Improved indigo dyeing methods

Abstract

The invention relates to methods for dyeing keratinous fibers, in particular human hair, using an indigo-producing plant powder and a post-treatment agent.

Description

[0001] Improved dyeing processes with indigo

[0002] The invention relates to methods for dyeing keratin-containing fibers, in particular human hair, using an indigo-producing plant powder and an after-treatment agent.

[0003] The desire to change one's hair color is a major need for many consumers. To satisfy this need, the cosmetics industry offers a diverse range of products. Hair dyes that achieve particularly long-lasting color with high coverage are usually oxidation dyes. These use oxidizing agents that can damage the hair structure. Certain cationic direct azo dyes are also capable of achieving hair color changes with excellent fastness properties. However, these azo dyes are synthetic dyes.

[0004] A growing number of consumers are demanding hair dyes and hair coloring processes based on natural dyes, even though these products and processes are often inferior to the aforementioned products and processes in terms of fastness, coverage and color variety.

[0005] In addition to dyeing with henna, which is obtained from the plant Lawsonia inermis, dyeing hair with plants from which indigo can be produced has also been known for a long time.

[0006] State of the art

[0007] There has been no lack of efforts in the state of the art to improve the coloring of keratin fibers, especially human hair, with indigo.

[0008] The addition of natural dyes to oxidative hair dyes is also popular. This involves mixing the coloring cream with an aqueous preparation containing hydrogen peroxide shortly before application to the hair. The coloring cream primarily contains oxidation dye precursors, such as toluene-2,5-diamine sulfate, 4-chlororesorcinol, 2-methylresorcinol, 2-amino-4-hydroxyethylaminoanisole sulfate, 4-amino-2-hydroxytoluene, 4-amino-m-cresol, and m-aminophenol; the natural dye content serves only to provide nuance. The resulting color is essentially a standard oxidative dye with high fastness properties. The problem of poor adhesion of the natural dye plays a minor role with such products.When dyeing with indigo-producing plants, it is often observed that the color changes continuously for up to two weeks after application of the dye, and the final shade only persists after this time. At a concentration of 2% by weight of indigo-producing plant powder in water, the color on the hair changes from an initial turquoise-blue tone to a redder and darker shade in the first few days after dyeing, creating a purple-like color impression.

[0009] WO2015082482A1 discloses a method for coloring hair using powdered plant parts from plants that produce indigo. After the indigo dyeing, which can be performed in the presence of hydrogen peroxide, the hair is treated with a strongly alkaline composition. This is intended to accelerate the development of the final color tone and prevent color change after the actual dyeing process. However, the alkaline pH and the oxidizing agent damage the hair.

[0010] Task

[0011] An object of the present invention was to provide methods for dyeing keratin-containing fibers, in particular human hair, using plants that produce indigo, with which the final color result of the indigo dyeing is obtained as quickly as possible after completion of the actual dyeing process.

[0012] Surprisingly, it was found that with the dyeing processes described in the patent claims using plants that produce indigo, dyeings can be achieved with which the final color result of the indigo dyeing is obtained as quickly as possible after completion of the actual dyeing process.

[0013] A first subject of the present invention is therefore a method for the non-oxidative coloring of keratin fibers, in particular human hair, which comprises the following process steps in the given order: a) providing an aqueous coloring composition (A) which contains at least one indigo-producing plant powder i), is free of cysteine ​​and has a pH of 2.0 to 10.0, preferably from 4.0 to 9.0, particularly preferably from 5.0 to 8.0, extraordinarily preferably from 6.0 to 7.4, in each case measured at 20°C, b) applying the aqueous coloring composition (A) to the keratin fibers, c) allowing it to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, d) rinsing the keratin fibers with water, e) optionally drying the keratin fibers, f) immediately thereafter within a time of zero seconds to 30 minutes, preferably 10 seconds to 10 minutes,particularly preferably 1 to 5 minutes, treating the keratin fibers with one of the following post-treatment steps: f)i. rinsing or soaking the keratin fibers with additive-free water for a period of 5 to 120 minutes, f)ii. rinsing or soaking the keratin fibers with an aqueous cysteine ​​solution (C) having a pH below 7.5 measured at 20°C for a period of 5 to 120 minutes, f)iii. rinsing or soaking the keratin fibers with an aqueous composition (G) containing at least one glycosylase (EC 3.2) for a period of 5 to 120 minutes, f)iv. rinsing or soaking the keratin fibers with an aqueous composition (L) containing laccase (EC 1.10.3.2) for a period of 5 to 120 minutes, f)v. Rinsing or soaking the keratin fibres with an aqueous composition (AT) containing, based on its weight, 1 - 20% by weight of an anionic surfactant and having a pH in the range of 3 - 6, measured at 20°C,for a period of 5 to 120 minutes, wherein the process does not use hydrogen peroxide and no ions and compounds of metals other than alkali metals and alkaline earth metals.

[0014] The terms “colorant used according to the invention” and coloring composition (A) are used synonymously in the present application.

[0015] Dyes preferably used according to the invention are characterized in that the indigo-producing plant(s) is / are selected from at least one species of the following genera:

[0016] - Indigofera, in particular Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata, Indigofera arrecta, Indigofera heterantha “Gerardiana”, Indigofera argentea or Indigofera longiracemosa;

[0017] - Isatis, especially Isatis tinctoria (woad);

[0018] - Persicaria, especially Persicaria tinctoria (dyer's knotweed);

[0019] - Wrightia, especially Wrightia tinctoria;

[0020] - Calanthe, especially Calanthe veratrifolia; and

[0021] - Baphicacanthus cusia, synonym Strobilanthes cusia.

[0022] Particularly preferred plants that produce indigo are selected from the genus Indigofera and in particular from Indigofera tinctoria.

[0023] The plants of the aforementioned genera and species contain no or only small amounts of indigo and indirubin. Instead, the plants contain the compound indican, a precursor to indigo and indirubin. The parts of the aforementioned plant genera and species that are rich in indican and also contain indigo are the leaves of these plants. For use as dyes for keratin fibers, the plant leaves of the aforementioned plant genera and species are dried and ground, and used as plant powder.

[0024] Plant powders preferred according to the invention have a particle size of less than 500 pm, particularly preferably in the range of 120 pm - 200 pm, extremely preferably in the range of 150 pm - 180 pm. Further plant powders preferred according to the invention have a bulk density in the range of 0.20 - 0.60 g / cm 3 , particularly preferably in the range of 0.25 - 0.40 g / cm 3Other plant powders preferred according to the invention have, based on their weight, a moisture content of less than 10% by weight, preferably 0.1-6.0% by weight, particularly preferably 0.2-3.0% by weight. The moisture content is determined after 3 hours of drying at 105°C.

[0025] According to the invention, it is preferred that the powder of the indigo-producing plant, based on its weight, consists of at least 50 wt.%, preferably at least 80 wt.%, particularly preferably more than 80-100 wt.%, of the leaves of the plant. Further colorants preferably used according to the invention are characterized in that the powder of the indigo-producing plant has a particle size of less than 500 pm, particularly preferably in the range of 120 pm-200 pm, extremely preferably in the range of 150 pm-180 pm, and also a bulk density in the range of 0.20-0.60 g / cm 3 , particularly preferably in the range of 0.25 - 0.40 g / cm 3and, based on its weight, has a moisture content of less than 10 wt.%, preferably 0.1 - 6.0 wt.%, particularly preferably 0.2 - 3.0 wt.%.

[0026] Further colorants preferably used according to the invention are characterized in that the powder of the indigo-producing plant contains the compound indican in an amount of 2 - 5 wt.%, preferably 2.5 - 4.5 wt.%, particularly preferably 3 - 4.1 wt.%, based on the weight of the powder.

[0027] Further colorants preferably used according to the invention are characterized in that at least one indigo-producing plant powder i) is contained in a total amount of 1 - 80 wt.%, preferably 2 - 50 wt.%, particularly preferably 3 - 25 wt.%, extraordinarily preferably 4 - 15 wt.%, further extraordinarily preferably 5 - 10 wt.%, further extraordinarily preferably 6 - 7 wt.%, based on the weight of the agent.

[0028] Further coloring agents preferably used according to the invention are characterized in that powdered leaves of Indigofera tinctoria are contained in an amount of 1 - 80 wt.%, preferably 2 - 50 wt.%, particularly preferably 3 - 25 wt.%, extraordinarily preferably 4 - 15 wt.%, further extraordinarily preferably 5 - 10 wt.%, further extraordinarily preferably 6 - 7 wt.%, based on the weight of the agent.

[0029] It has been found that the simultaneous application of an aqueous dispersion of at least one plant powder i) from at least one indigo-producing plant with cysteine ​​to keratin fibres leads to a red shift in the resulting colouration of the keratin fibres, which is undesirable in the present case.

[0030] The dyeing compositions (A) used according to the invention are therefore characterized in that they are free from cysteine, i.e., they do not contain cysteine.

[0031] Powders from the leaves of Indigofera tinctoria, which are preferably used according to the invention, react approximately neutrally in aqueous dispersion, with slight deviations between a slightly acidic and a slightly alkaline pH range. A 5 wt. % dispersion of ground leaves of Indigofera tinctoria in deionized water has a pH of 6.6 to 7.4, preferably 6.8 to 7.2, particularly preferably 6.9 to 7.1, each measured at 20°C.

[0032] The dyes used according to the invention also contain water. The water serves to disperse the plant powder and to dissolve the indican contained therein, making it available for reaction to produce indigo.

[0033] Colorants preferably used according to the invention are characterized in that water is contained in an amount of 19.9 - 95.0 wt.%, preferably 30.0 - 90.0 wt.%, particularly preferably 50.0 - 88.0 wt.%, extraordinarily preferably 60.0 - 85.0 wt.%, based on the weight of the agent.

[0034] In process step b), an aqueous dyeing composition (A) having a pH in the range from 2.0 to 10.0, preferably from 4.0 to 9.0, particularly preferably from 5.0 to 8.0, extraordinarily preferably from 6.0 to 7.4, in each case measured at 20°C, is applied to the keratin fibers to be dyed, which are preferably dry.

[0035] The colorants used according to the invention have a pH of 2.0 to 10.0, preferably of 4.0 to 9.0, particularly preferably of 5.0 to 8.0, extraordinarily preferably of 6.0 to 7.4, in each case measured at 20°C.

[0036] In a first preferred embodiment of the dyeing process according to the invention, the pH of the aqueous dyeing composition (A) is not influenced by the addition of an acid or a base, but corresponds to the pH generated by the dispersed plant powder. In a further preferred embodiment of the dyeing process according to the invention, the desired pH of the aqueous dyeing composition (A) is adjusted using an acid or a base. Preferred acids are selected from citric acid, lactic acid, gluconic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, galactaric acid (mucic acid), tartaric acid, malic acid, sulfuric acid, and phosphoric acid, as well as mixtures of these acids. Preferred bases are sodium hydroxide, potassium hydroxide, arginine, lysine, monoethanolamine, triethanolamine, 2-amino-2-methylpropan-1-ol, and mixtures of these bases.

[0037] In a further preferred embodiment of the dyeing process according to the invention, the desired pH of the aqueous dyeing composition (A) is adjusted with the aid of a buffer system selected from a mixture of a medium-strength or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a medium-strength or weak base with its conjugate or corresponding acid.

[0038] According to the invention, preferred suitable corresponding acid-base pairs are those which stabilize the aqueous dyeing composition (A) used according to the invention in the pH range from 2.0 to 10.0, preferably from 4.0 to 9.0, particularly preferably from 5.0 to 8.0, extraordinarily preferably from 6.0 to 7.4, in each case measured at 20°C.

[0039] Particularly preferred buffer systems according to the invention for the aqueous dyeing composition (A) used according to the invention are selected from

[0040] - Ammonia / ammonium salt mixtures, wherein the ammonium salt is preferably selected from ammonium chloride, ammonium bromide, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium acetate, ammonium glycolate, ammonium gluconate, ammonium tartrate, ammonium lactate, and mixtures of these ammonium salts, particularly preferably selected from ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, and ammonium carbonate, extremely preferably selected from ammonium chloride,

[0041] - mixtures of hydrogen phosphate and dihydrogen phosphate, in particular the alkali metal salts of hydrogen phosphate and dihydrogen phosphate, particularly preferably the sodium salts and / or the potassium salts of hydrogen phosphate and dihydrogen phosphate,

[0042] - mixtures of alkali metal bicarbonate with alkali metal carbonate, in particular mixtures of sodium or potassium bicarbonate with sodium or potassium carbonate,

[0043] - mixtures of citric acid and its salts, in particular the alkali metal citrates, in particular the sodium salts, in particular trisodium citrate,

[0044] - mixtures of tartaric acid and its salts, in particular the alkali metal tartrates, in particular the potassium salts, in particular potassium hydrogen tartrate, - mixtures of phthalic acid and its salts, in particular the potassium salts, in particular potassium hydrogen phthalate,

[0045] - mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures,

[0046] - mixtures of gluconic acid and its salts, in particular gluconic acid / sodium gluconate mixtures,

[0047] - mixtures of succinic acid and its salts, in particular the sodium salts, in particular sodium hydrogen succinate and disodium succinate, and

[0048] - mixtures of malic acid and its salts, in particular the sodium salts, in particular sodium hydrogen malate and disodium malate, and

[0049] - Ammonia / ammonium salt mixtures, wherein the ammonium salt is preferably selected from ammonium chloride, ammonium bromide, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium acetate, ammonium glycolate, ammonium gluconate, ammonium tartrate, ammonium lactate, and mixtures of these ammonium salts, particularly preferably selected from ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, and ammonium carbonate, extremely preferably selected from ammonium chloride.

[0050] Other buffer systems, such as acetic acid / sodium acetate, are also suitable in principle according to the invention. However, due to the vinegar odor, such a buffer is not acceptable for the production of a commercial cosmetic product.

[0051] To vary the pH value, further colorants and coloring processes preferably used according to the invention are characterized in that the aqueous coloring composition (A) contains a buffer system for pH adjustment, selected from a mixture of a medium-strength or weak acid or base with its conjugate or corresponding base or corresponding acid.

[0052] Further dyeing processes preferred according to the invention are characterized in that the aqueous dyeing composition (A) contains a buffer system selected from an ammonia / ammonium salt mixture for pH adjustment in the basic range. Preferred ammonium salts that buffer the strongly basic pH of the aqueous ammonia solution to a less basic pH are selected from ammonium chloride, ammonium bromide, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, ammonium carbonate, ammonium nitrate, ammonium acetate, ammonium glycolate, ammonium gluconate, ammonium tartrate, ammonium lactate, and mixtures of these ammonium salts. Ammonium chloride, ammonium hydrogen sulfate, ammonium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium bicarbonate, and ammonium carbonate are particularly preferred. Ammonium chloride is extremely preferred.

[0053] In principle, other buffer systems are also suitable.

[0054] Further dyeing processes preferred according to the invention are characterized in that the aqueous dyeing composition (A) contains a buffer system selected from a hydrogen phosphate salt / dihydrogen phosphate salt mixture for pH adjustment. Suitable salts are the sodium salts and the potassium salts of hydrogen phosphate and dihydrogen phosphate. With hydrogen phosphate salt / dihydrogen phosphate salt mixtures, pH values ​​in the range from 7.1 to about 8.2 can be adjusted.

[0055] For higher pH values, mixtures of sodium or potassium bicarbonate with sodium or potassium carbonate are suitable. Further dyeing processes preferred according to the invention are therefore characterized in that the aqueous dyeing composition (A) contains a buffer system selected from a mixture of sodium or potassium bicarbonate with sodium or potassium carbonate for pH adjustment. Suitable salts are the sodium salts and the potassium salts of bicarbonate and carbonate. With bicarbonate salt / carbonate salt mixtures, pH values ​​in the range from about 9.0 to about 11.0 can be adjusted.

[0056] The specialist can obtain the appropriate weights of buffer salts to adjust the desired pH value from the relevant manuals.

[0057] Preferred dyeing agents and dyeing processes according to the invention are further characterized in that no hydrogen peroxide is used in them.

[0058] Preferred dyes and dyeing processes according to the invention are further characterized in that they do not contain any ions or compounds of metals other than alkali metals and alkaline earth metals. The content of metal ions other than alkali metal ions and alkaline earth metal ions, which are present in trace amounts in the water used, e.g., in tap water or municipal water, is not taken into account. Tap water can contain an average of 2 mg of copper ions per liter, i.e., approximately 0.0002 wt.% copper ions. The maximum concentration of metal ions other than alkali metal ions and alkaline earth metal ions in preferred dyes according to the invention is 0.00001 to 0.002 wt.%, preferably 0.0001 to 0.001 wt.%, particularly preferably a maximum of 0.0007 wt.%, in each case based on the dye.If salts are to be present, the salts of alkali metals and alkaline earth metals, in particular the salts of sodium, potassium and magnesium, preferably the salts of sodium and potassium, are suitable according to the invention.

[0059] According to the invention, salts and compounds of aluminum, transition metals, and lanthanides are particularly undesirable. These metals, even in their elemental form, are not used in the dyes and dyeing processes according to the invention.

[0060] Conventional dyes and dyeing processes using natural dyes often use compounds, especially salts, of metals other than alkali metals and alkaline earth metals to improve the adhesion of the natural dye to the keratin fibers. The present dyes and dyeing processes according to the invention can dispense with the use of ions and compounds of metals other than alkali metals and alkaline earth metals.

[0061] Surprisingly, it was found that the temporal development of the coloring result on the keratin fibers can be accelerated if the coloring composition (A) is allowed to act with the addition of heat, for example, using a heat lamp, a hairdryer, or a hairdryer. Preferred coloring methods according to the invention are therefore characterized in that the coloring composition (A) is allowed to act with the addition of heat. Particularly preferred coloring methods according to the invention are characterized in that the coloring composition (A) is allowed to act with the addition of heat at a temperature of 25-60°C, particularly preferably at a temperature of 30-50°C, extremely preferably at a temperature of 35-40°C.

[0062] With regard to further preferred embodiments of the dyeing processes according to the invention, what has been said regarding the dyeing agents and dyeing compositions (A) used according to the invention applies mutatis mutandis.

[0063] In order to preserve the hair-protecting potential of natural dyes, the claimed method is preferably limited to those methods in which the keratin fibers have not been treated with an oxidizing agent within a period of up to 7 days prior to the application of the dyeing composition (A) according to the invention.

[0064] Oxidizing agents commonly used in hair cosmetics, but which are not intended to be used in hair treatments according to the invention, even as pretreatments, include hydrogen peroxide, persulfates, perbromates, percarbonates, perborates, and percarbamides. The oxygen contained in ambient air does not constitute an oxidizing agent in the context of the invention.

[0065] In order to preserve the hair-protecting potential of natural dyes, preferred methods according to the invention are limited to those methods in which the keratin fibers have not been treated with a keratin-reducing compound within a period of up to 7 days prior to the application of the coloring composition (A) according to the invention.

[0066] The keratin fibers are preferably dried after rinsing out the coloring composition (A). Drying can be carried out without actively applying heat. However, drying can also be carried out with the application of heat at a temperature of 25–120°C, particularly preferably at a temperature of 30–80°C, and extremely preferably at a temperature of 35–60°C. Heat is preferably applied using a heat lamp, a drying rod, a hair dryer, a straightening iron, or a hair dryer.

[0067] A further feature of the dyeing process according to the invention is that the dyeing composition (A) is allowed to act on the keratin fibers after application thereto for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 20 to 35 minutes, extraordinarily preferably 25 to 30 minutes.

[0068] After the exposure time for the dye composition (A) has elapsed, the keratin fibers are rinsed with water to wash out the dye composition (A).

[0069] Optionally, the keratin fibers can be dried after this rinsing step. This can be done with an absorbent cloth, such as a towel. Towel-dried hair can also be partially or completely dried with a hairdryer or other heat source. Allowing the keratin fibers to air dry is also possible.

[0070] Further dyeing processes preferred according to the invention are characterized in that no oxidation dye precursors are used in them. Typical oxidation dye precursors are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(1,2-dihydroxyethyl)phenol, 4-amino-2-(diethylaminomethyl)phenol, 2-(2,5-diaminophenyl)ethanol, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, N,N'-bis-(2-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-1,3-diamino-propan-2-ol, Bis-(2-hydroxy-5-aminophenyl)methane, 1,3-bis-(2,5-diaminophen- oxy)propan-2-ol, N,N'-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, 2,4,5,6-tetraaminopyrimidine, 4-Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo-[1,2-a]-pyrazol-1-one, 3-aminophenol, 5-amino-2-methylphenol,3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxy- ethanol, 5-Amino-4-chlor-2-methylphenol, 5-(2-Hydroxyethyl)-amino-2-methylphenol, 2,4-Dichlor-3- aminophenol, 2-Aminophenol, 3-Phenylendiamin, 2-(2,4-Diaminophenoxy)ethanol, 1 ,3-Bis(2,4-di- aminophenoxy)propan, 1-Methoxy-2-amino-4-(2-hydroxyethylamino)benzol, 1 ,3-Bis(2,4-diamino- phenyl)propan, 2, 6-Bis(2'-hydroxyethylamino)-1 -methylbenzol, 2-({3-[(2-Hydroxyethyl)amino]-4- methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methyl- phenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-Mor- pholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin, 1-Amino-3- bis-(2-hydroxyethyl)aminobenzol, Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 1 ,2,4-Trihydroxy- benzol, 2-Amino-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-di- methylpyridin, 3,5-Diamino-2,6-dimethoxypyridin, 1-Phenyl-3-methylpyrazol-5-on, 1-Naphthol,1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline and 7-hydro- xyindoline.,

[0071] The dye compositions (A) according to the invention and preferred according to the invention may optionally contain further additives to optimize the application properties of these compositions. Preferred additives are, in particular, thickeners, which ensure that the dye composition (A) adheres better to the hair during application.

[0072] Coloring compositions (A) used particularly preferably according to the invention contain at least one or more hydrophilic thickeners, which are preferably selected from polysaccharides that may be chemically and / or physically modified. Compounds from the group of polysaccharides are particularly preferred as hydrophilic thickeners according to the invention, since the basic structures of the polysaccharides are of natural origin and biodegradable. Preferred hydrophilic polysaccharide thickeners are selected from celluloses, cellulose ethers of C1-C4 alcohols, cellulose esters, xanthan gum, alginic acids (and their corresponding physiologically acceptable salts, the alginates), agar agar (with the polysaccharide agarose present in agar agar as the main constituent), starch fractions and starch derivatives such as amylose, amylopectin and dextrins, karaya gum, locust bean gum, gum arabic, pectins, dextrans and guar gum, and mixtures thereof.

[0073] Cellulose ethers of C1-C4 alcohols and cellulose esters preferred according to the invention are selected from methylcelluloses, ethylcelluloses, hydroxyalkylcelluloses (such as hydroxyethylcellulose), methylhydroxyalkylcelluloses and carboxymethylcelluloses (such as those with the INCI name Cellulose Gum) and their physiologically acceptable salts.

[0074] In preferred embodiments, xanthan gum is included as a hydrophilic thickener for reliable viscosity adjustment and residue-free application to keratin fibers and the scalp. In further preferred embodiments, carboxymethylcellulose (preferably carboxymethylcellulose with the INCI name Cellulose Gum) is included as a hydrophilic thickener for reliable viscosity adjustment and residue-free application to keratin fibers and the scalp. In a preferred embodiment, carboxymethylcellulose can be included as the sole hydrophilic thickener. A combination of carboxymethylcellulose and hydroxyethylcellulose is particularly preferred.

[0075] A combination of carboxymethylcellulose and xanthan (preferably xanthan with the INCI name Xanthan Gum) may also be preferred according to the invention. Particularly preferred coloring compositions (A) according to the invention contain at least one hydrophilic thickener in a total amount of 0.1 to 5 wt. %, preferably 0.5 to 4 wt. %, more preferably 1 to 3.5 wt. %, and most preferably 1.2 to 2 wt. %, based in each case on the weight of the respective coloring composition (A).

[0076] In a further preferred embodiment of the present invention, the coloring compositions (A) according to the invention contain, in each case based on their weight, 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, more preferably 1.2 to 2.0% by weight, of xanthan gum.

[0077] In a further preferred embodiment of the present invention, the dyeing compositions (A) according to the invention contain, in each case based on their weight, 0.1 to 4% by weight, preferably 1 to 2.8% by weight, of carboxymethylcellulose.

[0078] In a further preferred embodiment of the present invention, the dyeing compositions (A) according to the invention contain, in each case based on their weight, 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, more preferably 1.2 to 2.0% by weight, of hydroxyethylcellulose.

[0079] Particularly preferred dye compositions (A) according to the invention contain at least one organic solvent containing a phenyl group in the molecule. This solvent is preferably selected from phenoxyethanol, benzyl alcohol, and mixtures thereof. Surprisingly, it has been found that such aromatic solvents can have a positive effect on the dyeing results of the dyeing process according to the invention; this has been observed in particular when the dye composition (A) contains such an aromatic solvent.

[0080] In a further preferred embodiment of the present invention, the coloring compositions (A) preferred according to the invention contain, in each case based on their weight, 0.1 to 3 wt. %, preferably 0.5 to 2.5 wt. %, more preferably 0.8 to 1.0 wt. %, of at least one organic solvent which has a phenyl group in the molecule. In a further preferred embodiment of the present invention, the coloring compositions (A) according to the invention contain, in each case based on their weight, 0.1 to 3 wt. %, preferably 0.5 to 2.5 wt. %, more preferably 0.8 to 1.0 wt. %, of at least one organic solvent selected from phenoxyethanol, benzyl alcohol and mixtures thereof.

[0081] Particularly preferred dyeing compositions (A) according to the invention are characterized in that they contain at least one aliphatic solvent selected from C1-C4 alkanols and C2-C4 polyols, in particular selected from ethanol, isopropanol, n-propanol, ethylene glycol, 1,2-propanediol, glycerol and 1,3-butylene glycol, and mixtures of these solvents, but only in a total amount of 0.01-8 wt.%, preferably 0.1-6 wt.%, particularly preferably 0.5-4 wt.%, in each case based on the weight of the dyeing composition (A).

[0082] Other particularly preferred coloring compositions (A) according to the invention are characterized in that they do not contain an aliphatic solvent selected from C1-C4 alkanols and C2-C4 polyols. In order to make the coloring compositions (A) used according to the invention also sensorially attractive to the user, other particularly preferred coloring compositions (A) used according to the invention are characterized in that they contain at least one perfume oil containing at least one fragrance compound or odoriferous compound.

[0083] The definition of a fragrance substance within the meaning of this application corresponds to the standard definition 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. Examples of fragrance and perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate and jasmecyclate.Dyeing compositions (A) used with exceptional preference according to the invention are characterized in that they contain at least one fragrance in a total amount of 0.01 - 5 wt.%, preferably 0.1 - 3 wt.%, particularly preferably 0.5 - 2 wt.%, exceptionally preferably 1 - 1.5 wt.%, in each case based on the weight of the dyeing composition (A).

[0084] Post-treatment steps of the dyeing process according to the invention f)i)

[0085] In a first embodiment of the dyeing process according to the invention, the indigo-dyed keratin fibers are rinsed with additive-free water or soaked in additive-free water again for a period of 5 to 120 minutes, preferably 20 to 110 minutes, particularly preferably 30 to 100 minutes, extremely preferably 45 to 90 minutes, after rinsing out the dye.

[0086] According to the invention, additive-free water is understood to mean water that contains no other added substances. Preferred examples of this according to the invention are tap water and city water. However, deionized water is also considered additive-free water. f)ii)

[0087] In a second embodiment of the dyeing process according to the invention, the indigo-dyed keratin fibers are, after rinsing out the dye, rinsed again for a period of 5 to 120 minutes with an aqueous cysteine ​​solution (C) having a pH below 7.5 measured at 20°C, or soaked in an aqueous cysteine ​​solution (C) having a pH below 7.5 measured at 20°C.

[0088] Cysteine, as a chiral amino acid, possesses a stereogenic center and can occur in mirror-image form, namely in the form of L-cysteine ​​and D-cysteine. Both L-cysteine ​​and D-cysteine, as well as mixtures thereof, are encompassed by the present invention. Within the scope of the present invention, both possible enantiomers can therefore be used equally as specific compounds or as mixtures thereof, particularly as racemates. However, it is particularly advantageous according to the invention to use the naturally occurring isomer form, in this case L-cysteine.

[0089] Cysteine ​​solutions (C) used with exceptional preference according to the invention are characterized in that L-cysteine ​​is contained in an amount of 0.1 - 5.0 wt.%, preferably 0.5 - 3.0 wt.%, particularly preferably 0.8 - 2.0 wt.%, exceptionally preferably 1.0 - 1.5 wt.%, based on the weight of the cysteine ​​solution (C).

[0090] An aqueous solution of cysteine ​​reacts acidically. A 1 wt% solution of L-cysteine ​​in deionized water has a pH of 6.49, measured at 20°C. Cysteine ​​is therefore not an alkalizing agent.

[0091] Preferably used cysteine ​​solutions (C) have a pH of 2.0 to 7.1, preferably from 4.0 to 7.0, particularly preferably from 5.0 to 6.6, extraordinarily preferably from 5.5 to less than 6.5, in each case measured at 20°C. f)iii)

[0092] In a third embodiment of the dyeing process according to the invention, the indigo-dyed keratin fibers are, after rinsing out the dye, rinsed again for a period of 5 to 120 minutes with an aqueous composition (G) containing at least one glycosylase (EC 3.2) or soaked in an aqueous composition (G) containing at least one glycosylase (EC 3.2).

[0093] Glycosylases (EC 3.2)

[0094] In a preferred embodiment of the invention, the at least one glycosylase (EC 3.2) is selected from at least one glycosidase (EC 3.2.1). Among glycosidases (EC

[0095] 3.2.1) refers to enzymes that hydrolyze O-glycosyl components and S-glycosyl components. Glycosidases preferred according to the invention (EC 3.2.1) are selected from a group of enzymes generally referred to as cellulases.

[0096] The term "cellulase," as used herein, refers to enzymes that catalyze the hydrolysis of 1,4-beta-D-glucoside bonds present in cellulose (cellobiose) and / or lichenin and / or beta-D-glucans. Cellulases are often also capable of hydrolyzing the 1,4-bonds in beta-D-glucans, which possess 1,3-bonds in addition to the 1,4-bonds. Cellulases are capable of cleaving cellulose into beta-glucose. Consequently, cellulases act particularly on cellulose-containing or cellulose-derivative-containing residues and catalyze their hydrolysis. The decisive factor in determining whether an enzyme is a cellulase within the scope of the invention is its ability to hydrolyze 1,4-beta-D-glucoside bonds in cellulose.

[0097] The term "cellulase activity" is defined here as an enzyme that catalyzes the hydrolysis of 1,4-beta-D-glucoside bonds in beta-1,4-glucan (cellulose). Cellulose activity is measured using a standard method, e.g., as follows: Cellulases release glucose from CMC (carboxymethylcellulose). Samples are incubated with a substrate (1.25 wt% CMC) under defined reaction conditions (100 mM sodium phosphate buffer pH 7.5, 40°C, 15 min). Reaction with p-hydroxybenzoic acid hydrazide (PAHBAH) in the presence of bismuth produces a yellow dye that can be determined photometrically at 410 nm. An alkaline pH value is required during the color reaction. The amount of sugar released corresponding to the color is a measure of enzyme activity (Lever, Anal. Biochem., 1972, 47 & 1977, 81).

[0098] Cellulases can be divided into three categories:

[0099] 1. Endoglucanase (EC 3.2.1.4), also known as endo-1,4-beta-glucanase, beta-1,4-glucanase, avice-lase, beta-1,4-endoglucanhydrolase, endo-1,4-beta-D-glucanohydrolase,

[0100] Carboxymethylcellulase or celludextrinase;

[0101] 2. Cellulose-1,4-beta-cellobiosidase (non-reducing end) (EC 3.2.1.91), also known as exoglucanase, 1,4-beta-cellobiohydrolase, 4-beta-D-glucan cellobiohydrolase (non-reducing end), avicelase, exo-1,4-beta-D-glucanase or exocellobiohydrolase, releases cellobiose from the non-reducing ends of the ß-D-glucan chains by hydrolysis of the (1->4)-beta-D-glucosidic bonds in cellulose and cellotetraose;

[0102] 3. beta-Glucosidase (EC 3.2.1.21), also known as cellobiase, beta-D-glucoside glucohydrolase, amygdalase or gentobiase, hydrolyzes terminal, non-reducing beta-D-glucosyl groups to release beta-D-glucose.

[0103] In a further preferred embodiment of the invention, the at least one glycosidase (EC 3.2.1) is selected from endo-1,4-beta-glucanase (EC 3.2.1.4), beta-glucosidase (EC 3.2.1.21), exo-1,4-beta-glucosidase (EC 3.2.1.74), cellulose-1,4-beta-cellobiosidase (EC 3.2.1.176), exo-1,4-beta-D-glucanase (EC 3.2.1.91) and oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) as well as mixtures of these enzymes. In a further preferred embodiment of the invention, the at least one glycosidase (EC 3.2.1) is selected from endo-1,4-beta-glucanase (EC 3.2.1.4), beta-glucosidase

[0104] (EC 3.2.1 .21) and exo-1 ,4-beta-D-glucanase (EC 3.2.1 .91) as well as mixtures of these enzymes.

[0105] A particularly preferred embodiment of the invention is characterized in that the composition (G) used according to the invention contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4), at least one beta-glucosidase (EC 3.2.1.21) and at least one enzyme selected from at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) and at least one oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) and mixtures thereof.

[0106] A particularly preferred embodiment of the invention is characterized in that the composition (G) contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4), at least one beta-glucosidase (EC 3.2.1.21) and at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91).

[0107] A further particularly preferred embodiment of the invention is characterized in that the composition (G) contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4) in a total amount of 20-35% by weight, at least one beta-glucosidase (EC 3.2.1.21) in a total amount of 15-25% by weight, and - in a total amount of 25-35% by weight - at least one enzyme selected from at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) and at least one oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) and mixtures thereof, wherein the amounts are based on the total weight of the enzyme mixture.

[0108] A further particularly preferred embodiment of the invention is characterized in that the composition (G) contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4) in a total amount of 20 - 35 wt.%, at least one beta-glucosidase (EC 3.2.1.21) in a total amount of 15 - 25 wt.% and at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) in a total amount of 25 - 35 wt.%, wherein the amounts refer to the total weight of the enzyme mixture.

[0109] A further particularly preferred embodiment of the invention is characterized in that the composition (G) contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4) in a total amount of 20-35% by weight, at least one beta-glucosidase (EC 3.2.1.21) in a total amount of 15-25% by weight, furthermore - in a total amount of 25-35% by weight - at least one enzyme selected from at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) and at least one oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) and mixtures thereof, and in a total amount of up to 100% by weight at least one further enzyme with cellulase activity, wherein the amounts refer to the total weight of the enzyme mixture.

[0110] A further particularly preferred embodiment of the invention is characterized in that the composition (G) contains an enzyme mixture comprising at least one endo-1,4-beta-glucanase (EC 3.2.1.4) in a total amount of 20-35% by weight, at least one beta-glucosidase (EC 3.2.1.21) in a total amount of 15-25% by weight, and at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) in a total amount of 25-35% by weight, as well as at least one further enzyme with cellulase activity in a total amount of up to 100% by weight, the amounts being based on the total weight of the enzyme mixture. Compositions (G) preferably used according to the invention contain, in each case based on their weight, at least one glycosylase (EC 3.2) in a total amount of 0.0001 - 1% by weight, preferably 0.001 - 0.1% by weight, more preferably 0.002 - 0.05% by weight, particularly preferably 0.003 - 0.04% by weight, extraordinarily preferably 0.01 - 0.03% by weight.

[0111] A further particularly preferred embodiment of the invention is characterized in that the composition (G), based on its weight, contains at least one glycosidase (EC

[0112] 3.2.1) selected from at least one cellulase, in a total amount of 0.0001 - 1% by weight, preferably 0.001 - 0.1% by weight, more preferably 0.002 - 0.05% by weight, particularly preferably 0.003 - 0.04% by weight, extraordinarily preferably 0.01 - 0.03% by weight.

[0113] A further particularly preferred embodiment of the invention is characterized in that the composition (G), based on its weight, contains at least one glycosidase (EC

[0114] 3.2.1), selected from endo-1,4-beta-glucanase (EC 3.2.1.4), beta-glucosidase (EC 3.2.1.21) and exo-1,4-beta-D-glucanase (EC 3.2.1.91) and mixtures of these enzymes, in a total amount of 0.0001 - 1 wt.%, preferably 0.001 - 0.1 wt.%, more preferably 0.002 - 0.05 wt.%, particularly preferably 0.003 - 0.04 wt.%, extraordinarily preferably 0.01 - 0.03 wt.%.

[0115] A further particularly preferred embodiment of the invention is characterized in that the composition (G), based on its weight, contains at least one glycosidase (EC

[0116] 3.2.1) selected from at least one endo-1,4-beta-glucanase (EC 3.2.1.4), at least one beta-glucosidase (EC 3.2.1.21) and at least one enzyme selected from at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) and at least one oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) and mixtures thereof, in a total amount of 0.0001 - 1 wt.%, preferably 0.001 - 0.1 wt.%, further preferably 0.002 - 0.05 wt.%, particularly preferably 0.003 - 0.04 wt.%, extraordinarily preferably 0.01 - 0.03 wt.%.

[0117] In compositions (G) preferably used according to the invention, the water content is 40-99 wt.%, preferably 50-97 wt.%, particularly preferably 60-90 wt.%, in each case based on the weight of composition (G). f)iv)

[0118] In a fourth embodiment of the dyeing process according to the invention, the indigo-dyed keratin fibers are, after rinsing out the dye, rinsed again for a period of 5 to 120 minutes with an aqueous composition (L) containing laccase (EC 1.10.3.2) or soaked in an aqueous composition (L) containing laccase (EC 1.10.3.2).

[0119] Compositions (L) preferably used according to the invention contain, in each case based on their weight, 0.0001 - 1 wt.%, preferably 0.001 - 0.3 wt.%, further preferably 0.05 - 0.2 wt.%, particularly preferably 0.06 - 0.15 wt.%, extraordinarily preferably 0.07 - 0.1 wt.% laccase (EC 1.10.3.2).

[0120] In compositions (L) preferably used according to the invention, the water content is 40-99 wt.%, preferably 50-97 wt.%, particularly preferably 60-90 wt.%, in each case based on the weight of the composition (L). f)v)

[0121] In a fourth embodiment of the dyeing process according to the invention, the indigo-dyed keratin fibers are, after rinsing out the dyeing agent, rinsed again for a period of 5 to 120 minutes with an aqueous composition (AT) which, based on its weight, contains 1-20% by weight of an anionic surfactant and has a pH in the range of 3-6, measured at 20°C, or soaked in an aqueous composition (AT) which, based on its weight, contains 1-20% by weight of an anionic surfactant and has a pH in the range of 3-6, measured at 20°C.

[0122] Suitable anionic surfactants for the agents according to the invention 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, with the exception of linear and branched fatty acids with 8 to 30 carbon atoms and their salts (soaps). Additionally, the molecule may 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, polyethoxylated ether carboxylic acids, acyl sarcosides, acyl taurides, acyl isethionates,Sulfosuccinic acid mono- and dialkyl esters and sulfosuccinic acid mono-alkylpolyoxyethyl esters with 1 to 6 ethylene oxide groups, linear alkanesulfonates, linear alpha-olefinsulfonates, sulfonates of unsaturated fatty acids with up to 6 double bonds, alpha-sulfofatty acid methyl esters of fatty acids, C8-C2o-alkyl sulfates and C8-C2o-alkyl ether sulfates with 1 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 selected from C8-C2o-alkyl sulfates, C8-C2o-alkyl ether sulfates and C8-C2o-ether carboxylic acids,each with 8 to 20 C atoms in the alkyl group and 0 to 12 ethylene oxide groups in the molecule. Sodium laureth(2) sulfate is particularly preferred.

[0123] The anionic surfactant composition (AT) used according to the invention has a pH in the range of 3 - 6, preferably 4 - 5.5, particularly preferably 4.5 - 5, in each case measured at 20°C.

[0124] Implementation examples

[0125] The exemplary embodiments presented below are intended to explain the subject matter of the invention in more detail without limiting it thereto.

[0126] The color difference, also known as dE or AE, can be easily determined colorimetrically using a colorimeter that measures colors in the L*, a*, b* color space, for example, a Datacolor Spectraflash SF 600 colorimeter. All colorimetric measurements presented below were performed using the Datacolor Spectraflash SF 600 colorimeter.

[0127] The L*,a*,b* color space refers to the CIELAB color space. The L value represents the brightness of the color (black-white axis); the higher the L value, the brighter the color. The a value represents the red-green axis of the system; the higher this value, the more the color is shifted toward red. The b value represents the yellow-blue axis of the system; the higher this value, the more the color is shifted toward yellow.

[0128] The color shift AE, i.e. the color difference between two (hair) colors, for each of which an L*, a*, b* value combination has been determined, is calculated according to the following formula:

[0129] AE = (AL 2 + Aa 2 + From 2 ) 05

[0130] The larger the value for AE, the more pronounced the color difference.

[0131] A D65 illuminant and a diffuse / 8° optical configuration were used for the spectrophotometer measurements. The spectral reflectance data for each sample from 380 nm to 700 nm were converted to colorimetric data using DCI Color software. Reflectance measurements were determined for each hair sample, with the average of four measurements recorded.

[0132] The color difference (AE) between untreated strand and treated strand was calculated according to the following formula:

[0133] Lv, av, bv: Colorimetric values ​​for untreated strands

[0134] Ln, an, bn: Colorimetric values ​​for treated strand

[0135] In order to track the temporal development of the final color, measurements were taken on day 0 directly after coloring and 14 days after coloring and compared.

[0136] To prepare the dye composition (A) used according to the invention, 2.5 g of indigo powder were dispersed in 47.5 grams of demineralized water (5% by weight of the total dispersion). After stirring the dispersion for 2 minutes, a strand of buffalo belly hair (brush body tied round, approximately 8 cm of free hair) was placed in the dye composition (A) for 30 minutes while stirring (liquor ratio: 50 grams of dye composition to 1 gram of hair strand, pH: 6.46-7.29). The dye composition (A) was then washed off the strands by rinsing the strands under running deionized water for 30 seconds, combing them 20 times (20°C). The hair strands were then dried with a commercially available hair dryer at a defined distance (d = 10 cm) and a defined temperature (T = 80 ± 5 °C) with 20 combs.

[0137] The control strands were also treated as described above and were not further treated.

[0138] The following plant raw materials were used:

[0139] “C30-Indigo Leaves Powder” (Indigofera tinctoria L.) powdered leaves of Indigofera tinctoria pH of the 5 wt.% dispersion in water: 6.8 to 7.2 (20°C)

[0140] Source: Couleurs de Plantes, rue de l'Arsenal, 17300 Rochefort, France or

[0141] Indigo Powder (Indigofera tinctoria L.) powdered leaves of Indigofera tinctoria. pH of the 5 wt.% dispersion in water: 6.8 to 7.2 (20°C)

[0142] Source: Matha Exports International LLP, Ashram, India

[0143] Immediately after drying, i.e., within a time of zero seconds to 30 minutes, preferably 10 seconds to 10 minutes, particularly preferably 1 to 5 minutes, the strands were subjected to one of five different post-treatments, as described below, except for the control strands. f)i) Post-treatment with water

[0144] A first embodiment of the dyeing process according to the invention comprises the aftertreatment of the freshly indigo-dyed strands with pure, i.e., additive-free, demineralized water. For this purpose, the freshly dyed indigo strands were placed in 50 ml of demineralized water (20°C, liquor ratio: 50 grams of additive-free demineralized water to 1 gram of hair strand). They were stirred for 1.5 hours and then combed and dried as described above.

[0145] Directly after the treatment, a slightly less green and slightly more bluish color tone (AE 6.1) was observed compared to the control strand.

[0146] The AE value between the mean values ​​of the freshly dyed strands with water treatment and the strands 14 days after dyeing and water treatment is 1.8. The corresponding AE value of the control strands between the two measurement times is 18.5. The differences between the control strand and the strands with water treatment are listed below (individual measurements, mean values, and AE values, see Table 1).

[0147] Table 1: L*-, a*-, b*-, AE-values ​​(mean values) of indigo dyeings with water post-treatment

[0148] (according to the invention) and without water treatment (control)

[0149] Even after 14 days, the strands treated with water remained blue and displayed a significantly less pronounced red / purple tone than the control strands (see Table 1). The water treatment significantly reduced or stopped the formation of the red tint after 14 days.

[0150] The water-based post-treatment achieves a clearer blue tone right from the start. After coloring the strand, the color result remains more consistent and stable with an AE of 1.8 than the control strand with an AE of 18.5. f)ii) Post-treatment with cysteine

[0151] A second embodiment of the dyeing process according to the invention comprises the after-treatment of the freshly indigo-dyed strands with an aqueous cysteine ​​solution (C).

[0152] For this purpose, 0.5 g of (R)-(+)-cysteine ​​was dissolved in 49.5 grams of demineralized water (1 wt.% of the total solution, pH: 5.47), stirred for 2 minutes, and the freshly dyed indigo strands were added (liquor ratio: 50 grams of cysteine ​​solution (C) to 1 g of hair strand).

[0153] These were stirred for 30 minutes and then combed and dried as described above.

[0154] Directly after the treatment, a slightly less green and slightly more bluish color tone (AE 6.3) was observed compared to the control strand.

[0155] The AE value between the mean values ​​of the freshly dyed strands with cysteine ​​post-treatment and the strands 14 days after dyeing and cysteine ​​post-treatment is 3.9. The corresponding AE value of the control strand between both measurement times is 18.5. The differences between the control strand and the strands with cysteine ​​post-treatment are listed below (individual measurements, mean values, and AE values ​​can be found in Table 2).

[0156] Table 2: L*, a*, b*, AE values ​​(mean values) of indigo stainings with cysteine ​​post-treatment (according to the invention) and without cysteine ​​post-treatment (control)

[0157] Even after 14 days, the strand treated with cysteine ​​remains blue and displays a significantly less pronounced red / purple hue than the control strand (see Table 2). The cysteine ​​treatment significantly reduces or even stops the formation of the red tint after 14 days.

[0158] Post-treatment with 1 wt.% cysteine ​​in an aqueous solution results in a clearer blue tone right from the start. Over time, the color result remains more stable with an AE of 3.9 compared to the control strand with an AE of 18.5. f)iii) Post-treatment with glycosylase

[0159] A third embodiment of the dyeing process according to the invention comprises the after-treatment of the freshly indigo-dyed strands with an aqueous composition (G) containing at least one glycosylase (EC 3.2).

[0160] For the preparation of composition (G), a glycosylase mixture (EC 3.2) obtained from Novozymes was used, hereinafter referred to as “cellulase blend”. This enzyme mixture comprised at least one endo-1,4-beta-glucanase (EC 3.2.1.4) in a total amount of 20 - 35 wt.%, at least one beta-glucosidase (EC 3.2.1.21) in a total amount of 15 - 25 wt.%, furthermore at least one enzyme selected from at least one exo-1,4-beta-D-glucanase (EC 3.2.1.91) and at least one oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) and mixtures thereof in a total amount of 25 - 35 wt.%, and in a total amount of up to 100 wt.% at least one further enzyme with glycosylase activity, wherein the amounts refer to the total weight of the enzyme mixture. The enzyme active substance content in the raw material used, which was present as an aqueous composition, was 190 pg / pl, i.e. 19 wt%.Furthermore, the “cellulase blend” contained, based on its weight, 66 wt% water and 15 wt% of a sucrose / D-glucose mixture.

[0161] To prepare composition (G), 100 μl of "cellulase blend" was made up to 50 grams of solution (0.038 wt% enzyme content, pH 7 (20°C)) with demineralized water, stirred for 2 minutes, and the freshly dyed indigo strands were added (liquor ratio: 50 grams of solution to 1 gram of hair strand). These strands were stirred for 30 minutes and then combed and dried as described above. Immediately after the post-treatment, a slightly less green shade (AE 4.1) was observed compared to the control strand.

[0162] The AE value between the mean values ​​of the freshly dyed cellulase-treated strands and the cellulase-treated strands 14 days after dyeing and cellulase post-treatment is 4.8. The corresponding AE value of the control strand between both measurement times is 18.5. The differences between the control strand and the strands with added cellulase are listed below (individual measurements, mean values, and AE values, see Table 3).

[0163] Table 3: L*, a*, b*, AE values ​​[mean values] of indigo dyeings with cellulase post-treatment (according to the invention) and without cellulase post-treatment (control)

[0164] Even after 14 days, the strand treated with cellulase remains blue and displays a significantly less pronounced red / purple tone than the control strand (see Table 3). Cellulase post-treatment significantly reduces or even stops the development of the red tint after 14 days. The cellulase post-treatment achieves a clearer blue tone right from the start. Over time, the strand color remains more stable with an AE of 4.8 than the control strand, which has an AE of 18.5. f)iv) Post-treatment with laccase

[0165] A fourth embodiment of the dyeing process according to the invention comprises the after-treatment of the freshly indigo-dyed strands with an aqueous composition (L) containing laccase (EC 1.10.3.2).

[0166] For the preparation of the aqueous composition (L), an aqueous laccase preparation (EC 1.10.3.2) from Novozymes was used, which had an active substance content of 6.25 wt.%.

[0167] To prepare the aqueous composition (L), 600 μl of laccase preparation was made up to 50 grams with demineralized water (0.075 wt% enzyme content, pH 7 (20°C)), stirred for 2 minutes, and the freshly dyed indigo strands were added (liquor ratio: 50 grams of laccase solution (L) to 1 g of hair strand). These strands were stirred for 30 minutes and then combed and dried as described above.

[0168] Directly after the treatment, a slightly less green and slightly more bluish color tone (AE 4.6) was observed compared to the control strand. The AE value between the mean values ​​of the freshly dyed strands treated with laccase and the strands treated with laccase 14 days after dyeing and laccase treatment is 7.0. The corresponding AE value of the control strand between the two measurement times is 18.5. The differences between the control strand and the strands with added laccase are listed below (individual measurements, mean values, and AE values ​​can be found in Table 4).

[0169] Table 4: L*, a*, b*, AE values ​​[mean values] of indigo dyeings with laccase post-treatment (according to the invention) and without laccase post-treatment (control)

[0170] After 14 days, the strand treated with laccase is blue in color and shows a less pronounced red / purple tone than the control strand (see Table 4). Laccase treatment reduces the formation of the reddish tint after 14 days.

[0171] The laccase post-treatment achieves a clearer blue tone right from the start. After coloring the strand, the color result remains more stable with an AE of 7.0 than the control strand with an AE of 18.5. f)v) Post-treatment with acidic anionic surfactant solution

[0172] A fifth embodiment of the dyeing process according to the invention comprises the after-treatment of the freshly indigo-dyed strands with an aqueous composition (AT) which, based on its weight, contains 1-20 wt.% of an anionic surfactant and has a pH in the range of 3-6, measured at 20°C.

[0173] To prepare the aqueous composition (AT), an aqueous solution of 12.5 wt.% sodium laureth sulfate was prepared, adjusted to a pH of 4.5 (20°C) with citric acid, and the freshly dyed indigo strands were added (liquor ratio: 50 grams of anionic surfactant solution (AT) to 1 g of hair strand). These strands were stirred for 30 minutes and then combed and dried as described above.

[0174] Directly after the anionic surfactant treatment, a slightly less green and slightly more bluish color tone (AE 6.8) was observed compared to the control strand.

[0175] The AE value between the mean values ​​of the freshly dyed strands treated with the anionic surfactant and these strands 14 days after dyeing and post-treatment is 6.1. The corresponding AE value of the control strand between the two measurement times is 18.5. The differences between the control strand and the strands with wash test post-treatment are listed below (individual measurements, mean values, and AE values, see Table 5). Table 5: L*, a*, b*, AE values ​​[mean values] of the indigo dyeings with anionic surfactant post-treatment (according to the invention) and without anionic surfactant post-treatment (control)

[0176] After 14 days, the strand treated with anionic surfactant is blue in color and shows a less pronounced red / purple tone than the control strand (see Table 5s). The anti-ionic surfactant treatment reduces the formation of the reddish tint after 14 days.

[0177] The anti-ionic surfactant post-treatment achieves a clearer blue tone right from the start. After coloring, the color result remains more stable with an AE of 6.6 compared to the control strand with an AE of 18.5.

Claims

Patent claims 1. A process for the non-oxidative coloring of keratin fibers, in particular human hair, comprising the following process steps in the given order: a) providing an aqueous coloring composition (A) which contains at least one indigo-producing plant powder i), is free of cysteine ​​and has a pH of 2.0 to 10.0, preferably from 4.0 to 9.0, particularly preferably from 5.0 to 8.0, extraordinarily preferably from 6.0 to 7.4, in each case measured at 20°C, b) applying the aqueous coloring composition (A) to the keratin fibers, c) leaving to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, d) rinsing the keratin fibers with water, e) optionally drying the keratin fibers, f) immediately thereafter within a time of zero seconds to 30 minutes, preferably 10 seconds to 10 minutes, preferably 1 to 5 minutes,Treating the keratin fibers with one of the following post-treatment steps: f)i. Rinsing or soaking the keratin fibers with additive-free water for a period of 5 to 120 minutes, f)ii. Rinsing or soaking the keratin fibers with an aqueous cysteine ​​solution (C) having a pH below 7.5 measured at 20°C for a period of 5 to 120 minutes, f)iii. Rinsing or soaking the keratin fibers with an aqueous composition (G) containing at least one glycosylase (EC 3.2) for a period of 5 to 120 minutes, f)iv. Rinsing or soaking the keratin fibers with an aqueous composition (L) containing laccase (EC 1.10.3.2) for a period of 5 to 120 minutes, f)v. Rinsing or soaking the keratin fibres with an aqueous composition (AT) containing, based on its weight, 1-20% by weight of an anionic surfactant and having a pH in the range of 3-6, measured at 20°C,for a period of 5 to 120 minutes, whereby the process does not use hydrogen peroxide and no ions and compounds of metals other than alkali metals and alkaline earth metals.

2. Dyeing process according to claim 1, characterized in that the dyeing composition (A) is allowed to act with the addition of heat, preferably at a temperature of 25 - 60 °C, particularly preferably at a temperature of 30 - 50 °C, extraordinarily preferably at a temperature of 35 - 40 °C. Dyeing process according to claim 1 or 2, characterized in that the indigo-producing^) plant(s) is / are selected from at least one species of the following genera: - Indigofera, in particular Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata, Indigofera arrecta, Indigofera heterantha “Gerardiana”, Indigofera argentea or Indigofera longi-racemosa; - Isatis, especially Isatis tinctoria (woad); - Persicaria, especially Persicaria tinctoria (dyer's knotweed); - Wrightia, especially Wrightia tinctoria; - Calanthe, especially Calanthe veratrifolia; and - Baphicacanthus cusia, synonym Strobilanthes cusia, wherein the indigo-producing plant(s) is / are preferably selected from the genus Indigofera and in particular from Indigofera tinctoria. Dyeing process according to one of claims 1 to 3, characterized in that the powder of the indigo-producing plant, based on its weight, consists of at least 50 wt.%, preferably at least 80 wt.%, particularly preferably more than 80-100 wt.%, of the leaves of the plant. Dyeing process according to one of claims 1 to 4, characterized in that the powder of the indigo-producing plant contains indican in an amount of 2-5 wt.%, preferably 2.5-4.5 wt.%, particularly preferably 3-4.1 wt.%, based on the weight of the powder. Dyeing process according to one of claims 1-5, characterized in that the composition (A) comprises at least one indigo-producing plant powder i) in a total amount of 1-80% by weight, preferably 2-50% by weight.-%, particularly preferably 3 - 25 wt.%, extraordinarily preferably 4 - 15 wt.%, further extraordinarily preferably 5 - 10 wt.%, further extraordinarily preferably 6 - 7 wt.%, based on the weight of the composition (A). Dyeing process according to one of claims 1 - 6, characterized in that the composition (A) contains powdered leaves of Indigofera tinctoria in an amount of 1 - 80 wt.%, preferably 2 - 50 wt.%, particularly preferably 3 - 25 wt.%, extraordinarily preferably 4 - 15 wt.%, further extraordinarily preferably 5 - 10 wt.%, further extraordinarily preferably 6 - 7 wt.%, based on the weight of the composition (A). Dyeing process according to one of claims 1-8, characterized in that the composition (A) contains water in an amount of 19.9-95.0 wt.%, preferably 30.0-90.0 wt.%, particularly preferably 50.0-88.0 wt.%, extraordinarily preferably 60.0-85.0 wt.%, based on the weight of the composition (A). Dyeing process according to one of claims 1-7, characterized in that the aqueous cysteine ​​solution (C) in step f)ii) contains, based on its weight, 0.1-5 wt.%, preferably 0.2-1.5 wt.%, particularly preferably 0.5-1 wt.% cysteine. Staining method according to one of claims 1-9, characterized in that the cysteine ​​solution (C) has a pH in the range from 2.0 to 7.1, preferably from 4.0 to 7.0, particularly preferably from 5.0 to 6.6, extraordinarily preferably from 5.5 to less than 6.5, in each case measured at 20°C. Staining method according to one of claims 1-10, characterized in that in step f)iii) the at least one glycosylase (EC3.2) is selected from at least one glycosidase (EC 3.2.1). The dyeing process according to claim 11, characterized in that the at least one glycosidase (EC 3.2.1) is selected from at least one cellulase. Dyeing process according to one of claims 11 or 12, characterized in that the at least one glycosidase (EC 3.2.1) or at least one cellulase is selected from endo-1,4-beta-glucanase (EC 3.2.1.4), beta-glucosidase (EC 3.2.1.21), exo-1,4-beta-glucosidase (EC 3.2.1.74), cellulose-1,4-beta-cellobiosidase (EC 3.2.1.176), exo-1,4-beta-D-glucanase (EC 3.2.1.91) and oligooxyloglucan-reducing end-specific cellobiohydrolase (EC 3.2.1.150) as well as mixtures of these enzymes. Dyeing process according to one of claims 1-13, characterized in that the composition (G), based on its weight, contains at least one glycosylase (EC 3.2) in a total amount of 0.0001-1 wt.%, preferably 0.001-0.1 wt.-%, more preferably 0.002 - 0.05 wt.%, particularly preferably 0.003 - 0.04 wt.%, extraordinarily preferably 0.01 - 0.03 wt.%. Dyeing process according to one of claims 1-14, characterized in that in step f)iv, the composition (L), based on its weight, contains 0.0001 - 1 wt.%, preferably 0.

001. - 0.3 wt.%, more preferably 0.05 - 0.2 wt.%, particularly preferably 0.06 - 0.15 wt.%, extraordinarily preferably 0.07 - 0.1 wt.% laccase (EC 1.10.3.2).

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