids, dicarboxylic acid esters of linear or branched O2-Cio 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, mineral oil, isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols having 6-30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C 1-80 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. 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 fatty 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 docosane, Butyrospermum Parkii (Shea Butter), mango butter, cocoa butter and esters of saturated, monohydric Ca-Cia alcohols with saturated Ci2-Cia monocarboxylic acids, in particular stearyl laurate, cetearyl stearate, cetyl palmitate and myristyl myristate, esters of a saturated, monohydric Cie-Ceo alkanol and a saturated Ca-Cse monocarboxylic acid, in particular cetyl behenate, stearyl behenate C2o-C4o-alkyl stearate, candelilla wax, carnauba wax and beeswax, glycerol triesters of saturated linear C12 - CaO-carboxylic acids, which may be hydroxylated, in particular castor wax,as well as mixtures of the aforementioned substances. Agent according to one of points 1-15, characterized in that the at least one fatty component which is different from the non-ionic water-in-oil emulsifiers c) is present in a total amount of 0.1-5 wt.%, preferably 0.2-4 wt.%, particularly preferably 0.5-3 wt.%, and extraordinarily preferably 1 to 2 wt.%, in each case based on the weight of the agent. Agent according to one of points 1-16, 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 present, 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. Agent according to one of points 1 - 17, characterized in thatthat the at least one alkalizing agent is selected from alkanolamines, alkali metal hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali metal phosphates, and dialkali monohydrogen phosphates, as well as mixtures of these substances. Agent according to any one of items 1 to 18, characterized in that it contains no ammonia and no ammonium hydroxide. Agent according to any 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. %, extraordinarily preferably 0.6 to 3.0 wt. %, in each case based on the weight of the agent. Agent according to one of points 1 to 20, characterized in that the at least one non-ionic water-in-oil emulsifier is present 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.is contained. Agent according to one of points 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.%, further preferably 0.15 to 0.35 wt.%, particularly preferably 0.2 to 0.3 wt.%, extraordinarily preferably 0.21 to 0.25 wt.%, in each case based on the weight of the agent. 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. Agent according to any 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, as well as mixtures thereof, is present in a total amount of 0.1-5 wt.%, particularly preferably 0.2-3 wt.%, extraordinarily preferably 0.5-2.5 wt.%, in each case based on the weight of the agent (M1). Use of an agent according to any one of items 1 to 24 for the oxidative color change of keratin fibers, in particular human hair. A method for oxidative color change, comprising the following process steps: i) providing a cosmetic agent (M1) for oxidative color change of keratin fibers according to one of points 1 to 24, containing a) 40 wt.% to 85 wt.% 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 wt.% 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 present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22°C, and ii) providing an oxidizing agent preparation (M2) containing 40-96% by weight, preferably 65-90% by weight, particularly preferably 70-80% by weight, water, furthermore hydrogen peroxide in a total amount of 0.5 to 23% by weight, further preferably 2.5 to 21 % by weight, particularly preferably 4 to 20 % by weight,very particularly preferably 5 to 18 wt.% and extraordinarily preferably 6 to 12 wt.%, and having a pH in the range from 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 relate in each case to the weight of the oxidizing agent preparation (M2), optionally comprising 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, directly thereafter iv) applying the mixture obtained in step iii) to the hair and leaving this mixture for a time of 1 to 60 minutes, preferably from 20 to 45 minutes, at room temperature and / or at 30 - 60°C, preferably 32 - 50°C on the hair, v) rinsing the hair with water and / or a cleansing composition,and vi) if necessary, applying a post-treatment product to the hair and, if necessary, rinsing and then drying. Packaging unit (kit of parts) which - packaged separately - comprises the following: i) at least one container (C1) containing an agent for the oxidative color change of keratin fibers according to one of points 1 to 24, containing: a) 40 wt.% to 85 wt.% 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 wt.% at least one non-ionic water-in-oil emulsifier, preferably with an HLB value greater than 1.0 and less than / equal to 7.0, d) at least one alkalizing agent, e) zero to less than 0.1 wt.% 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, in each case 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, further 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 a pH in the range from 2.0 to 6.5, preferably 2.5- 5.5, particularly preferably 2.8 to 4.5, each measured at 20°C, wherein the wt.% data refer in each case to the weight of the oxidizing agent preparation (M2),optionally containing at least one oil and / or at least one surfactant.,

[0169] The following examples are intended to illustrate the subject matter of the invention without limiting it thereto.

[0170] Examples

[0171] The temperature stability of the emulsions (M1) for oxidative color change is determined using the phase separation temperature test described below.

[0172] Determination of the phase separation temperature of the emulsion

[0173] A standardized sample of the emulsion to be tested was placed in a test tube and slowly heated to 50°C. After maintaining the sample at 50°C for 5 minutes, the temperature was slowly increased (approximately 2°C in 3-5 minutes). Trained testers visually observed the temperature at which the emulsion began to show separation. This temperature was recorded as the "phase separation temperature."

[0174] A phase separation temperature determined in this way should be at least 63°C to characterize the emulsion product as sufficiently stable for storage. Phase separation temperatures below 63°C indicate that the temperature stability is insufficient when exposed to higher temperatures for longer periods (e.g., > 50°C, preferably > 60°C).

[0175] The table below shows nine different oil-in-water emulsions representing the alkalizing component (M1) of a two-part oxidative dye, along with their phase separation temperatures determined according to the method described above. Samples marked (E) are in accordance with the invention, while (V) are comparative formulations.

[0176] Examples

[0177] The following colorant 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)

[0178] The following oxidation compositions (M2) were prepared (all amounts in wt%):

[0179] Developer emulsion (M2-1) (9 wt% H2O2) Developer emulsion (M2-2) (12 wt% H2O2)

[0180] Developer emulsion (M2-3) (6 wt% H2O2)

[0181] Developer emulsion (M2-4) (3 wt% H2O2) Coloring

[0182] To produce ready-to-use oxidative coloring agents, 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).

[0183] The oxidative dyes prepared in this way were applied in a defined amount (4 g of oxidative dye per 1 g of yak hair) to flat strands of yak hair (12 strands per oxidative dye) and left on the strands for a contact time of 30 minutes at 32°C. The remaining dyes were then rinsed out of the strands with lukewarm water for 2 minutes. The strands were first towel-dried and then blow-dried.

[0184] Intensely colored strands were obtained in each case.

[0185] When applying the aforementioned coloring agents according to the invention to the hair of test subjects, the agents could be easily prepared homogeneously by mixing components (M1) and (M2) by hand. They were then effortlessly applied to the hair to be colored, remaining there for the 30-minute exposure time without dripping. Here, too, intense and homogeneous colorations were achieved along the entire length of the keratin fibers.

Claims

Patent claims:

1. An agent for the oxidative color change of keratin fibers, in particular human hair, which agent is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, 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 is present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C.

2. Agent according to 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.%, extraordinarily preferably 0.5 to 1.0 wt.%, in each case based on the weight of the agent.

3. Agent according to claim 1 or 2, characterized in that the polysaccharide is selected from iota-carrageenan.

4. Agent according to one of 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.

5. Agent according to one of claims 1-4, characterized in that the at least one non-ionic water-in-oil emulsifier is selected from i. linear, saturated C12-C10-alkanols, ii. ethylene glycol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, iii. Glycerol mono- and diesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, iv. Propylene glycol mono- and diesters of linear, saturated and unsaturated C12-C10-carboxylic acids, which may be hydroxylated, v. Sorbitan mono-, di- and triesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vi. Pentaerythrityl mono-, di-, tri- and tetraesters of linear or branched, saturated or unsaturated C12-C10-carboxylic acids, which may be hydroxylated, vii. Methylglucose mono- and diesters of linear or branched, saturated or unsaturated C12-C50 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 Cs - Cso fatty acid residues, x. as well as mixtures of the aforementioned substances.

6. Agent according to one of 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 C12 - C50 carboxylic acids, which may be hydroxylated, having the formula (II): (II), wherein R1, R2 and R3 independently represent a hydrogen atom or a group of formula (III), (III), wherein R4 represents a linear, saturated or linear, unsaturated Cn-C29 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. Agent according to one of 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.

8. Agent according to one of claims 1 - 7, characterized in that the at least one non-ionic water-in-oil emulsifier selected from mixtures of at least one linear, saturated C12 - CaO-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 C12 - CaO-carboxylic acids, which may be hydroxylated.

9. Agent according to one of claims 1 - 8, characterized in that additionally 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.

10. Agent according to one of claims 1 - 9, characterized in that it additionally contains at least one fatty 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 fatty components having a melting point in the range from >25°C to 120°C, and mixtures thereof.

11. Agent according to claim 10, characterized in that the at least one fatty component which is different from the non-ionic water-in-oil emulsifiers c) is selected from branched and saturated or unsaturated alkanols having 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated, optionally hydroxylated C 10 - 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, mineral oil, isoparaffins, polydecenes, silicone oils and mixtures thereof, preferably selected from branched and saturated or unsaturated alkanols having 6 - 30 carbon atoms, glycerol triesters of linear or branched, saturated or unsaturated,optionally hydroxylated Ca-ao fatty acids, dicarboxylic acid esters of linear or branched O2-Cio 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.

12. Agent according to one of claims 1-11, characterized in that in addition at least one polyol selected from polyols having 2 to 20 carbon atoms and 2 to 15 hydroxy groups, whose carbon atom chain is interrupted by one or more oxygen atoms may be, is contained, 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.

13. Use of an agent according to one of claims 1 to 12 for the oxidative color change of keratin fibers, in particular human hair.

14. A process for oxidative color change, comprising the following process steps: i) providing a cosmetic agent (M1) for oxidative color change of keratinic fibers, in particular human hair, according to one of claims 1 to 12, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, 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 present, 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, extraordinarily preferably 8.5 to 9.5, in each case 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.%, further preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, most particularly preferably 5 to 18 % by weight and most preferably 6 to 12 % by weight.-%, and a pH in the range from 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 relate in each case to the weight of the oxidizing agent preparation (M2), optionally comprising 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, directly thereafter. iv) applying the mixture obtained in step iii) to the hair and leaving this mixture on the hair for a time of 1 to 60 minutes, preferably 20 to 45 minutes, at room temperature and / or at 30 - 60°C, preferably at 32 - 50°C, v) rinsing the hair with water and / or a cleansing composition, and vi) optionally applying a post-treatment agent to the hair and optionally rinsing, then drying.

15. Packaging unit (kit of parts) which - packaged separately - comprises the following: i) at least one container (C1) containing an agent for the oxidative color change of keratinic fibers, in particular human hair, according to one of claims 1 to 12, which is in the form of an oil-in-water emulsion and which contains, in each case based on its weight, 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 / 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 present, 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, extraordinarily preferably 8.5 to 9.5, in each case measured at a temperature of 22 °C, and ii) at least one container (C2) containing an oxidizing agent preparation (M2) which contains 40-96 wt.%, preferably 65-90 wt.%, particularly preferably 70-80 wt.%, water, furthermore hydrogen peroxide in a total amount of 0.5 to 23 wt.%, further preferably 2.5 to 21 wt.%, particularly preferably 4 to 20 wt.%, very particularly preferably 5 to 18 wt.% and most preferably 6 to 12 wt.%.-%, and has a pH in the range from 2.0 to 6.5, preferably 2.5 - 5.5, particularly preferably 2.8 to 4.5, in each case measured at 20°C, wherein the wt. % data relate in each case to the weight of the oxidizing agent preparation (M2), optionally containing at least one oil and / or at least one surfactant.

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