DE10152940A1 - Treatment of keratinous fibers, especially human hair, to remove colorant or change nuance involves coloring in usual way, then treating with agent containing dithionite salt and surfactant - Google Patents

Abstract

Method of treating keratinous fibers comprises coloring in the usual way and treating with an agent containing dithionite salt(s) (I) and surfactant(s) (II). An Independent claim is also included for agent for changing the color of colored keratinous fibers, obtained by mixing an aqueous or aqueous-alcoholic formulation (A) with an anhydrous formulation (B) containing (I), where at least one of the formulations contains (II), immediately before use.

Description

The present invention relates to a special color-changing method for Hair treatment based on dithionite salts, corresponding compositions containing them Dithionite salts and the use of these agents to accelerate washing out of coloring and to change the color shade.

Preparations for tinting and coloring hair are an important type of cosmetic products. They can serve to match the natural hair color Desires of the corresponding person to be nuanced slightly or more, an entirely achieve different hair color or undesirable shades, such as shades of gray cover. Common hair dyes are, depending on the desired color or Durability of the coloring, either based on oxidation dyes or based formulated by direct dyes. Combinations of Oxidation dyes and substantive dyes to achieve special shades used.

Colorants based on oxidation dyes lead to brilliant and long-lasting Colors. However, they require the use of strong oxidizing agents, such as for example hydrogen peroxide solutions. Such colorants contain Oxidation dye precursors, so-called developer components and coupler components. The Developer components form under the influence of oxidizing agents or Atmospheric oxygen with each other or with coupling with one or more Coupler components from the actual dyes.

Colorants based on direct dyes are often used for temporary Colorings used. The direct dyes are Dye molecules that pull directly onto the hair and do not have an oxidative process Need training of color. This already belongs to these dyes, for example Henna known from antiquity for coloring body and hair.

In all of these staining processes, it can happen that the staining consists of different Reasons should be reversed in whole or in part. A partial one Removal of the staining is useful, for example, if the staining result is due to the Fibers turn out darker than desired. It is therefore an object of the present Invention to provide a method and corresponding means with which a targeted Subsequent refinement of colored fibers is possible without the fiber itself to attack unnecessarily.

On the other hand, complete staining can also be removed in some cases be desired. For example, it is conceivable that the hair for a specific Occasion to be colored or tinted in a certain shade and after some Days the original color should be recovered. Therefore it is one further object of the present invention a method and corresponding means for To provide a complete color print without the fibers harm yourself unnecessarily.

Means and methods for color proofing are already known from the literature. Usually will Colorings oxidative, for example using a conventional bleaching process again reversed. In this process, however, the fibers can be stronger by using them Oxidizing agents are damaged. Reductive processes have also been used Color proof already described. For example, the German patent discloses DE-197 37 987-C 1 agent for decolouring colored hair, which contains at least one alcohol and contain a sulfur-containing reducing agent. These prior art methods can, however, with regard to the effect achieved, in particular the uniformity of the resulting color, not yet completely convincing.

It has now surprisingly been found that hair treatment compositions based on Dithionite salts and surfactants meet the requirements placed on color-changing agents to a high degree and at the same time protect the fibers.

A first object of the present invention is therefore a method for treatment keratin fibers, in which the fibers are dyed in the usual way in a first step and in a second step the fibers with an agent (M) containing a Dithionite salt and at least one surfactant, are treated.

Among keratin fibers are furs, wool, feathers and especially human hair to understand.

The term "to be colored in the usual way" in the first step of the invention The method includes all methods known to the person skilled in the art, in which the Hair a dye is applied and this either for a time between a few Leave minutes and about 45 minutes on the hair and then with water or rinsed with a surfactant or left entirely on the hair. It is in this context expressly based on the known monographs, e.g. B. Kh. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced, which reflect the corresponding knowledge of the expert. The composition of the conventional colorant is not subject to any principle Limitations.

• - Oxidationsfarbstoffvorprodukte vorn Entwickler- und Kuppler-Typ,
• - synthetische direktziehende Farbstoffe und
• - natürliche Farbstoffe, wie beispielsweise Henna,

sowie Mischungen von Vertretern einer oder mehrerer dieser Gruppen eingesetzt werden. Can as a dye (intermediate)

• - Oxidation dye intermediates from developer and coupler type,
• - synthetic direct dyes and
• - natural dyes, such as henna,

as well as mixtures of representatives of one or more of these groups.

In a first embodiment of the method according to the invention, the first step is an oxidative stain. Within the scope of this embodiment Oxidation dye intermediate products of the developer and coupler type with the formation of actual dyes oxidized.

Developer-type oxidation dye precursors are usually primary aromatic amines with a further free one in the para or ortho position or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic Hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used. Suitable developer components are, for example, p- Phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'- Diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2- Hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxymethylamino-4-aminophenol, bis (4-aminophenyl) amine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2 - ((diethylamino) - methyl) phenol, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) - diazacycloheptane, 1,3-bis (N (2'-hydroxyethyl) -N (4'-aminophenylamino)) - 2-propanol, 4- Amino-2- (2'-hydroxyethoxy) phenol, 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10- tetraoxadecane and 4,5-diaminopyrazole derivatives according to EP 0 740 931 or WO 94/08970 such as B. 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

Particularly advantageous developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2- Aminomethyl-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.

• - m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, 5- (3-Hydroxypropylamino)-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino- 2-chlor-6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2- methylphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1,3-Dihydroxy-5-(methylamino)-benzol, 3-(Ethylamino)-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• - o-Aminophenol und dessen Derivate,
• - m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2,4-diaminophenyl)-propan, 2,6-Bis-(2-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• - o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• - Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• - Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6- Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• - Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• - Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• - Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• - Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• - Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4- methylendioxybenzol.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as oxidation dye precursors of the coupler type. Examples of such coupler components are

• m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 , 6-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2 ' -Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-3-aminophenol,
• o-aminophenol and its derivatives,
• m-diamino benzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1 , 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly suitable coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5- Methylresorcinol, 2,5-dimethylresorcinol, 2,6-di- (β-hydroxyethylamino) toluene and 2,6-dihydroxy-3,4-dimethylpyridine.

Furthermore, the agents for oxidative hair coloring can be used for further shading direct dyes included. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'- carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, Picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2- Chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In a second preferred embodiment of this subject of the present Invention is the first step of the method according to the invention, a dyeing based of direct dyes. Regarding the preferred direct dyes At this point, please refer explicitly to the explanations given above.

For further shading, in addition to the Dye (intermediate) also direct-occurring dyes occurring in nature, such as for example henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and Alkanna root can be used.

It is not necessary that the oxidation dye precursors or the substantive Dyes each represent uniform compounds. Rather, in the Hair colorants, due to the manufacturing process for the individual dyes, in subordinate quantities may also contain other components, insofar as these are not that Adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

Regarding those that can be used in the hair coloring and tinting agents according to the invention Dyes are further expressly referred to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), appeared as Volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and Personal Care Products, Mannheim, referred to.

Both the oxidation dye precursors and the substantive dyes are in the agents preferably in amounts of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, in each case based on the total composition.

Hair dye, especially if the coloration is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually slightly acidic to alkaline, d. H. adjusted to pH values in the range of about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines. preferred Alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino- 2-methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. In particular monoethanolamine, triethanolamine and 2-amino-2-methylpropanol and 2-Amino-2-methyl-1,3-propanediol are preferred in this group. Also the Use of ω-amino acids such as ω-aminocaproic acid as an alkalizing agent possible.

The actual hair colors are developed as part of an oxidative process Process, so can usual oxidizing agents such as hydrogen peroxide or whose adducts with urea, melamine or sodium borate are used.

However, oxidation with atmospheric oxygen as the only oxidizing agent can be preferred his. It is also possible to carry out the oxidation with the aid of enzymes, where the enzymes are used to generate oxidizing per compounds as well as to enhance the effect of a small amount present Oxidant.

So the enzymes (enzyme class 1: oxidoreductases) can remove electrons from suitable Transfer developer components (reducing agents) to atmospheric oxygen. Are preferred oxidases such as tyrosinase and laccase but also glucose oxidase, uricase or Pyruvate. The procedure should also be mentioned, the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide by peroxidases to reinforce.

The preparation of the oxidizing agent is then expediently immediately before Coloring the hair mixed with the preparation with the dye precursors. That included The resulting ready-to-use hair dye preparation should preferably have a pH value in the Range from 6 to 10. The use of is particularly preferred Hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C, preferably at the temperature of the scalp. After an exposure time of approx. 5 to 45, in particular 15 to 30, minutes, this becomes Hair dye removed by rinsing from the hair to be dyed. The washing up with a shampoo, if a strong surfactant carrier, e.g. B. a coloring shampoo, was used.

Especially with hair that is difficult to dye, the preparation can be used with the Dye precursors without prior mixing with the oxidation component on the hair be applied. After an exposure time of 20 to 30 minutes, optionally after an intermediate rinse - the oxidation component applied. After a further exposure time of 10 to 20 minutes, rinse and post-shampooed if desired. In this embodiment, according to a first Variant in which the previous application of the dye precursors is better Penetration in the hair is said to bring the appropriate agent to a pH of set about 4 to 7. According to a second variant, air oxidation is performed first sought, the applied agent preferably having a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidic adjusted peroxidisulfate solutions may be preferred as the oxidizing agent.

Regardless of which of the above-mentioned procedures is chosen in the context of the method according to the invention, the formation of the color can be supported and increased by adding certain metal ions to the agent. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

The second step of the method according to the invention is the treatment of the keratin Fibers with an agent (M) containing at least one dithionite salt and at least one Surfactant.

In principle, all physiologically acceptable salts of dithionite, such as for example sodium dithionite, potassium dithionite and ammonium dithionite are suitable. On Dithionite salt which is particularly preferred according to the invention is sodium dithionite.

The agent (M) used in the process according to the invention contains preferably 0.5 to 20% by weight of a dithionite salt, amounts of 2 to 10% by weight are particularly preferred.

The agents (M) according to the invention contain at least one surfactant, in principle both anionic, nonionic and zwitterionic, ampholytic and cationic Surfactants are suitable. The anionic ones are particularly preferred according to the invention Surfactants. In many cases, however, it has also proven to be advantageous that the funds or several further surfactants, in particular selected from the zwitterionic and contain nonionic surfactants.

• - lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• - Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• - Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates with 12 to 18 carbon atoms,
• linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

• - Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C- Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

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

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

• - im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• - im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• - im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• - im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Alkylpolyglycosides in which R ¹

• essentially from C ₈ and C ₁₀ alkyl groups,
• essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C ₁₆ alkyl groups or
• - consists essentially of C ₁₂ - to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. Usually sugar with 5 or 6 carbon atoms and the corresponding Oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 Sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. All alkyl glycosides in which x is 1.1 to 1.4 are particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve for fixation of fragrance components to improve hair. The specialist is therefore in the event that the effect of the perfume oil goes beyond the duration of the hair treatment the hair is desired, preferably to this class of substances as an additional ingredient of the preparations according to the invention.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also are used according to the invention. These homologues can average up to 10 Contain ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl -3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

According to the invention, cationic surfactants are in particular those of the type of quaternary ammonium compounds, the esterquats and the amidoamines used.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above The surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances that both have at least one Contain ester function as well as at least one quaternary ammonium group as a structural element. Preferred ester quats 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-dihydroxypropyl dialkylamines. Such products will be for example under the trademarks Stepantex®, Dehyquart® and Armocare distributed. The products Armocare® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 Examples of such ester quats.

The alkylamidoamines are usually made more natural or by amidation synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A According to the invention, this compound is particularly suitable from this group of substances the name Tegoamid® S 18 commercially available stearamidopropyl-dimethylamine represents.

Other quaternized cationic surfactants that can be used according to the invention are the quaternized ones Protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided is the commercial product Glucquat®100, according to INCI nomenclature a "Lauryl Methyl Gluceth-10 hydroxypropyl dimonium chloride ".

The compounds with alkyl groups used as surfactant can in each case be act uniform substances. However, it is usually preferred in manufacturing of these substances from natural plant or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these addition products can represent both products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution Mixtures of homologs understood, which one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrowing homolog distributions will be on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

• - organischen, natürlichen Verdickungsmitteln, wie beipielsweise Agar-Agar, Xanthan- Gum, Carrageen, Traganth, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Leinsamengummen, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Dextrane, Gelatine oder Casein,
• - organischen, abgewandelten Naturstoffen, wie beispielsweise Kernmehlether oder Cellulose-Derivate, wie beispielsweise Methylcellulose, Hydroxyalkylcellulose, insbesondere Hydroxyethyl- und -propylcellulose, Carboxymethylcellulose sowie Celluloseester,
• - organische, vollsynthetische Verdickungsmittel, wie beispielsweise Polyacryl- u. Polymethacryl-Verbindungen, Vinylpolymere, wie beispielsweise Polyvinylpyrrolidon oder Poylvinylakohol, Polycarbonsäuren, Polyether, Polyimine oder Polyamide, oder
• - anorganischen Verdickungsmitteln, wie beispielsweise Polykieselsäuren, Tonmineralien wie Montmorillonite, Bentonit, Zeolithe oder Kieselsäuren

zu verdicken. Die erfindungsgemäß verdickten Mittel zeichnen sich durch deutlich gleichmäßigere Färbeergebnisse aus, als dies bei vergleichbaren dünnflüssigen Mitteln der Fall ist. It has proven to be preferred according to the invention if the agent M has a sufficient viscosity in the course of the process, so that it can be distributed well on the fibers without running easily. In principle, the viscosities can be set using all conventional methods. For example, it has proven advantageous to use funds

• - Organic, natural thickening agents, such as agar-agar, xanthan gum, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob bean gum, linseed gums, starch fractions and derivatives such as amylose, amylopectin and dextrins, dextrans , Gelatin or casein,
• organic, modified natural substances, such as, for example, powdered meal ether or cellulose derivatives, such as, for example, methyl cellulose, hydroxyalkyl cellulose, in particular hydroxyethyl and propyl cellulose, carboxymethyl cellulose and cellulose esters,
• - Organic, fully synthetic thickeners, such as polyacrylic and. Polymethacrylic compounds, vinyl polymers, such as polyvinylpyrrolidone or polyvinyl alcohol, polycarboxylic acids, polyethers, polyimines or polyamides, or
• - inorganic thickeners, such as polysilicic acids, clay minerals such as montmorillonites, bentonite, zeolites or silicas

to thicken. The agents thickened according to the invention are distinguished by significantly more uniform dyeing results than is the case with comparable low-viscosity agents.

In many cases, however, it has proven sufficient to use a Thicken fatty alcohol system.

The means (M) of the process according to the invention preferably have a pH of 4 to 12, in particular from 6 to 10.

The action time of the agent (M) in the process according to the invention is preferably between 5 and 60 minutes, contact times are particularly preferred between 15 and 45 minutes.

According to one embodiment of the present, it can increase the storage stability Invention may be preferred to formulate the agent (M) as a two-component system, whose individual preparations are mixed immediately before use.

In the context of this embodiment, the agent (M) can be used immediately before use by mixing a first, aqueous or aqueous-alcoholic preparation (I) with a second anhydrous preparation (II) containing at least one dithionite salt, are obtained, at least one of the preparations (I) or (II) at least one Contains surfactant.

For the purposes of the present invention, preparations having an Water content under 1 wt .-% understood.

In a preferred embodiment, the anhydrous preparation (II) is in powder form. If the dithionite salt is formulated in a powdered preparation, it can be preferred according to the invention, this preparation before mixing with the aqueous or pre-dissolve aqueous alcoholic preparation (I) in a little water, as this rapid and improved homogenization is achieved.

In a likewise preferred embodiment, the anhydrous preparation (II) can also be present as an anhydrous paste. Although the present invention is in no way limited with regard to the suitable paste base, it has proven to be preferable if the base is a combination of water-insoluble liquid, if the base is a combination of water-insoluble liquid oil components, nonionic emulsifiers with an HLB value of 5 or more, preferably selected from a group consisting of C ₁₆ thickeners, - C ₁₈ -Fettsäurepartialestern of C ₂ -C ₆ polyols with 2 to 6 hydroxyl groups and C ₁₆ -C ₁₈ - contains fatty acid metal soaps and optionally water-soluble polyols or polyethylene glycols , Furthermore, it has proven to be advantageous if the paste bases also contain diluents, such as, for example, alkylene carbonates, in particular propylene carbonate.

For the purposes of the present invention, aqueous-alcoholic preparations are understood to mean aqueous solutions containing 3 to 70% by weight of a C ₁ -C ₄ alcohol, in particular ethanol or isopropanol.

With regard to the timing of the method according to the invention are in principle no limits. Rather, the timing is strongly influenced by the desired one Effect of hair treatment dominates. For example, if it is intended to change the nuance of the to optimize the achieved coloring, so the second step of the invention Procedure take place immediately after the dyeing process. Does that come The method according to the invention is used to completely restore the coloration achieved remove, so the second step in the process of dissatisfaction with the color also take place immediately after the dyeing process. The second step but can also according to the invention at a later point in time, for example after a few Days when hair coloring is no longer desired. In these Cases is specifically washed out using the method according to the invention achieved coloring accelerated.

In the course of the applicant's experiments, it has been shown that it is according to the invention may be preferred, the fibers during the exposure time of the agent (M) containing the Shield dithionite salt and at least one surfactant from the immediate air supply. This can be achieved, for example, by immediately after the fibers Application of the agent (M) with a foil, in particular with an aluminum foil, wrapped.

Furthermore, it has proven to be advantageous to use the fibers according to the invention Treatment method with an acidic solution of a physiological treat compatible inorganic and / or organic acid. This flush preferably has a pH between 2 and 6, in particular between 3 and 4, on. The use of such an acidic rinse improves the one hand Fiber structure and thus the shine and condition of the fibers. On the other hand but also the result of the color change caused by such acidic rinsing improved.

In a preferred embodiment of this invention, the agent (M) with a such acidic rinse washed from the fibers. It has been shown that then Coloring result is more uniform and better decolorization can be achieved.

A second object of the present invention are color change agents dyed keratin fibers made just before use by mixing one first, aqueous or aqueous-alcoholic preparation (I) with a second anhydrous preparation (II) containing at least one dithionite salt is obtained, wherein at least one of the preparations (I) or (II) contains at least one surfactant.

With regard to the definition of the terms used, explicit reference is made to the referenced above.

Within the scope of this subject matter of the invention, it is particularly preferred if at least one of the preparations (I) or (II) contains at least one anionic surfactant.

Although both preparations of the two-part agent according to the invention in principle Can contain surfactant, it is particularly preferred if the surfactant in the preparation (I) is included.

Furthermore, the agents according to the invention preferably contain at least one Oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances and their mixtures with solid paraffins and waxes. As According to the invention, water-insoluble substances are defined whose solubility in Water at 20 ° C is less than 0.1 wt .-%. The melting point of each oil or fat components is preferably below about 40 ° C. Oil and Fat components that are at room temperature, i.e. H. are liquid below 25 ° C be particularly preferred according to the invention. When using multiple oil and However, it is usually also fat components as well as solid paraffins and waxes sufficient if the mixture of oil and fat components as well as paraffins and Grow these conditions.

A preferred group of oil components are vegetable oils. Examples of such Oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, Wheat germ oil, peach seed oil and the liquid parts of coconut oil.

However, other triglyceride oils such as the liquid portions of beef tallow are also suitable as well as synthetic triglyceride oils.

Another; particularly preferred group according to the invention as an oil component Compounds that can be used are liquid paraffin oils and synthetic hydrocarbons as well Di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms Atoms such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n- undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether and Di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl noctyl ether and 2-methyl-pentyl-n-octyl ether. The available as commercial products Compounds 1,3-di- (2-ethylhexyl) cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE) can be preferred.

Oil components which can likewise be used according to the invention are fatty acid and fatty alcohol esters. The monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances concerns the products of the esterification of fatty acids with 8 to 24 carbon atoms such as, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. B. in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical blends, and brassidyl alcohol and their mixtures. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, isopropyl myristate, isononanoic acid C _16-18 alkyl ester (Cetiol® SN), stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate / caprylate and n-butyl stearate are particularly preferred.

Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, Di- (2-ethylhexyl) succinate and di-isotridecylacelaate as well as diol esters such as Ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), Propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and Oil components which can be used according to the invention are neopentyl glycol di-capylate, likewise complex esters such as B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used according to the invention acting oil components are used. The fatty alcohols can be saturated or be unsaturated and linear or branched. Can be used in the sense of the invention for example decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, Cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, Caprinal alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, this list being exemplary and not limiting should have. However, the fatty alcohols derive from preferably natural fatty acids, usually from a recovery from the esters of fatty acids by reduction can be assumed. Such can also be used according to the invention Fatty alcohol cuts, which are reduced by reducing naturally occurring triglycerides such as beef tallow, Palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from their transesterification products with corresponding alcohols resulting fatty acid esters are generated, and thus represent a mixture of different fatty alcohols.

Fatty alcohols are particularly preferred oil components according to the invention. Although the Such components may also contain oil components in preparation (II) preferred according to the invention, in which at least one in preparation (I) Oil component is included.

In a preferred embodiment of the present invention, the agents according to the invention in addition to the dithionite salt at least one other Reducing agent. Examples of suitable reducing agents are thioglycolic acid, Thiolactic acid, thioglycerol, mercaptopropionic acid, sodium bisulfite, Ammonium bisulfite, cysteamine, dithiothreitol, thio malic acid or α- Mercaptoethylsulfonsäure. The sulfite and disulfite salts are also preferred Reducing agent. A particularly preferred reducing agent is sodium disulfite. It can According to the invention, it may be preferred that the further reducing agent in the preparation (II) is included.

The agents according to the invention preferably contain the further reducing agent in Amounts from 0.2 to 5.0% by weight, in particular in amounts from 0.5 to 2.0% by weight.

• - nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• - kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid-Copolymere und quaternierter Polyvinylalkohol,
• - zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylatltert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid- Terpolymere,
• - Strukturanten wie Maleinsäure und Milchsäure,
• - haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• - Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• - faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• - quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• - Entschäumer wie Silikone,
• - Farbstoffe zum Anfärben des Mittels,
• - Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• - Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• - Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen, sowie Substanzen zur Stabilisierung des eingestellten pH-Wertes, wie beispielsweise anorganische Sulfatsalze,
• - Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• - Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• - Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmann, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• - Cholesterin,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• - Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• - Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• - Pigmente,
• - Stabilisierungsmittel für Wassserstoffkeroxid und andere Oxidationsmittel,
• - Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• - Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidaternolino-copolymers,
• zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
• - structurants such as maleic acid and lactic acid,
• hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as customary acids, in particular edible acids and bases, and substances for stabilizing the adjusted pH, such as inorganic sulfate salts,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosmann, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• - opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agents for hydrogen keroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding other optional components and the amounts used Components is expressly referred to the relevant manuals known to the expert, z. B. Kh. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989.

A third object of the present invention is the use of a Application preparation containing at least one dithionite salt and at least one Surfactant, to accelerate the washing out of colorations of keratin fibers.

A fourth object of the present invention is the use of a Application preparation containing at least one dithionite salt and at least one Surfactant, for the nuance of dyeings in keratin fibers.

Use has also been made within the scope of these objects of the present invention at least one anionic surfactant has proven to be particularly preferred.

The following examples are intended to explain the subject matter of the present invention in more detail without however restricting it.

Examples

Unless stated otherwise, the information in the examples is in percent by weight. 1. Composition of the color-changing composition (Ia) Texapon® NSO ¹ 8.0 Lorol®, technical ² 3.5 Hydrenol® D ³ 4.5 Eumulgin® O5 ⁴ 2.0 AMPD ⁵ 0.6 water ad 100.0 The pH of this composition is 9.3. ¹ lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (HENKEL) ² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (HENKEL) ³ C ^16-18 fatty alcohol (INCI name: Cetearyl alcohol) (HENKEL) ⁴ oleyl-cetyl alcohol with approx. 5 EO units (INCI name: Oleth-5) (HENKEL) ⁵ 2-amino-2-methyl-1,3-propanediol (INCI name: aminomethyl propanediol) Texapon® NSO 8.0 Lorol®, technical 3.5 Hydrenol® D 4.5 Eumulgin® O5 2.0 citric acid 0.3 phenoxyethanol 0.5 methylparaben 0.3 Propylparaben 0.3 The pH of this composition is 6.8. Sodium Dithionite 95 sodium metabisulfite 5

2. Composition of the colorants

The following colorants were made: Colorant A Akypo® RLM 45 N ⁶ 3.00 Hydrenol® D 2.00 Lorol, techn. 2.50 Aminol® A 15 ⁷ 0.50 Paridol® M ⁸ 0.30 Paridol® P ⁹ 0.20 phenoxyethanol 0.80 tartaric acid 0.20 HC Violet ¹⁰ 0.25 HC Red No. 3 ¹¹ 0.45 HC Blue No. 2 ¹² 0.30 Lowadene® violet 1 ¹³ 0.30 Carbopol® ETD 2001 ¹⁴ 0.15 AMP ¹⁵ 0.80 Perfume 0.10 Merquat® 280 ¹⁶ 0.50 d-Panthenol 0.20 d, 1-α-tocopherol acetate 0.20 water ad 100.00 ⁶ C _12-14 fatty alcohol-4.5-EO-acetic acid sodium salt (approx. 80 to 84% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y) ⁷ alkyl ether carboxylate monoethanolamide (approx. 97 to 100% active substance content, INCI name: Trideceth-2 Carboxamide Mea) (Chem-Y) ⁸ 4-Hydroxybenzoic acid methyl ester (INCI name: Methylparaben) (Naarden) ⁹ 4-hydroxybenzoic acid propyl ester (INCI name: Propylparaben) (Naarden) ¹⁰ 1,4-bis [(2'-hydroxyethyl) amino) -2-nitrobenzene ¹¹ N '(2-hydroxyethylamino) -2-nitro-4-aminobenzene ¹² N, N, N'-tris (2-hydroxyethyl) -2-nitro-1,4-phenylenediamine ¹³ 1,4-diaminoanthraquinone ¹⁴ polyacrylic acid (approx. 98 to 100% active substance; INCI name: carbomer) (Goodrich) ¹⁵ 2-amino-2-methylpropanol (approx. 95% active substance content; INCI name: aminomethyl propanol) ¹⁶ dimethyldiallylammonium chloride-acrylic acid copolymer (approx. 35% active substance content; INCI name: Polyquaternium-22) (Chemviron) Akypo® RLM 45 N 3.00 Hydrenol® D 2.00 Lorol, techn. 2.50 Aminol® A 15 0.50 Paridol® M 0.30 Paridol® P 0.20 phenoxyethanol 0.80 tartaric acid 0.20 HC Red No. 1 ¹⁷ 0.20 HC Orange No. 1 ¹⁸ 0.60 HC Red BN ¹⁹ 0.20 HC Red No. 3 0.50 Carbopol® ETD 2001 0.15 AMP 0.75 Perfume 0.10 Merquat® 280 0.50 d-Panthenol 0.20 d, 1-α-tocopherol acetate 0.20 water ad 100.00 ¹⁷ 4-amino-2-nitrodiphenylamine ¹⁸ 2-nitro-4'-hydroxydiphenylamine ¹⁹ 4 - [(3'-hydroxypropyl) amino) -3-nitrophenol

3. Composition of the aftertreatment agent

The following aftertreatment agent was produced: Rewoquat® W 75 PG ²⁰ 2.5 Dehyquart® F75 ²¹ 1.0 Cetylstearylalcohol 2.5 Tego Amid® S 18 ²² 0.8 glycerol monostearate 0.8 isopropyl 1.0 p-hydroxybenzoate 0.2 Citric acid (at least 46%) 0.9 Gluadin® W 20 ²³ 1.0 Dow Corning® 1401 Fluid ²⁴ 2.0 Mandelproteinhydrolysat 1.0 Panthenol 75 L. 0.2 phenoxyethanol 0.4 Perfume 0.3 water ad 100.0 ²⁰ 1-methyl-2-nortalgalkyl-3-tallow fatty acid amidoethylimidazolinium methosulfate in propylene glycol (approx. 74 to 77% active substance content; INCI name: Quaternium-27, propylene glycol) (Goldschmidt) ²¹ fatty alcohol-methyltriethanolammonium methylsulfate dialkyl ester mixture (INCI name: distearoylethyl hydroxyethylmonium methosulfate, cetearyl alcohol) (Cognis) ²² stearic acid N- (3-dimethylamino) propylamide (INCI name: Stearamidopropyl Dimethylamine) (Degussa) ²³ Wheat protein hydrolyzate (mmd. 20% solids; INCI name: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (Cognis) ²⁴ dimethylcyclosiloxane-dimethylpolysiloxanol mixture (approx. 13% solids; INCI name: Cyclomethicone, Dimethiconol) (Dow Corning) The pH of the aftertreatment agent was 3.1.

4. Implementation of the method according to the invention 4.1 coloring

The coloring cream A or B was applied to 5 cm long strands (natural Euro hair, white, from Kerling) and left there at 32 ° C for 30 min. After that, the hair rinsed, washed out with a normal shampoo and then dried.

4.2 Color change

Compositions (Ia) and (Ib) were mixed with composition (II) mixed in accordance with the information in table 1 and onto the dyed fibers (see point 4.1) applied. The exposure time of the color-changing preparation was 30 minutes 35 ° C. The fibers were then treated with the aftertreatment agent (see point 3). rinsed and dried.

The measured color residues, based in each case on the coloration before the treatment with the color-changing agent, which were obtained with the preparation (Ia), are shown in Table 2. Table 1

Table 2

Claims (22)

1. Process for the treatment of keratin fibers, in which the Fibers are dyed in the usual way and the fibers in a second step an agent (M) containing at least one dithionite salt and at least one surfactant, be treated. 2. The method according to claim 1, characterized in that the agent (M) at least contains an anionic surfactant. 3. The method according to any one of claims 1 or 2, characterized in that the first Step is an oxidative stain. 4. The method according to any one of claims 1 or 2, characterized in that the first Step is a coloring based on substantive dyes. 5. The method according to any one of claims 1 to 4, characterized in that the Dithionite salt is sodium dithionite. 6. The method according to any one of claims 1 to 5, characterized in that the Exposure time of the agent (M) between 5 and 60 minutes, in particular between 15 and is 45 minutes. 7. The method according to any one of claims 1 to 6, characterized in that the Treatment with the agent (M) immediately after the coloring to change the achieved nuance occurs. 8. The method according to any one of claims 1 to 7, characterized in that the Treatment with the agent (M) to accelerate the washing out of the coloring he follows. 9. The method according to any one of claims 1 to 8, characterized in that the fibers be wrapped with a film immediately after application of the agent (M). 10. The method according to any one of claims 1 to 9, characterized in that the agent (M) is washed out of the fibers using an acidic rinse. 11. Means for changing the color of colored keratin fibers, which immediately before the Application by mixing a first, aqueous or aqueous-alcoholic Preparation (I) with a second anhydrous preparation (II) containing at least a dithionite salt is obtained, at least one of the two preparations contains at least one surfactant. 12. Composition according to claim 11, characterized in that the surfactant in the preparation (I) is included. 13. Composition according to one of claims 11 or 12, characterized in that the surfactant is an anionic surfactant. 14. Composition according to one of claims 11 to 13, characterized in that one of the Preparations contains at least one oil component. 15. Composition according to claim 14, characterized in that the oil component Is fatty alcohol. 16. Composition according to one of claims 14 or 15, characterized in that the Oil component in the preparation (I) is included. 17. Composition according to one of claims 11 to 16, characterized in that it is a contains further reducing agent. 18. Composition according to claim 17, characterized in that the further reducing agent is a disulfite salt. 19. Composition according to one of claims 17 or 18, characterized in that the further Reducing agent is contained in the preparation (II). 20. Use of an application preparation containing at least one dithionite salt and at least one surfactant to accelerate the washing out of colorings keratin fibers. 21. Use of an application preparation containing at least one dithionite salt and at least one surfactant, for the nuance of dyeings of keratin fibers. 22. Use according to one of claims 20 or 21, characterized in that the application preparation contains at least one anionic surfactant.