Two-step dyeing method using natural dyes with improved color intensity

Abstract

The invention relates to a two-step method for dyeing keratin-containing fibers, in particular human hair, using a natural dye based on flavones or flavone glycosides in combination with at least one glycosylase (E.C. 3.2) and subsequent application of an iron (II) salt, and to compositions and kits for carrying out said dyeing method.

Description

[0001] Two-stage dyeing process with natural dyes with improved color intensity

[0002] The invention relates to a two-stage process for dyeing keratin-containing fibers, in particular human hair, using a natural dye based on flavones or flavone glycosides in combination with at least one glycosylase (EC 3.2) and subsequent application of an iron(II) salt, as well as compositions and kits for carrying out this dyeing process.

[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 coloration 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 enabling hair color changes with excellent fastness properties. These azo dyes are synthetic dyes. However, a growing number of consumers desire hair dyes and hair coloring processes based on natural dyes, even if these products and processes are often inferior to the aforementioned products and processes in terms of fastness properties, coverage, and color variety.

[0004] State of the art

[0005] The patent specification KR102102671 B1 discloses the large-scale production of the antioxidant flavone luteolin from extracts of chrysanthemum by fermentation with lactic acid bacteria of the genus Lactobacillus, which contain the enzyme beta-glucosidase.

[0006] Task

[0007] The object of the present invention was to provide a process for coloring keratin-containing fibers, in particular human hair, using naturally occurring substances. A further object of the present invention was to provide a process for coloring keratin-containing fibers, in particular human hair, using naturally occurring substances, which achieve colorations with good coloring properties, in particular with high color intensity, good wash, light, and / or rubbing fastness, good homogeneity, and good balancing ability, i.e., low selectivity between damaged and undamaged areas along the keratin fibers.

[0008] Surprisingly, it was found that by the combined application of at least one flavone-containing or flavone glycoside-containing plant part and at least one glycosylase (EC 3.2) located outside the plant part to keratin fibers and a subsequent treatment with the solution of an iron(II) salt, colorations of the keratin fibers with good application properties are achieved.

[0009] A first aspect of the present invention is a process for the non-oxidative coloring of keratin fibers, in particular human hair, with natural dyes, which comprises the following process steps in the given order: a) providing a composition (F) which contains at least one flavone or flavone glycoside and providing a composition (E) which contains at least one glycosylase (EC 3.2), b) preparing a mixture (M) from the compositions (F) and (E), c) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying the mixture (M) to the keratin fibers, d) leaving it to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, e) rinsing the keratin fibers with water, f) optionally drying the keratin fibers, g) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying an aqueous composition (FE) which contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.-%, in each case based on the weight of the composition (FE), and has a pH in the range of 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extraordinarily preferably 4.5 to 5.2, in each case measured at 20°C, h) leaving to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, i) rinsing the keratin fibers with water, j) optionally drying the keratin fibers.

[0010] Another object of the present invention is a kit for the non-oxidative coloring of keratinic fibers, in particular human hair, which comprises the following compartments which are physically separate from one another: a composition (F) which contains at least one flavone or flavone glycoside, a composition (E) which contains at least one glycosylase (EC 3.2) and an aqueous composition (FE) which contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0% by weight, preferably 0.01 - 2% by weight, particularly preferably 0.1 - 1% by weight, in each case based on the weight of the composition (FE), and has a pH in the range of 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extraordinarily preferably 4.5 to 5.2, in each case measured at 20°C.

[0011] Source of flavones and flavonglycosides

[0012] Flavones and flavone glycosides preferably used according to the invention are present a) as extracts from plants or plant parts containing flavones or flavone glycosides; b) as plant parts containing flavones or flavone glycosides. In this case, the glycosylases separately provided according to the invention do not include those glycosylases that are naturally present in the flavone (glycoside)-containing plant parts used.

[0013] A preferred embodiment of the invention is characterized in that the flavone-containing or flavone glycoside-containing plant part, which is used as such in dried form or its extract, is selected from the flowers, leaves, stems, branches, bark, trunk wood, berries, fruits, aggregate nuts, aggregate stone fruits, stone fruits, apple fruits, peels, seeds, cones or roots of at least one flavone-containing or flavone glycoside-containing plant.

[0014] A further preferred embodiment of the invention is characterized in that the at least one flavone or flavone glycoside is selected from luteolin, apigenin, apiin, rutin, kaempferol, quercetin, salvigenin, myricetin and the glycosides derived from the above-mentioned flavones, as well as mixtures of these substances.

[0015] In a further preferred embodiment of the invention, the composition (F) is characterized in that it contains, based on its weight, at least one flavone or flavone glycoside selected from luteolin, apigenin, apiin, rutin, kaempferol, quercetin, salvigenin, myricetin and the glycosides derived from the above-mentioned flavones, as well as mixtures of these substances in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0016] In a further preferred embodiment of the invention, the composition (M) is characterized in that it contains, based on its weight, at least one flavone or flavone glycoside selected from luteolin, apigenin, apiin, rutin, kaempferol, quercetin, salvigenin, myricetin, and the glycosides derived from the aforementioned flavones, as well as mixtures of these substances, in a total amount of 0.01-5 wt.%, preferably 0.05-2 wt.%, particularly preferably 0.1-1 wt.%, extraordinarily preferably 0.2-0.6 wt.%, further extraordinarily preferably 0.3-0.5 wt.%. a) Extracts from plants or parts of plants containing flavones or flavone glycosides

[0017] In an extremely preferred embodiment of the invention, at least one extract from at least one flavone-containing or flavone glycoside-containing plant part is used. Plant parts preferred according to the invention, from which at least one extract preferred according to the invention can be obtained, are the flowers, leaves, stems, branches, bark, trunk wood, berries, fruits, aggregate nuts, aggregate drupes, stone fruits, apple fruits, peels, seeds, cones, or roots of at least one flavone-containing or flavone glycoside-containing plant.

[0018] Suitable extractants are water, in particular hot water at a temperature of 45 - 100 °C, furthermore C1-C4-alkanols and C2-C4-polyols, in particular ethanol, isopropanol, n-propanol, ethylene glycol, 1,2-propanediol, glycerol and 1,3-butylene glycol, and mixtures of these extractants, in particular mixtures of water and at least one C1-C4-alkanol, mixtures of water and at least one C2-C4-polyol, particularly preferably water / ethanol mixtures.

[0019] The extract itself can preferably be used in concentrated form, obtainable by partially distilling off the extractant after extraction, as a viscous liquid. Other extracts preferred according to the invention are used in powder form, obtainable by drying, preferably spray drying, the solvent-containing extract.

[0020] A preferred embodiment of the invention is characterized in that the at least one flavone or flavone glycoside used according to the invention originates from at least one extract of a plant selected from Reseda, in particular Reseda luteola and Reseda lutea, Genista tinctoria, Matricaria chamomilla, Chrysanthemum, Petroselinum crispum, Cynara, Citrus sinensis, Daucus carota, Apium, Mentha piperita and Perilla frutescens.

[0021] In a particularly preferred embodiment of the invention, the at least one flavone or flavone glycoside used according to the invention originates from a plant selected from Reseda, in particular Reseda luteola and Reseda lutea, Genista tinctoria, Chrysanthemum and Matricaria chamomilla.

[0022] In a particularly preferred embodiment of the invention, the at least one flavone or flavone glycoside used according to the invention originates from an extract of the flowers, leaves and stems of Reseda luteola.

[0023] In a particularly preferred embodiment of the invention, the at least one flavone or flavone glycoside used according to the invention originates from an aqueous-ethanolic extract of the flowers, leaves and stems of Reseda luteola.

[0024] Of course, the compositions (F) used according to the invention and preferably according to the invention may also contain plant parts and / or plant extracts from two or more different plants.

[0025] Extracts preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside in a total amount of 1-100 wt.%, preferably 10-85 wt.%, particularly preferably 20-80 wt.%, extraordinarily preferably 40-75 wt.%. Compositions (F) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside in a total amount of 0.01-5 wt.%, preferably 0.05-2 wt.%, particularly preferably 0.1-1 wt.%, extraordinarily preferably 0.2-0.6 wt.%, further extraordinarily preferably 0.3-0.5 wt.%.

[0026] Compositions (M) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0027] Compositions (F) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Reseda luteola in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0028] Compositions (M) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Reseda luteola in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0029] Compositions (F) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Reseda lutea in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0030] Compositions (M) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Reseda lutea in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0031] Compositions (F) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Chrysanthemum in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0032] Compositions (M) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Chrysanthemum in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0033] Compositions (F) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Genista tinctoria in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%.

[0034] Compositions (M) preferably used according to the invention contain, in each case based on their weight, at least one flavone or flavone glycoside from Genista tinctoria in a total amount of 0.01-5 wt.%, preferably 0.05-2 wt.%, particularly preferably 0.1-1 wt.%, extraordinarily preferably 0.2-0.6 wt.%, further extraordinarily preferably 0.3-0.5 wt.%. b) Use of comminuted plant parts

[0035] In a further preferred embodiment of the invention, the plant parts used are used in dried and comminuted form. In an extremely preferred embodiment of the invention, flowers and / or leaves and / or stems are used as the flavone-containing or flavone glycoside-containing plant part, particularly preferably in dried and comminuted form. In a further extremely preferred embodiment of the invention, the flowers and / or leaves and / or stems of Reseda luteola are used as the flavone-containing or flavone glycoside-containing plant part, particularly preferably in dried and comminuted form. In a further extremely preferred embodiment of the invention, the flowers and / or leaves and / or stems of Reseda lutea are used as the flavone-containing or flavone glycoside-containing plant part, particularly preferably in dried and comminuted form.In another extremely preferred embodiment of the invention, the flowers and / or leaves and / or stems of Chrysanthemum are used as the flavone- or flavone glycoside-containing plant part, particularly preferably in dried and comminuted form. In another extremely preferred embodiment of the invention, the flowers and / or leaves and / or stems of Genista tinctoria are used as the flavone- or flavone glycoside-containing plant part, particularly preferably in dried and comminuted form.

[0036] In a further extremely preferred embodiment of the invention, the at least one flavone-containing or flavonglycoside-containing plant part is used in powder form.

[0037] In a further preferred embodiment of the invention, the composition (F) is characterized in that it contains, based on its weight, at least one flavone-containing or flavone glycoside-containing plant part in a total amount of 0.05 - 20 wt.%, preferably 0.1 - 10 wt.%, more preferably 0.5 - 5 wt.%, particularly preferably 0.7 - 2 wt.%, extraordinarily preferably 1 - 1.5 wt.%.

[0038] In a further preferred embodiment of the invention, the composition (F) is characterized in that it contains, based on its weight, at least one flavone-containing or flavone glycoside-containing plant part selected from the flowers and / or leaves and / or stems of at least one plant selected from Reseda, in particular Reseda luteola or Reseda lutea, Genista tinctoria, Matricaria chamomilla, Chrysanthemum, Petroselinum crispum, Cynara, Citrus sinensis, Daucus carota, Apium, Mentha piperita and Perilla frutescens, in a total amount of 0.05 - 20 wt.%, preferably 0.1 - 10 wt.%, further preferably 0.5 - 5 wt.%, particularly preferably 0.7 - 2 wt.%, extraordinarily preferably 1 - 1.5 wt.%.

[0039] In a further preferred embodiment of the invention, the composition (M) is characterized in that it contains, based on its weight, at least one flavone-containing or flavone glycoside-containing plant part in a total amount of 0.05 - 20 wt.%, preferably 0.1 - 10 wt.%, more preferably 0.5 - 5 wt.%, particularly preferably 0.7 - 2 wt.%, extraordinarily preferably 1 - 1.5 wt.%.

[0040] In a further preferred embodiment of the invention, the composition (M) is characterized in that it contains, based on its weight, at least one flavone-containing or flavone glycoside-containing plant part selected from the flowers and / or leaves and / or stems of at least one plant selected from Reseda, in particular Reseda luteola or Reseda lutea, Genista tinctoria, Matricaria chamomilla, Chrysanthemum, Petroselinum crispum, Cynara, Citrus sinensis, Daucus carota, Apium, Mentha piperita and Perilla frutescens, in a total amount of 0.05 - 20 wt.%, preferably 0.1 - 10 wt.%, further preferably 0.5 - 5 wt.%, particularly preferably 0.7 - 2 wt.%, extraordinarily preferably 1 - 1.5 wt.%.

[0041] Compositions (F) preferably used according to the invention are water-containing and further comprise 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.

[0042] According to the invention, particularly suitable corresponding acid-base pairs are those which stabilize the aqueous composition (F) used according to the invention in the pH range from 1.0 to 8.0, preferably 2.5 to 7.0, particularly preferably 3.6 to 6.0, extraordinarily preferably 4.5 to 5.6, in each case measured at 20°C. Buffer systems particularly preferred according to the invention are selected from

[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 alkali metal tartrates, in particular potassium salts, in particular potassium hydrogen tartrate,

[0045] - mixtures of phthalic acid and its salts, in particular potassium salts, in particular potassium hydrogen phthalate,

[0046] - mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures,

[0047] - mixtures of gluconic acid and its salts, in particular gluconic acid / sodium gluconate mixtures,

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

[0049] - Mixtures of malic acid and its salts, in particular the sodium salts, in particular sodium hydrogen malate and disodium malate.

[0050] A particularly preferred buffer system according to the invention is formed from citric acid and at least one sodium salt of citric acid; mixtures of citric acid and trisodium citrate are extremely preferred.

[0051] 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.

[0052] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains a buffer system in an amount of 0.5 - 5 wt.%, preferably 0.8 - 4.5 wt.%, particularly preferably 1.5 - 3.5 wt.%, extraordinarily preferably 2.1 - 3.0 wt.%.

[0053] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% citric acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% trisodium citrate.

[0054] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% gluconic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% sodium gluconate.

[0055] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% lactic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% sodium lactate.

[0056] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% succinic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% disodium succinate.

[0057] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% succinic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% sodium hydrogen succinate.

[0058] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% malic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% disodium malate.

[0059] Dyeing processes preferred according to the invention are characterized in that the aqueous composition (F), in each case based on its weight, contains as buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extraordinarily preferably 0.6 - 0.9 wt.% malic acid and 0.3 - 3.5 wt.%, preferably 0.5 - 3.1 wt.%, particularly preferably 1.0 - 2.4 wt.%, extraordinarily preferably 1.5 - 2.1 wt.% sodium hydrogen malate.

[0060] In compositions (F) preferably used according to the invention, the water content is 40-95% by weight, preferably 50-90% by weight, particularly preferably 60-85% by weight, in each case based on the weight of the composition (F).

[0061] Glycosylases (EC 3.2)

[0062] 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). Glycosidases (EC 3.2.1) are understood to be enzymes that hydrolyze O-glycosyl components and S-glycosyl components.

[0063] Glycosidases preferred according to the invention (EC 3.2.1) are selected from a group of enzymes generally referred to as cellulases.

[0064] 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 as to 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.

[0065] 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).

[0066] Cellulases can be divided into three categories:

[0067] 1. Endoglucanase (EC 3.2.1.4), also known as endo-1,4-beta-glucanase, beta-1,4-glucanase, avicelase, beta-1,4-endoglucanhydrolase, endo-1,4-beta-D-glucanohydrolase, carboxymethylcellulase or celludextrinase;

[0068] 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;

[0069] 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.

[0070] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein-engineered mutants are included. Suitable cellulases are cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, e.g., the fungal cellulases from Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum, disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, and WO 89 / 09259. Particularly suitable cellulases can be alkaline or neutral cellulases with color-care properties. Examples of such cellulases are cellulases described in EP495257, EP531372, WO 96 / 11262, WO 96 / 29397, WO 98 / 08940. Other examples are cellulase variants as described in WO 94 / 07998, EP531315, EP3212777, EP3502243, EP3653705, EP 3653706, US 5457046, US 5686593, US 5763254, WO 95 / 24471, WO 98 / 12307, WO 99 / 01544, and WO 2019 / 122520.

[0071] Examples of glycosylases and glycosidases with endo-1,4-glucanase activity (EC 3.2.1.4) are described in WO 2002 / 099091, e.g., those with a sequence of at least 97% identity to the amino acid sequence of positions 1 to 773 of SEQ ID NO:2 of WO 2002 / 099091. Another example may comprise a GH44 xyloglucanase, e.g., a xyloglucanase enzyme with a sequence of at least 60% identity to positions 40 to 559 of SEQ ID NO:2 of WO 2001 / 062903.

[0072] Other examples of cellulases suitable according to the invention include the GH45 cellulases described in WO 96 / 29397 and in particular variants thereof with substitution, insertion and / or deletion at one or more of the positions corresponding to the following positions in SEQ ID NO:8 of WO 2002 / 099091: 2, 4, 7, 8, 10, 13, 15, 19, 20, 21, 25, 26, 29, 32, 33, 34, 35, 37, 40, 42, 42a, 43, 44, 48, 53, 54, 55, 58, 59, 63, 64, 65, 66, 67, 70, 72, 76, 79, 80, 82, 84, 86, 88, 90, 91, 93, 95, 95d, 95h, 95j, 97, 100, 101, 102, 103, 113, 114, 117, 119, 121, 133, 136, 137, 138, 139, 140a, 141, 143a, 145, 146, 147, 150e, 150j, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160c, 160e, 160k, 161 , 162, 164, 165, 168, 170, 171, 172, 173, 175, 176, 178, 181, 183, 184, 185, 186, 188, 191, 192, 195, 196, 200, and / or 20, preferably selected from P19A, G20K, Q44K, N48E, Q119H or Q146R.

[0073] Commercially available cellulases include Celluzyme™, Carezyme™, Carezyme Premium™, Celluclean™ (e.g. Celluclean™ 5000L and Cellulclean™ 4000T), Celluclean Classic™, Cellusoft™, Endolase®, Renozyme® and Whitezyme™ (Novozymes A / S), Clazinase™ and Puradax HA™ (Genencor International Inc.), KAC-500(B)™ (Kao Corporation), Revitalenz™ 1000, Revitalenz™ 2000 and Revitalenz™ 3000 (DuPont), as well as Ecostone® and Biotouch® (AB Enzymes).

[0074] 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.

[0075] 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) and exo-1,4-beta-D-glucanase (EC 3.2.1.91) as well as mixtures of these enzymes.

[0076] A particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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. A particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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).

[0077] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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.

[0078] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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.

[0079] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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.%, furthermore - in a total amount of 25-35 wt.% - 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 wt.% at least one further enzyme with cellulase activity, wherein the amounts refer to the total weight of the enzyme mixture.

[0080] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (E) 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.%, as well as at least one further enzyme with cellulase activity in a total amount of up to 100 wt.%, wherein the amounts refer to the total weight of the enzyme mixture.

[0081] Compositions (E) used with preference according to the invention contain, in each case based on their weight, at least one glycosylase (EC 3.2) in a total amount of 1-50 wt.%, preferably 5-40 wt.%, more preferably 7-30 wt.%, particularly preferably 10-25 wt.%, extraordinarily preferably 15-19 wt.%, and furthermore 5-99 wt.%, preferably 10-90 wt.%, particularly preferably 20-80 wt.%, extraordinarily preferably 40-70 wt.% water. Compositions (E) used with particular preference according to the invention contain, in addition to water and the at least one glycosylase (EC 3.2), in each case based on their weight, at least one sugar selected from sucrose and D-glucose and mixtures thereof in a total amount of 1-20 wt.%, preferably 5-15 wt.%.

[0082] Another particularly preferred embodiment of the invention (dyeing process, dyeing kit) is characterized in that the weight-based mixing ratio of composition (E) and composition (F) is in the range of 0.5-10 parts by weight of (E) to 500 parts by weight of (F), preferably from 1 to 5 parts by weight of (E) to 500 parts by weight of (F). The composition (F) preferably used according to the invention thus undergoes only a very slight dilution upon mixing with composition (E).

[0083] A further particularly preferred embodiment of the invention (dyeing process, dyeing kit) is characterized in that the composition (M), 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.%.

[0084] A further particularly preferred embodiment of the invention (dyeing process, dyeing kit) is characterized in that the composition (M), based on its weight, contains at least one glycosidase (EC 3.2.1) 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.%.

[0085] A further particularly preferred embodiment of the invention (dyeing process, dyeing kit) is characterized in that the composition (M), based on its weight, contains at least one glycosidase (EC 3.2.1) selected from at least one cellulase, 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.%.

[0086] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (M), based on its weight, contains at least one glycosidase (EC 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.%, further preferably 0.002 - 0.05 wt.%, particularly preferably 0.003 - 0.04 wt.%, extraordinarily preferably 0.01 - 0.03 wt.%.

[0087] A further particularly preferred embodiment of the invention (staining method, staining kit) is characterized in that the composition (M), based on its weight, contains at least one glycosidase (EC 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.%, more preferably 0.002 - 0.05 wt.%, particularly preferably 0.003 - 0.04 wt.%, most preferably 0.01 - 0.03 wt.%.

[0088] incubation period

[0089] In this context, incubation time is understood to be the time between the addition of the glycosylase solution (E) to the composition (F) containing the flavone or flavone glycoside and the contact of the mixed composition (M) with the keratin fibers to be treated.

[0090] The incubation time according to the invention is zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds.

[0091] A further preferred subject of the present invention is a process for the non-oxidative coloring of keratinic fibers, in particular human hair, with natural dyes, which comprises the following process steps in the given order: a) Providing a composition (F) which contains at least one flavone or flavone glycoside and providing a composition (E) which contains at least one glycosylase (EC 3.2), b) preparing a mixture (M) from the compositions (F) and (E), c) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying the mixture (M) to the keratin fibers, d) leaving it to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, e) rinsing the keratin fibers with water, f) optionally drying the keratin fibers, g) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying an aqueous composition (FE) which contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.-%, in each case based on the weight of the composition (FE), and has a pH in the range of 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extremely preferably 4.5 to 5.2, in each case measured at 20°C, h) leaving to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, i) rinsing the keratin fibers with water, optionally drying the keratin fibers, wherein the mixture (M) and / or the aqueous composition (FE) have a temperature of 15 - 50 °C, preferably 20 - 40 °C, preferably 25 - 35 °C and / or wherein the keratin fibers are heated during the entire exposure time of (M) and / or (FE) or at least during part of the exposure time of (M) and / or (FE). Heat is preferably applied using a heat lamp, a hair dryer, or a hairdryer. The heat supplied is within physiologically acceptable limits.

[0092] The keratin fibers are preferably dried after rinsing out the compositions (M) and / or (FE). 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.

[0093] After each rinsing step, the keratin fibers can be dried with an absorbent cloth, such as a towel. Towel-dried hair can optionally be partially or completely dried with a hairdryer or other heat source. It is also possible to let the keratin fibers air dry.

[0094] Further preferred embodiments of the invention (dyeing process, dyeing kit) are characterized in that the compositions (F), (E), (M) and (FE) used according to the invention have the following pH values, each measured at 20°C:

[0095] Compositions (F) preferably used according to the invention have a pH in the range from 1.0 to 8.0, preferably 2.5 to 7.0, particularly preferably 3.6 to 6.0, extremely preferably 4.5 to 5.6.

[0096] Compositions (E) preferably used according to the invention have a pH in the range from 1.0 to 8.0, preferably 2.5 to 7.0, particularly preferably 3.6 to 6.0, extremely preferably 4.5 to 5.6.

[0097] Compositions (M) preferably used according to the invention have a pH in the range from 1.0 to 8.0, preferably 2.5 to 7.0, particularly preferably 3.6 to 6.0, extremely preferably 4.5 to 5.6.

[0098] Compositions (FE) preferably used according to the invention have a pH in the range from 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extremely preferably 4.5 to 5.2.

[0099] The composition (FE) used according to the invention has a pH in the range from 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extremely preferably 4.5 to 5.2, in each case measured at 20°C, and contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extremely preferably 0.2 - 0.5 wt.%, in each case based on the weight of the composition (FE).

[0100] A further essential step of the dyeing process according to the invention is the application of at least one salt of the divalent iron cation Fe(II) in an amount of 0.001-3.0 wt.%, preferably 0.01-2 wt.%, particularly preferably 0.1-1 wt.%, extraordinarily preferably 0.2-0.5 wt.%, in each case based on the weight of the composition (FE). The sequential application of the Fe(II) salt used according to the invention surprisingly improves the intensity of the coloration of the keratin fibers achieved with the at least one flavone or flavone glycoside. According to the invention, "divalent" is understood to mean an iron salt whose cationic portion comprises iron with the oxidation state "two."

[0101] According to the invention, physiologically compatible anions are preferred as anionic counterions for the at least one Fe(II) salt. These preferably include halides, particularly preferably chlorides, sulfates, and the anions of C1-C6 carboxylic acids, most preferably lactic acid, gluconic acid, citric acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, galactaric acid (mucous acid), tartaric acid, and malic acid, as well as mixtures of these anions.

[0102] Dyeing processes preferred according to the invention are therefore characterized in that the composition (FE) contains as Fe(II) salt at least one compound selected from iron(II) lactate, iron(II) gluconate, iron(II) citrate, iron(II) chloride, iron(II) sulfate, iron(II) acetate, iron(II) propionate, iron(II) oxalate, iron(II) malonate, iron(II) succinate, iron(II) glutarate, iron(II) galactarate, iron(II) tartrate and iron(II) malate and from mixtures of these salts in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.5 wt.%, in each case based on the weight of the composition (FE). If the composition (FE) contains several Fe(II) salts, their total amount is 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.5 wt.%, in each case based on the weight of the composition (FE).

[0103] Particularly preferred dyeing processes according to the invention are characterized in that the composition (FE) contains iron(II) lactate as Fe(II) salt in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.5 wt.%, in each case based on the weight of the composition (FE).

[0104] In compositions (FE) preferably used according to the invention, the water content is 40-98 wt.%, preferably 50-97 wt.%, particularly preferably 60-90 wt.%, in each case based on the weight of the composition (FE).

[0105] Optionally, the composition (FE) used according to the invention may contain a buffer system as described above for the composition (F).

[0106] Further preferred embodiments of the invention (dyeing processes, dyeing kits) are characterized in that the compositions (F), (E) and (FE) used according to the invention each comprise a cosmetic carrier.

[0107] In a first preferred embodiment of the invention, the carrier is water. Compositions (F), (E), and (FE) preferably used according to the invention contain, based on their weight, at least 40% by weight of water.

[0108] In order to optimize the applicability of the composition and its residence time on the keratin fibers, it is preferred that the compositions (F), (E), and (FE) used according to the invention or preferably according to the invention have a thickened consistency, with compositions (F) and (FE) particularly preferably having a thickened consistency. Since composition (E) preferably only makes up a small proportion of mixture (M), (E) can also be as thin as water without impairing application. Preferably used compositions (F) and (FE) are in the form of a gel, cream, or paste. Such carriers ensure homogeneous distribution and a sufficient residence time of the composition on the keratin fibers.

[0109] The compositions of the kits according to the invention, and those used with preference according to the invention, may optionally contain further additives to optimize the application properties of this composition. Preferred additives are, in particular, thickeners, which ensure that the composition adheres better to the hair during application.

[0110] Compositions particularly preferred according to the invention contain at least one or more hydrophilic thickeners, which are preferably selected from polysaccharides other than cellulose, which may be chemically and / or physically modified. Compounds from the group of polysaccharides other than cellulose 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 other than celluloses, cellulose ethers and cellulose esters and are selected from xanthan gum, alginic acids (as well as their corresponding physiologically acceptable salts, the alginates), agar agar (with the polysaccharide agarose present in agar agar as the main component), 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.

[0111] In preferred embodiments, xanthan gum is included as a hydrophilic thickener with a view to reliable viscosity adjustment and residue-free application to keratin fibers and the scalp.

[0112] Further preferred compositions according to the invention contain, with a view to reliably adjusting the viscosity, at least one polymeric thickener selected from non-ionic polymers, such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone / vinyl acetate copolymers and polyethylene glycols with a molecular weight of 100,000 to 10,000,000 Daltons; cationic polymers such as dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers, such as acrylamidopropyl trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, diallyldimethylammonium chloride / acrylate-

[0113] Copolymers, t-butylaminoethyl methacrylate / N-(1,1,3,3-tetramethylbutyl)acrylamide / acrylate( / methacrylate) copolymers, anionic homo- and copolymers based on polyacrylic acids, polymethacrylic acids, cross-linked polyacrylic acids, cross-linked polymethacrylic acids, the esters and amides of optionally cross-linked poly(meth)acrylic acids, homo- and copolymers of acrylamido-2-methylpropanesulfonic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymers, each in their acid or salt form. Compositions particularly preferably used according to the invention contain, in each case based on their weight, at least one hydrophilic thickener in a total amount of from 0.1 to 5 wt.%, preferably from 0.5 to 4 wt.%, more preferably from 1 to 3.5 wt.% and most preferably from 1.2 to 2 wt.%.

[0114] Compositions particularly preferred 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.

[0115] In a further preferred embodiment of the present invention, the compositions 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 compositions 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.

[0116] Further compositions particularly preferably used according to the invention contain at least one aliphatic solvent selected from C1-C4 alkanols and C2-C12 polyols, in particular selected from ethanol, isopropanol, n-propanol, ethylene glycol, 1,2-propanediol, glycerol, diethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-hexanediol, 1,6-hexanediol and 1,2-octanediol, and mixtures of these solvents.

[0117] Further compositions particularly preferably used according to the invention contain, based on their weight, at least one aliphatic solvent selected from C1-C4 alkanols and C2-C12 polyols, in a total amount of 0.01-60 wt.%, preferably 0.1-30 wt.%, particularly preferably 0.5-20 wt.%, extraordinarily preferably 1-10 wt.%, further preferably 2-5 wt.%.

[0118] Other compositions particularly preferably used according to the invention are characterized in that they do not contain an aliphatic solvent selected from C1-C4 alkanols and C2-C12 polyols.

[0119] Compositions particularly preferably used according to the invention contain at least one oil. Preferred cosmetic oils are selected from natural and synthetic hydrocarbons, particularly preferably from paraffin oils, Cs-Cs-isoparaffins, in particular isoeicosane, polyisobutenes and polydecenes, Cs-Ci6-isoparaffins, and 1,3-di-(2-ethylhexyl)cyclohexane; the benzoic acid esters of linear or branched Cs-22-alkanols; fatty alcohols having 6-30 carbon atoms, which are unsaturated or branched and saturated or branched and unsaturated; triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated Cs-6 fatty acids, in particular natural oils; the dicarboxylic acid esters of linear or branched Cs-2-Ci6-alkanols;the esters of linear or branched saturated or unsaturated fatty alcohols with 2 - 30 carbon atoms with linear or branched saturated or unsaturated fatty acids with 2 - 30 carbon atoms, which may be hydroxylated; the addition products of 1 to 5 propylene oxide units with mono- or polyhydric C8-22 alkanols; the addition products of at least 6 ethylene oxide and / or propylene oxide units with mono- or polyhydric C8-22 alkanols; the C8-C22 fatty alcohol esters of monohydric or polyhydric C2-C7 hydroxycarboxylic acids; the symmetrical, asymmetrical or cyclic esters of carbonic acid with C8-22 alkanols, C8-22 alkanediols or C8-22 alkanetriols; the esters of dimers of unsaturated C12-C22 fatty acids (dimer fatty acids) with monohydric linear, branched, or cyclic C2-C18 alkanols or with polyhydric linear or branched C2-C6 alkanols; silicone oils and mixtures of the aforementioned substances.

[0120] Further compositions particularly preferably used according to the invention contain at least one surfactant or one emulsifier.

[0121] Surfactants and emulsifiers within the meaning of the present application are amphiphilic (bifunctional) compounds consisting of at least one hydrophobic and at least one hydrophilic moiety. The hydrophobic residue is preferably a hydrocarbon chain with 8-28 carbon atoms, which can be saturated or unsaturated, linear or branched. This C8-C28 alkyl chain is particularly preferably linear. Basic properties of surfactants and emulsifiers are oriented absorption at interfaces, aggregation into micelles, and the formation of lyotropic phases. When selecting surfactants suitable according to the invention, it may be preferable to use a mixture of surfactants in order to optimally adjust the stability of the compositions according to the invention. Preferred surfactants and emulsifiers are selected from anionic, cationic, zwitterionic, amphoteric, and nonionic surfactants and emulsifiers, as well as mixtures of these substances.

[0122] Further compositions particularly preferred according to the invention contain at least one linear saturated alkanol having 12 - 30 carbon atoms.

[0123] Preferred linear saturated alkanols having 12-30 carbon atoms, in particular having 16-22 carbon atoms, are selected from cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lanolin alcohol, as well as mixtures of these alkanols. Particularly preferred alkanol mixtures according to the invention are those obtainable from the industrial hydrogenation of vegetable and animal fatty acids. The total amount of at least one linear saturated alkanol having 12-30 carbon atoms is preferably 0.1-20% by weight, preferably 0.5-16.5% by weight, and particularly preferably 3-10% by weight, in each case based on the weight of the composition according to the invention. Preferred non-oxidative dyeing processes and dyeing kits according to the invention are further characterized in that they do not contain any oxidizing agents other than atmospheric oxygen.In particular, the oxidizing agents hydrogen peroxide, persulfates, perbromates, percarbonates, perborates, and percarbamides are excluded. Atmospheric oxygen is not an oxidizing agent in the context of the invention.

[0124] In order to make the compositions used according to the invention also olfactory attractive for the user, further compositions used particularly preferably according to the invention are characterized in that they contain at least one fragrance compound or odoriferous compound.

[0125] Compositions used with exceptional preference according to the invention are characterized in that they contain, based on their weight, 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.%.

[0126] What has been said regarding preferred embodiments of the dyeing process according to the invention applies mutatis mutandis to preferred embodiments of the dyeing kits according to the invention and their individual components, the compositions (F), (E) and (FE).

[0127] Implementation examples

[0128] The exemplary embodiments presented below are intended to explain the subject matter of the invention in more detail without limiting it thereto.

[0129] The dyeing process according to the invention was carried out on strands of white buffalo belly hair (tied in a round shape, approx. 8 cm of free hair).

[0130] For all dyeing experiments described below, a 1 wt.% solution of the raw material “Weid Extract C08” from Croda, a powdered extract of flowers, leaves and / or stems of Reseda luteola, in water, adjusted to a pH of 5.6 with a sodium citrate buffer, measured at 20°C, was prepared and used as the test dye (composition (F)).

[0131] The raw material used was "Weid Extract C08" from Croda. According to the manufacturer, it is a spray-dried aqueous-ethanolic extract of the flowers, leaves, and / or stems of Reseda luteola. It contains 15-35% by weight of maltodextrin, based on the weight of the raw material "Weid Extract C08," to improve storage stability.

[0132] As composition (E), a glycosylase mixture (EC 3.2) was used, which was purchased from Novozymes, 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.%, as well as at least one further enzyme with glycosylase activity in a total amount of up to 100 wt.%, wherein the amounts refer to the total weight of the enzyme mixture.

[0133] The enzyme active substance content in the mixture used, which was available as an aqueous composition (E), was 190 pg / μl, or 19 wt.%. Furthermore, the cellulase blend contained, based on its weight, 66 wt.% water and 15 wt.% of a sucrose / D-glucose mixture.

[0134] After stirring composition (F) for 2 minutes, 100 μl of cellulase blend corresponding to composition (E) used according to the invention was added. This mixture, corresponding to composition (M) used according to the invention, was stirred for a further 2 minutes.

[0135] Buffalo belly hair strands were immersed in Composition (M) for 30 minutes while stirring. The liquor ratio (amount of Composition (M) per gram of hair) was 50 ml of Composition (M) per gram of hair.

[0136] Unless otherwise stated, hair treatment solutions (F), (E), (M) and (FE) were at 20°C (room temperature).

[0137] After treatment with composition (M), the hair strands were rinsed for 30 seconds under running deionized water (20°C) and combed 20 times. The hair strands were then dried with a standard hairdryer at a defined distance (d = 10 cm) and a defined temperature (T = 80 ± 5 °C) and combed 20 times. Subsequently, an initial colorimetric measurement of the strands was performed.

[0138] After treatment with the mixture Reseda / uteo / a / Cellulase, no color change was observed on the hair fiber.

[0139] As a subsequent treatment, the strands treated with Reseda / uteo / a / cellulase were placed for a further 30 minutes in 50 ml of an aqueous solution of 1 wt.% iron(II) lactate (FeI_ac) with a pH of 5.2 (20°C), see Table 1 (liquor ratio: 50 ml metal salt solution to 1 g strand of hair). After the contact time, the strand was rinsed again and dried (see above). The color impression is immediately visible. Table 1: Composition used according to the invention (FE)

[0140] Compared to the control (same dyeing conditions, without cellulase addition), the cellulase-dyed strand appears darker. They differ by an AE of 10.94 according to the CIELAB color space (see Table 2).

[0141] Staining with Reseda luteola without enzyme addition

[0142] For control purposes, hair strands were dyed – not according to the invention – only with "Weid Extract C08" without added enzymes. The colorimetric values ​​are summarized in Table 2.

[0143] Table 2: CIELAB measured values ​​with Reseda luteola and Fe(ll) treated strands (control: without cellulase) with mean values ​​and AE value from the control strands to the untreated strand and AE value from the mean value of the Reseda / uteo / a / Cellulase / Fe(ll)-treated strands to the mean value of the control strands

[0144] The treatment of hair strands with Reseda (Reseda luteola flower / leaf / stem extract) in combination with a cellulase blend and subsequent treatment with iron(II) lactate led to an intensified color result.

[0145] Determination of the color tone achieved by the inventive method

[0146] All colorimetric measurements were performed using a Datacolor Spectraflash SF 600 colorimeter. 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, such as a Datacolor Spectraflash SF 600 colorimeter.

[0147] The L*,a*,b* color space refers to the CIELAB color space. The L value represents the brightness of the color (black-white axis) and the intensity of the color: the higher the L value, the brighter the color; the lower the L value, the more intense 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.

[0148] 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:

[0149] AE = (AL 2 + Aa 2 + From 2 ) 05

[0150] The larger the value for AE, the more pronounced the color difference.

[0151] 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.

[0152] The color difference (AE) between the uncolored strand and the colored strand was calculated according to the following formula:

[0153] AE = / (Lv — Lri) 2+ (av — an) 2 + (bv — bn) 2 mit

[0154] Lv, av, bv: colorimetric values ​​for dyed strands

Claims

Patent claims 1. A process for the non-oxidative coloring of keratin fibers, in particular human hair, with natural dyes, which comprises the following process steps in the given order: a) providing a composition (F) which contains at least one flavone or flavone glycoside and providing a composition (E) which contains at least one glycosylase (EC 3.2), b) preparing a mixture (M) from the compositions (F) and (E), c) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying the mixture (M) to the keratin fibers, d) leaving it to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, e) rinsing the keratin fibers with water, f) optionally drying the keratin fibers, g) directly thereafter within a time of zero seconds to 10 minutes, preferably 10 seconds to 5 minutes, particularly preferably 30 to 120 seconds, applying an aqueous composition (FE) which contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.-%, in each case based on the weight of the composition (FE), and has a pH in the range of 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extraordinarily preferably 4.5 to 5.2, in each case measured at 20°C, h) leaving to act for a time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, i) rinsing the keratin fibers with water, j) optionally drying the keratin fibers.

2. The method according to claim 1, characterized in that the at least one glycosylase (EC 3.2) is selected from at least one glycosidase (EC 3.2.1).

3. The method according to claim 2, characterized in that the at least one glycosidase (EC 3.2.1) is selected from at least one cellulase.

4. The method according to claim 2 or 3, 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. Method according to one of claims 1 to 4, characterized in that the composition (E) 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.%, as well as at least one further enzyme with cellulase activity in a total amount of up to 100 wt.%, wherein the amounts refer to the total weight of the enzyme mixture in the composition (E).Process according to one of claims 1 to 5, characterized in that the composition (M), 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.%. Process according to one of claims 1 to 6, characterized in that the composition (E), in each case based on its weight, contains at least one glycosylase (EC 3.2) in a total amount of 1 - 50 wt.%, preferably 5 - 40 wt.%, more preferably 7 - 30 wt.%, particularly preferably 10 - 25 wt.%, extraordinarily preferably 15 - 19 wt.%, and furthermore 5 - 99 wt.%, preferably 10 - 90 wt.%, particularly preferably 20 - 80 wt.%, extraordinarily preferably 40 - 70 wt.% of water.Method according to one of claims 1 to 7, characterized in that the at least one flavone or flavone glycoside originates from at least one extract of a plant selected from Reseda, in particular Reseda luteola and Reseda lutea, Genista tinctoria, Matricaria chamomilla, Chrysanthemum, Petroselinum crispum, Cynara, Citrus sinensis, Daucus carota, Apium, Mentha piperita and Perilla frutescens, with Reseda luteola being particularly preferred. A method according to claim 8, characterized in that the extractant is selected from water, in particular water with a temperature of 45 - 100 °C, furthermore C1-C4 alkanols and C2-C4 polyols, in particular ethanol, isopropanol, n-propanol, ethylene glycol, 1,2-propanediol, glycerol and 1,3-butylene glycol, and mixtures of these extractants, in particular mixtures of water and at least one Ci-C4 alkanol, mixtures of. Water and at least one C2-C4 polyol, particularly preferably water / ethanol mixtures. The process according to any one of claims 1 to 9, characterized in that the at least one flavone or flavone glycoside is selected from luteolin (CI 75590, Natural Yellow 2), apigenin (CI 75580; Natural Yellow 1), apiin, rutin (CI 75730; Natural Yellow 10), kaempferol (CI 75460, Natural Yellow 13), quercetin (CI 75670), salvigenin, myricetin, and the glycosides derived from the aforementioned flavones, as well as mixtures of these substances. Process according to one of claims 1 to 10, characterized in that the composition (F), based on its weight, contains at least one flavone or flavone glycoside in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%. Process according to one of claims 1 to 11, characterized in that the composition (M), based on its weight, contains at least one flavone or flavone glycoside in a total amount of 0.01 - 5 wt.%, preferably 0.05 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, extraordinarily preferably 0.2 - 0.6 wt.%, further extraordinarily preferably 0.3 - 0.5 wt.%. A process according to any one of claims 1 to 12, characterized in that the composition (M) has a pH in the range of 1.0 to 8.0, preferably 2.5 to 7.0, particularly preferably 3.6 to 6.0, extraordinarily preferably 4.5 to 5.6, each measured at 20°C. A kit for the non-oxidative coloring of keratin fibers, in particular human hair, with natural dyes, comprising the following compartments, which are physically separate from one another: - a composition (F) containing at least one flavone or flavone glycoside, - a composition (E) containing at least one glycosylase (EC 3.2) and - an aqueous composition (FE) which contains at least one salt of the divalent iron cation Fe(II) in an amount of 0.001 - 3.0 wt.%, preferably 0.01 - 2 wt.%, particularly preferably 0.1 - 1 wt.%, in each case based on the weight of the composition (FE), and a pH in the range of 1.0 to 6.0, preferably 2.5 to 5.5, particularly preferably 3.6 to 5.3, extremely preferably 4.5 to 5.2, in each case measured at 20°C.

15. Kit according to claim 14, characterized in that the compositions (F), (E) and (FE) are designed as described in any one of claims 1-13.

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