MORD-FREE HAIR DYE WITH PLANT DYES

Description

[0001] The present invention relates to a cosmetic composition for the oxidant-free and mordant-free coloring of keratinous fibers, in particular human hair, using selected natural dyes in an aqueous composition buffered to a pH value in the range of 3 to 5.9. The present invention further relates to a method for coloring keratin-containing fibers, in particular human hair, using selected natural dyes in an aqueous composition. State of the art

[0002] The desire to change one's hair color is a major need for many consumers. To satisfy this need, the cosmetic industry offers a diverse range of products. Hair dyes that achieve particularly long-lasting color with high coverage are usually oxidative dyes, see for example DE102011085416A1. These use oxidizing and alkalizing agents, which can damage the hair structure. Certain cationic direct dyes are also capable of achieving hair color changes with high color intensity and chroma, as well as excellent fastness properties, see for example EP850638A1. The aforementioned dyes contain synthetic dyes.

[0003] A growing number of consumers desire hair dyes and hair coloring processes based on natural dyes, even if these products and processes are inferior to the aforementioned products and processes in terms of fastness properties, coverage, color intensity and color variety, see for example WO2010063533A1.

[0004] Besides dyeing with henna, which comes from the plant Lawsonia unarmedThe dyeing of hair with certain polyphenols, especially tannins and pseudotannins, has been known for a long time, as is the process of obtaining these substances; see, for example, EP2438900A1 and WO2019 / 034770A1. Such polyphenols are extracted from certain plant parts. However, it is also possible to use powdered plant parts with a high polyphenol content in the dye; see, for example, DE19905707A1. Furthermore, it is possible to use pure polyphenols, especially tannic acid, according to the invention. The adhesion of the polyphenol dye to the hair or to the keratin fibers, and thus the colorfastness, is to be positively influenced by certain divalent or trivalent metal salts.

[0005] JP2001270812A discloses a two-stage dyeing process using a first composition containing a tannin-containing plant dye and sodium sulfite, and a second composition containing an Fe(II) salt with an inorganic counterion, wherein the keratin fibers are rinsed between the application of the two compositions. The patent application WO2010094207A1 discloses a process for dyeing hair in which the hair is first treated with a keratin reducing agent, thereby breaking down and weakening the hair structure, and then a composition containing a tannin-containing plant dye, sodium sulfite, cysteine ​​hydrochloride, and an Fe(II) salt with an inorganic counterion is applied to the hair.

[0006] Multi-step dyeing processes are time-consuming for the user and therefore less preferred than single-step processes. Pre-treatments that affect the hair structure to prepare it for dye absorption are also time-consuming and therefore less attractive to the user. Furthermore, multiple formulations must be prepared for a multi-step process, resulting in increased packaging for the entire dye. This is less desirable for environmental reasons. Using mordants produces dark colors. Light shades with satisfactory wash fastness are not yet available using a single-step process. Task

[0007] The present invention was based on the objective of providing dyeing compositions for a one-step process for dyeing keratin-containing fibers, in particular human hair, which achieves light shades with good fastness properties, in particular with high wash fastness.

[0008] The present invention was further based on the objective of providing compositions and methods for dyeing keratin-containing fibers, in particular human hair, using natural dyes that cause the least possible damage or weakening of the keratin structure.

[0009] Another task was to provide compositions and methods for dyeing keratin-containing fibers, especially human hair, using natural dyes that achieve light shades with high color intensity or high chromaticity.

[0010] Surprisingly, it was found that the dyeing compositions and dyeing processes described in the patent claims enable convenient hair coloring, with which light shades with satisfactory wash fastness can be achieved, comparable to a demi-permanent hair coloring, i.e. an oxidative hair coloring under mild conditions (weakly alkaline medium, low hydrogen peroxide concentration), without damaging the hair structure.

[0011] A first object of the present invention is a cosmetic composition for the oxidizing agent-free and mordant-free coloring of keratinous fibers, in particular human hair, with natural dyes, comprising: i. at least one coloring extract from a dyewood, furthermore ii. water, iii. a buffer system selected from a mixture of a moderately strong or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a moderately strong or weak base with its conjugate or corresponding acid, iv. wherein the composition has a pH value in the range of 3.0 - 5.9, measured at 20°C, the composition contains no mordant selected from the salts of magnesium, calcium, aluminium, transition metals and lanthanides, no cysteine, no N-acetylcysteine, no oxidation dye precursor and no fatty substances which have a water solubility of no more than 0.01 g / l at 20°C.

[0012] All solubility data refer to a normal pressure of 1013 hPa.

[0013] Dye compositions according to the invention contain, as a natural dye, at least one coloring extract from a dyewood. Dyewoods are understood to be wood species that contain a dye suitable for dyeing. These include logwood ( Haematoxylum campechianum, Bloodwood (logwood, Campeche tree), Fissettwood (fustik, wig tree, Rhus cotinus, Cotinus coggygria ), Yellowwood (Dyeing lice, Dyer's mulberry) and redwood ( Haematoxylum brasiletto L., Brazilian bloodwood tree).

[0014] Preferred dyeing compositions and dyeing processes according to the invention are characterized in that the at least one coloring dyewood extract is derived from dyewoods selected from logwood ( Haematoxylum campechianum, Bloodwood (logwood, Campeche tree), Fissettwood (fustik, wig tree, Rhus cotinus, Cotinus coggygria ) , Yellowwood (Tinker stain, Dyer's mulberry) and redwood ( Haematoxylum brasiletto L., Brazilian bloodwood tree) as well as mixtures of these dyewoods.

[0015] Preferred dyeing compositions and dyeing processes according to the invention are characterized in that the at least one dyeing dyewood extract is derived from the heartwood of dyewoods selected from logwood ( Haematoxylum campechianum, Bloodwood (logwood, Campeche tree), Fissettwood (fustik, wig tree, Rhus cotinus, Cotinus coggygria ), Yellowwood (Tinker stain, Dyer's mulberry) and redwood ( Haematoxylum brasiletto L., Brazilian bloodwood tree) as well as mixtures of these dyewoods.

[0016] Suitable extraction agents are water, in particular hot 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, as well as mixtures of these extraction agents, in particular mixtures of water and at least one C1–C4 alkanol, mixtures of water and at least one C2–C4 polyol, and especially preferably water / ethanol mixtures. An exceptionally preferred extraction agent according to the invention is water.

[0017] Further dyeing compositions and dyeing processes that are particularly preferred according to the invention are characterized in that an extract from the heartwood of the smoke tree ( Rhus cotinus, Cotinus coggygriaThe extract is obtained by extraction with water, preferably water at a temperature of 45–100 °C. The extract itself is preferably used in powder form, obtainable by drying, preferably spray drying, of the aqueous extract.

[0018] Further dyeing compositions and dyeing processes that are particularly preferred according to the invention are characterized in that an extract from the heartwood of the Brazilian bloodwood tree ( Haematoxylum brasiletto L. ) is used, wherein the extract is obtained by extraction with water, preferably with water at a temperature of 45–100 °C. The extract itself is preferably used in powder form, obtainable by drying, preferably spray drying, of the aqueous extract. Other extracts preferred according to the invention are from the heartwood of Haematoxylum brasiletto L.They are used in concentrated form, obtained by partial distillation of the extraction solvent after extraction, as a viscous liquid.

[0019] Further dyeing compositions and dyeing processes that are particularly preferred according to the invention are characterized in that an extract from the heartwood of the bloodwood tree ( Haematoxylum campechianum, (also known as logwood or campeche tree) is used, wherein the extract is obtained by extraction with water, preferably with water at a temperature of 45–100 °C. The extract itself is preferably used in concentrated form, obtainable by partial distillation of the extraction solvent after extraction, as a viscous liquid. Other extracts preferred according to the invention are from the heartwood of Haematoxylum campechianum are used in powder form, obtainable by drying, preferably spray drying, of the aqueous extract.

[0020] A preferred polyphenol from Haematoxylum campechianumis hematoxylin.

[0021] One of the primary color components from Haematoxylum campechianum The neoflavonoid hematein is produced by the fermentation of hematoxylin, which is derived from the heartwood of Haematoxylum campechianum is extracted. Hematein (molar mass 300.26 g / mol) has the following structural formula (I):

[0022] Further dyeing compositions and dyeing processes that are particularly preferred according to the invention are characterized in that the at least one polyphenol is selected from hematein and hematoxylin as well as mixtures thereof.

[0023] According to the invention, exceptionally preferred dyeing compositions and dyeing processes are characterized in that, if the polyphenol is selected from hematoxylin, no other polyphenol is contained besides hematoxylin and its fermentation product hematein.

[0024] Further dyeing compositions and dyeing processes that are particularly preferred according to the invention are characterized in that the at least one polyphenol, which is preferably selected from tannins and pseudotannins, is in the form of an extract from the heartwood of the dyer's mulberry tree ( Tincture of the maclura, also Chlorophora dyeing or Mulberry dyeing ) is used, wherein the extract is obtained by extraction with water, preferably with water at a temperature of 45–100 °C. The extract itself is preferably used in concentrated form, obtainable by partial distillation of the extraction solvent after extraction, as a viscous liquid. Other extracts preferred according to the invention are from the heartwood of Haematoxylum brasiletto L. are used in powder form, obtainable by drying, preferably spray drying, of the aqueous extract.

[0025] According to the invention, preferred dyeing compositions and dyeing processes are characterized in that the composition, based on its weight, contains the at least one dyeing wood extract i in an amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%, extremely preferably 1 - 4 wt.%, and even more preferably 2 - 3 wt.%. Polyphenols

[0026] The coloring components extracted from the dyewoods are polyphenols. According to Quideau's definition of polyphenols, polyphenols are compounds obtainable via the shikimate biosynthesis pathway and furthermore possess at least two hydroxyl groups in the molecule, with a molar mass in the range of 170 to 20,000 g / mol, preferably 290 to 3,000 g / mol. According to the invention, preferred polyphenols have at least 12 hydroxyl groups and at least five phenyl groups.

[0027] The dyewood extracts used in the dyeing compositions and dyeing processes preferred according to the invention typically have a total polyphenol content of 10-100 wt.%, preferably 15-95 wt.%, particularly preferably 20-80 wt.%, and most preferably 30-70 wt.%, based on their weight.

[0028] According to the invention, preferred dyeing compositions and dyeing processes are characterized in that the composition, based on its weight, contains at least one polyphenol, each in an amount of 0.05 - 10 wt.%, preferably 0.1 - 5 wt.%, particularly preferably 0.5 - 4 wt.%, and most preferably 1 - 2 wt.%.

[0029] Preferred polyphenols according to the invention are selected from brasilin, brasilein, hematoxylin, hematein, maclurin, kaempferol, morin and mixtures thereof.

[0030] According to the invention, preferred dyeing compositions and dyeing processes are characterized in that the at least one dyeing wood extract i contains a polyphenol selected from brasilin, brasilein, hematoxylin, hematein, maclurin, kaempferol, morin and mixtures thereof.

[0031] Further dyeing compositions and dyeing processes preferred according to the invention are characterized in that the composition, based on its weight, contains at least one polyphenol selected from brasilin, brasilein, hematoxylin, hematein, maclurin, kaempferol, morin and mixtures thereof, each in an amount of 0.05 - 10 wt.%, preferably 0.1 - 5 wt.%, particularly preferably 0.5 - 4 wt.%, and most preferably 1 - 2 wt.%. Water

[0032] In dyeing compositions and dyeing processes preferred according to the invention, the water content of the dyeing composition is 40 - 98 wt.%, preferably 50 - 97 wt.%, particularly preferably 60 - 85 wt.%, in each case based on the weight of the dyeing composition. PH value

[0033] The dyeing composition according to the invention has a pH value in the range of 3.0 to 5.9, preferably in the range of 4.0 to 5.5, particularly preferably in the range of 4.5 to 5.2, and most preferably in the range of 4.8 to 5.0, in each case measured at 20°C. Particularly bright, luminous shades in the reddish-blonde to light brown range were achieved in this pH range.

[0034] The dyeing composition used in the dyeing process according to the invention has a pH value in the range of 3.0 to 10.5, preferably in the range of 4.0 to 10.0, particularly preferably in the range of 5.5 to 9.5, and most preferably in the range of 7.0 to 8.0, in each case measured at 20°C. Particularly bright, luminous shades in the reddish-blond to light brown range were achieved in acidic pH ranges. Darker shades were achieved in neutral to alkaline pH ranges, even without the addition of mordants. buffer

[0035] The dye composition according to the invention further comprises a buffer system selected from a mixture of a medium-strength or weak acid with its conjugated or corresponding base (or the respective salt) and a mixture of a medium-strength or weak base with its conjugated or corresponding acid.

[0036] According to the invention, preferably suitable corresponding acid-base pairs are those that stabilize the dyeing composition according to the invention in the pH range of 3.0 to 5.9, preferably in the range of 4.0 to 5.5, particularly preferably in the range of 4.5 to 5.2, and most preferably in the range of 4.8 to 5.0, in each case measured at 20°C. Particularly preferred buffer systems according to the invention are selected from Mixtures of citric acid and its salts, in particular the alkali metal citrates, in particular the sodium salts, in particular trisodium citrate; 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; mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures; mixtures of gluconic acid and its salts, in particular gluconic acid / sodium gluconate mixtures; mixtures of succinic acid and its salts, in particular the sodium salts, in particular sodium hydrogen succinate and disodium succinate; and mixtures of malic acid and its salts, in particular the sodium salts, in particular sodium hydrogen malate and disodium malate.

[0037] A buffer system that is particularly preferred 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.

[0038] Other buffer systems, e.g., 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 cosmetic market product.

[0039] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, a buffer system in an amount of 0.5 - 5 wt.%, preferably 0.8 - 4.5 wt.%, particularly preferably 1.5 - 3.5 wt.%, and extraordinarily preferably 2.1 - 3.0 wt.%.

[0040] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% trisodium citrate.

[0041] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% sodium gluconate.

[0042] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% sodium lactate.

[0043] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% disodium succinate.

[0044] According to the invention, preferred dye compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% sodium hydrogen succinate.

[0045] According to the invention, preferred coloring compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% disodium malate.

[0046] According to the invention, preferred coloring compositions are characterized in that they contain, based on their weight, as a buffer system 0.2 - 1.5 wt.%, preferably 0.3 - 1.4 wt.%, particularly preferably 0.5 - 1.1 wt.%, extremely 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.%, extremely preferably 1.5 - 2.1 wt.% sodium hydrogen malate.

[0047] The dyeing composition used in the dyeing process according to the invention also contains a buffer system, selected from a mixture of a moderately strong or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a moderately strong or weak base with its conjugate or corresponding acid. Preferably suitable corresponding acid-base pairs for the dyeing process according to the invention are those that stabilize the dyeing composition according to the invention in the pH range of 3.0 to 10.5, preferably in the range of 4.0 to 10.0, particularly preferably in the range of 5.5 to 9.5, and most preferably in the range of 7.0 to 8.0, in each case measured at 20°C. Particularly preferred buffer systems according to the invention are selected from Mixtures of phosphate and hydrogen phosphate salts, in particular alkali metal salts, in particular sodium salts, in particular trisodium phosphate / disodium hydrogen phosphate mixtures and disodium hydrogen phosphate / sodium dihydrogen phosphate mixtures; mixtures of carbonate and hydrogen carbonate salts, in particular alkali metal salts, in particular sodium salts, in particular disodium carbonate / sodium hydrogen carbonate mixtures; mixtures of citric acid and its salts, in particular alkali metal citrates, in particular sodium salts, in particular trisodium citrate; mixtures of tartaric acid and its salts, in particular alkali metal tartrates, in particular potassium salts, in particular potassium hydrogen tartrate; mixtures of phthalic acid and its salts, in particular potassium salts, in particular potassium hydrogen phthalate; mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures; mixtures of gluconic acid and its salts.in particular gluconic acid / sodium gluconate mixtures, mixtures of succinic acid and its salts, in particular the sodium salts, especially sodium hydrogen succinate and disodium succinate, and mixtures of malic acid and its salts, in particular the sodium salts, in particular sodium hydrogen malate and disodium malate.

[0048] In dye compositions preferred according to the invention, the water content is 40 - 95 wt.%, preferably 50 - 90 wt.%, particularly preferably 60 - 85 wt.%, in each case based on the weight of the dye composition.

[0049] To improve the dyeing result, it may be preferred that the dyeing compositions according to the invention contain sodium sulfite (Na₂SO₃). Sodium sulfite (Na₂SO₃) is particularly preferably present in an amount of 0.1 to 3.0 wt.%, preferably 0.5 to 2 wt.%, particularly preferably 0.7 to 1.5 wt.%, and most preferably 1.0 to 1.2 wt.%, in each case based on the weight of the composition.

[0050] Surprisingly, it was found that the reducing agent sodium disulfite with the formula Na₂S₂O₅, also known as sodium metabisulfite, actually worsens the staining results. Therefore, particularly preferred staining compositions and staining processes according to the invention are characterized in that the staining composition does not contain metabisulfite, in particular sodium metabisulfite.

[0051] The dye compositions according to the invention are further characterized in that they contain no cysteine ​​or cysteine ​​derivatives, in particular no N-acetylcysteine. The term "cysteine" also includes the salts of cysteine, such as cysteine ​​hydrochloride. The term "cysteine ​​derivatives" includes in particular N-acylcysteines, especially N-acetylcysteine. Cysteine ​​and cysteine ​​derivatives are capable of reducing the disulfide bridges in keratin. Such reaction mechanisms weaken the fiber structure, which is undesirable according to the invention.

[0052] The dyeing compositions and dyeing processes according to the invention do not require the addition of so-called mordants. For the purposes of this application, mordants are understood to be salts of magnesium, calcium, aluminum, transition metals, and lanthanides. In particular, the dyeing compositions and dyeing processes according to the invention do not require the addition of an iron(II) salt, an iron(III) salt, or a titanium salt.

[0053] The dyeing compositions and dyeing processes according to the invention do not require the addition of oxidation dye precursors. Oxidation dye precursors are well known in the trade; for example, reference is made to the oxidation dye precursors mentioned in DE102016225379A1.

[0054] The dyeing compositions and dyeing processes according to the invention do not require the addition of fatty substances that have a water solubility of at most 0.01 g / l or less at 20°C. It has been found that water-insoluble fatty substances can impair the dyeing result. Without being bound to this theory, it is suspected that a hydrophobization of the keratin fibers occurs, which hinders the dye uptake.

[0055] Examples of water-insoluble fatty substances that are not to be included in the compositions and processes according to the invention are vegetable butters, in particular shea butter (Butyrospermum parkii), cocoa butter (Theobroma cacao), butter from Shorea stenoptera, illipe butter, butter from Madhuca species, mango butter (Mangifera indica), murumuru butter, butter from Garcinia indica, butter from Virola sebifera, animal butters, vegetable oils, hydrogenated vegetable oils, vegetable waxes, e.g. candelilla wax, carnauba wax, sunflower wax, fruit waxes such as orange wax, animal waxes, e.g. beeswax, shellac wax and spermaceti, hydrogenated or hydrogenated waxes, chemically modified waxes, in particular hard waxes, such as...Montan ester waxes, hydrogenated jojoba waxes and sasol waxes, polyalkylene waxes and polyethylene glycol waxes, C20-C40 dialkyl esters of dimer acids, C30-50 alkyl beeswax, alkyl and alkyl aryl esters of dimer fatty acids, so-called fatty alcohols, i.e., non-alkoxylated alkanols and alkenols with at least 8 carbon atoms, which may be linear or branched, saturated or unsaturated, the mono-, di- and triesters of C2-C6 polyols, such as glycerol or ethylene glycol, with fatty acids with at least 8 carbon atoms, which may be linear or branched, saturated or unsaturated, and also the non-alkoxylated fatty acids with at least 8 carbon atoms, which may be linear or branched, saturated or unsaturated.

[0056] Surfactants and emulsifiers can have a fat-like structure, but they do not fall under the category of water-insoluble fatty substances as defined in this application. Surfactants and emulsifiers as defined in this application are amphiphilic (bifunctional) compounds consisting of at least one hydrophobic and at least one hydrophilic molecular moiety. The hydrophobic moiety is preferably a hydrocarbon chain with 8-28 carbon atoms, which can be saturated or unsaturated, linear or branched. A linear C8-C28 alkyl chain is particularly preferred. The basic properties of surfactants and emulsifiers are oriented absorption at interfaces in aqueous systems, as well as aggregation into micelles and the formation of lyotropic phases in aqueous systems. In contrast, water-insoluble fatty substances do not form micelles on their own in aqueous systems.

[0057] Fragrance compounds or odorant compounds, as defined below, are also not among the water-insoluble fatty substances defined above.

[0058] Another object of the present invention is a method for the oxidizing agent-free and mordant-free dyeing of keratinous fibers, in particular human hair, with natural dyes, wherein a dyeing composition containing i. at least one coloring extract from a dyewood, ii. water, iii. a buffer system selected from a mixture of a moderately strong or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a moderately strong or weak base with its conjugate or corresponding acid, iv. wherein the dyeing composition has a pH value in the range of 3.0 - 10.5, measured at 20°C, wherein the dyeing composition contains no mordant selected from the salts of magnesium, calcium, aluminium, transition metals and lanthanides, no cysteine, no N-acetylcysteine, no oxidation dye precursor and no fatty substances which have a water solubility of at most 0.01 g / l at 20°C, The process is applied to the keratinous fibers, especially human hair, and rinsed off with water after an exposure time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, wherein the process does not include the application of a mordant selected from salts of magnesium, calcium, aluminium, transition metals and lanthanides.

[0059] A preferred method according to the invention for dyeing keratinous fibers, in particular human hair, without oxidizing agents or mordants, as described above, is characterized in that the keratinous fibers were not treated with an oxidizing agent or with a keratin-reducing agent for a period of up to 7 days before the application of the dyeing composition used according to the invention or preferably according to the invention.

[0060] Oxidizing agents commonly used in hair cosmetics, but which are not intended for hair treatment according to the invention, including as a pretreatment, include hydrogen peroxide, persulfates, perbromates, percarbonates, perborates, and percarbamides. Atmospheric oxygen is not considered an oxidizing agent in the context of the invention.

[0061] Among the keratin-reducing compounds commonly used in hair cosmetics, but which are not intended for hair treatment according to the invention, including as a pretreatment, are thioglycolic acid, thiolactic acid, cysteine, N-acetylcysteine, cysteamine and the salts of the aforementioned compounds, as well as mixtures of these keratin-reducing compounds.

[0062] Regarding further preferred embodiments of the dyeing process according to the invention, what has been said about the compositions according to the invention applies mutatis mutandis - with the exception of the pH value.

[0063] The compositions according to the invention and those preferred according to the invention may optionally contain further additives to optimize their application properties. Preferred additives are, in particular, thickening agents that ensure that the compositions according to the invention and those preferred according to the invention remain better on the hair during application.

[0064] According to the invention, particularly preferred compositions contain at least one or more hydrophilic thickeners, 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 as the main component in agar-agar), starch fractions and starch derivatives such as amylose, amylopectin and dextrins, karaya gum, locust bean gum, gum arabic, pectins, dextrans and guar gum, as well as mixtures thereof.

[0065] Preferred cellulose ethers of C1-C4 alcohols and cellulose esters 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) as well as their physiologically acceptable salts.

[0066] In preferred embodiments, xanthan gum is included as a hydrophilic thickener to ensure 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 to ensure reliable viscosity adjustment and residue-free application to keratin fibers and the scalp. In a preferred embodiment, carboxymethylcellulose may be the sole hydrophilic thickener. A combination of carboxymethylcellulose and hydroxyethylcellulose is particularly preferred. A combination of carboxymethylcellulose and xanthan gum (preferably xanthan gum with the INCI name Xanthan Gum) may also be preferred according to the invention.

[0067] According to the invention, particularly preferred compositions 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.%, in each case based on the weight of the composition.

[0068] In a further preferred embodiment of the present invention, the compositions according to the invention contain, based on their weight, 0.1 to 3 wt.%, preferably 0.5 to 2.5 wt.%, more preferably 1.2 to 2.0 wt.%, xanthan gum.

[0069] In a further preferred embodiment of the present invention, the compositions according to the invention contain, based on their weight, 0.1 to 4 wt.%, preferably 1 to 2.8 wt.%, carboxymethylcellulose.

[0070] In a further preferred embodiment of the present invention, the compositions according to the invention contain, based on their weight, 0.1 to 3 wt.%, preferably 0.5 to 2.5 wt.%, more preferably 1.2 to 2.0 wt.%, hydroxyethylcellulose.

[0071] Particularly preferred compositions according to the invention contain at least one organic solvent having a phenyl group in the molecule. Preferably, this solvent is selected from phenoxyethanol, benzyl alcohol, and mixtures thereof. Surprisingly, it was found that such aromatic solvents can have a positive effect on the dyeing results of the dyeing compositions and the dyeing process according to the invention.

[0072] In a further preferred embodiment of the present invention, the compositions according to the invention contain, based on their weight, 0.1 to 3 wt.%, preferably 0.5 to 2.5 wt.%, more preferably 0.8 to 1.0 wt.%, at least one organic solvent having a phenyl group in the molecule. In a further preferred embodiment of the present invention, the dye compositions according to the invention contain, based on their weight, 0.1 to 3 wt.%, preferably 0.5 to 2.5 wt.%, more preferably 0.8 to 1.0 wt.%, at least one organic solvent selected from phenoxyethanol, benzyl alcohol, and mixtures thereof.

[0073] Particularly preferred dye compositions 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, as well as 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 composition.

[0074] Other dye compositions particularly preferred according to the invention are characterized in that they do not contain an aliphatic solvent selected from C 1 -C 4 -alkanols and C 2 -C 4 -polyols.

[0075] In order to make the compositions according to the invention also sensorially attractive to the user, further coloring compositions that are particularly preferred according to the invention are characterized in that they contain at least one perfume oil which contains at least one fragrance compound or odor compound.

[0076] The definition of an odorant within the meaning of the present application corresponds to the skilled-skilled definition as found in the RÖMPP Chemistry Lexicon, dated December 2007. According to this definition, an odorant is a chemical compound with an odor and / or taste that excites the receptors of the hair cells of the olfactory system (adequate stimulus). The necessary physical and chemical properties are a low molar mass of no more than 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. To distinguish volatile, low-molecular-weight substances, which are usually not considered odorants but primarily solvents, such as ethanol, propanol, isopropanol, and acetone, from odorants according to the invention,Odorants according to the invention have a molar mass of 74 to 300 g / mol, contain at least one osmophoric group in the molecule, and possess an odor and / or taste, that is, they excite the receptors of the hair cells of the olfactory system. Examples of ester-type fragrance and odorant compounds are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexyl propionate, styralyllipropionate, benzyl salicylate, cyclohexyl salicylate, Floramate, Melusate, and Jasmecyclate. Examples of fragrance and odorant compounds of the ether type are benzyl ethyl ether and ambroxane; examples of fragrance and odorant compounds of the aldehyde type are the linear alkanals with 8–18 carbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamenaldehyde, lilial, and bourgeonal.Examples of ketone-type fragrance and odor compounds are the ionones, alpha-isomethyl ionone and methylcedryl ketone; examples of alcohol-type fragrance and odor compounds are anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; examples of terpene-type fragrance and odor compounds are limonene and pinene. Examples of fragrance and aromatic compounds include pine, citrus, jasmine, patchouli, rose, ylang-ylang oil, clary sage oil, chamomile oil, clove oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil, orange blossom oil, neroli oil, orange peel oil, and essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, and cajeput oil.Calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, niaouli oil, orange oil, oregano oil, palmarosa oil, patchouli oil, Peruvian balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, juniper berry oil, wormwood oil, wintergreen oil, hyssop oil, cinnamon oil, citronella oil, lemon oil, and cypress oil. Other fragrance and odorant compounds include ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, and farnesol.Fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptyne carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamaldehyde alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methylquinoline, methyl β-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonylacoal, n-octylaldehyde p-Oxy-acetophenone, Pentadecanolide, β-Phenylethyl alcohol, Phenylacetaldehyde dimethyl acetal, Phenylacetic acid, Pulegone, Safrole, Isoamyl salicylate, Methyl salicylate, Hexyl salicylate, Cyclohexyl salicylate, Santalol, Skatole, Terpineol, Thymene, Thymol, Gamma-Undecalactone, Vanillin, Veratraldehyde, Cinnamaldehyde, Cinnamyl alcohol, Cinnamic acidEthyl cinnamic acid esters and benzyl cinnamic acid esters.

[0077] Other (more volatile) fragrance substances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral and citrinellalal.

[0078] Preferably, mixtures of different fragrances are used, which together create an appealing scent.

[0079] Suitable perfume oils can also contain natural fragrance mixtures obtained from plant or animal sources, e.g., pine, citrus, jasmine, rose, lily, or ylang-ylang oil. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g., sage oil, chamomile oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, laudanum oil, clove oil, iso-eugenol, thyme oil, bergamot oil, geranium oil, and rose oil. Particularly preferred compositions 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.%, and most preferably 1–1.5 wt.%, in each case based on the weight of the composition.

[0080] Fragrance compounds or odorant compounds, as defined above, do not fall under the category of water-insoluble fatty substances defined above. Example

[0081] The exemplary embodiment shown below is intended to explain the subject matter of the invention in more detail, without limiting it thereto. Dye composition according to the invention (quantities in wt.%) Color wood extract * 2,00 Citrate buffer (sodium salt) at pH 3.0 - 5.9 Water, demineralized to 100 Total 100,00 pH value (20°C) 3,0 - 5,9

[0082] Dye composition used in the dyeing process according to the invention (quantities in wt.%) Color wood extract * 2,00 Phosphate buffer (sodium salt) at pH 7.0 - 8.0 Water, demineralized to 100 Total 100,00 pH value (20°C) 7,0 - 8,0

[0083] Dye composition used in the dyeing process according to the invention (quantities in wt.%) Color wood extract * 2,00 Carbonate buffer (sodium salt) at pH 9.5 - 10.5 Water, demineralized to 100 Total 100,00 pH value (20°C) 9,5 - 10,5 * The following were used as dyewood extracts: * "Otto Dille" logwood extract ( Haematoxylum campechianum ); powdered hot water extract from the heartwood of Haematoxylum campechianum, pH value of the 10 wt% solution in water: 5.5 ± 1.0 "Otto Dille" redwood extract ( Haematoxylum brasiletto ); powdered hot water extract from the heartwood of Haematoxylum brasiletto pH value of the 10 wt% solution in water: 6.5 ± 1.0 "Otto Dille" Yellowwood extract from dyer's mulberry tree ( Chlorophora tinctoria, Morus tinctoria, Maclura tinctoria ); powdered hot water extract from the heartwood of Maclura tinctoria, pH value of the 10 wt% solution in water: 5.4 ± 1.0 Source: Baeck GmbH & Co. KG, DE-22844 Norderstedt

[0084] The coloring was performed on strands of completely unpigmented Caucasian hair from Kerling International Haarfabrik GmbH (Backnang, Germany). The strands were 10 cm long, of which 8 cm were available for coloring. The remaining 2 cm at the top of the strands served for attachment. Each strand weighed 0.45 ± 0.05 grams.

[0085] The strands were pre-cleaned with an acidic solution (pH 4.5) and dried before dyeing.

[0086] The hair strands were treated for 30 minutes in the dyeing composition according to the invention or used according to the invention, as shown in the table above (100 ml / g strand), and then rinsed for one minute under running deionized water with 20 combing cycles.

[0087] Afterwards, the hair strands were dried with a standard hairdryer at a defined distance (d = 10 cm) and a defined temperature (T = 80 ± 5 °C) by combing 20 times with a hairdryer.

[0088] All colorimetric measurements, namely the determination of the parameters L, a, b in the L,a,b color space, were carried out with the Spectraflash SF 600 colorimetric device from the company Datacolor.

[0089] L-values ​​describe the black / white scale. The lower the L-value, the darker the color; the higher the L-value, the lighter the color.

[0090] a-values ​​describe the red / green scale. Positive a-values ​​represent a red color; negative a-values ​​represent a greenish color.

[0091] b-values ​​describe the yellow / blue scale. Positive b-values ​​represent yellow; negative values ​​represent bluish hues. Result of the colorimetric measurement for dyes with logwood extract (mean of n=10 measurements)

[0092] L a b untreated strands 77,03 0,83 2,91 Staining at pH 3.0 67,71 10,61 32,84 Staining at pH 5.0 51,53 9,77 23,78 Staining at pH 5.9 44,91 11,76 18,84 Staining at pH 7.0 42,19 8,68 8,77 Staining at pH 8.0 44,02 9,54 5,19 Staining at pH 9.5 43,66 9,54 -1,37 Staining at pH 10.5 44,16 6,39 -6,06

[0093] As the pH increases, the L-value decreases, meaning the strands become darker. Dyes with the highest red content are achieved at pH 3.0 to 5.9.

[0094] A constant increase in blue coloration was observed with increasing pH. Wash fastness of the dye

[0095] The dyed strands were subjected to 4 wash cycles (6 hair washes each) with pH 4.5 shampoo (Schauma 7 Herbs) and a pH 10 shampoo and measured colorimetrically.

[0096] Tests on the colorfastness showed that when the pH of the dye and the pH of the shampoo differed, the dye washed out and the color changed. When the dye and shampoo had the same or a similar pH value, only the color faded, while the shade remained.

Claims

1. Cosmetic composition for the oxidant-free and mordant-free dyeing of keratinous fibers, in particular human hair, with natural dyes, containing: i. at least one coloring extract from a dye wood, ii. Water, iii. a buffer system selected from a mixture of a moderately strong or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a moderately strong or weak base with its conjugate or corresponding acid, iv. wherein the composition has a pH value in the range of 3 - 5.9, measured at 20°C, wherein the composition contains no mordant selected from the salts magnesium, calcium, aluminum, transition metals and lanthanides, no cysteine, no N-acetylcysteine, no oxidation dye precursor and no fatty substances which have a water solubility of at most 0.01 g / l at 20°C.

2. A process for the oxidant-free and mordant-free dyeing of keratinous fibers, in particular human hair, with natural dyes, wherein a dyeing composition comprising: i. at least one coloring extract from a dye wood, ii. Water, iii. a buffer system selected from a mixture of a moderately strong or weak acid with its conjugate or corresponding base (or the respective salt) and a mixture of a moderately strong or weak base with its conjugate or corresponding acid, iv. wherein the coloring composition has a pH in the range of 3.0 - 10.5, measured at 20°C, wherein the dyeing composition contains no mordant selected from the salts magnesium, calcium, aluminum, transition metals and lanthanides, no cysteine, no N-acetylcysteine, no oxidation dye precursor and no fatty substances which have a water solubility of at most 0.01 g / l at 20°C, is applied to the keratinous fibers, in particular to human hair, and rinsed with water after an exposure time of 30 seconds to 60 minutes, preferably 5 to 45 minutes, particularly preferably 15 to 30 minutes, wherein the process does not comprise application of a mordant selected from salts magnesium, calcium, aluminum, transition metals and lanthanides.

3. Composition according to claim 1 or process according to claim 2, characterized in that the at least one colouring dye wood extract i. is selected from extracts from the wood of Haematoxylum brasiletto L. (Brazilian bloodwood tree), Haematoxylum campechianum (bloodwood tree, bluewood tree, campeche tree), and Maclura tinctoria (dyer's mulberry tree).

4. Composition or process according to any one of the preceding claims, characterized in that the at least one coloring dyewood extract i comprises a polyphenol selected from brazilin, brazilin, hematoxylin, hematein, maclurin, kaempferol, morin and mixtures thereof.

5. Composition or process according to one of the preceding claims, characterized in that the composition contains, in each case based on its weight, the at least one colouring coloured wood extract i in an amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%, exceptionally preferably 1 - 4 wt.%, still more preferably 2 - 3 wt.%.

6. Composition or process according to one of the preceding claims, characterized in that the composition contains, in each case based on its weight, at least one polyphenol, in each case in an amount of 0.05 - 10 wt.%, preferably 0.1 - 5 wt.%, particularly preferably 0.5 - 4 wt.%, exceptionally preferably 1 - 2 wt.%.

7. Composition or process according to one of the preceding claims, characterized in that the composition contains, in each case based on its weight, at least one polyphenol selected from brazilin, brazilin, hematoxylin, hematein, maclurin, kaempferol, morin and mixtures thereof, in each case in an amount of 0.05 - 10 wt.%, preferably 0.1 - 5 wt.%, particularly preferably 0.5 - 4 wt.%, exceptionally preferably 1 - 2 wt.%.

8. Composition or process according to any one of the preceding claims, characterized in that, when the polyphenol is selected from hematoxylin, no other polyphenol is present except hematoxylin and its fermentation product hematein.

9. Composition or process according to one of the preceding claims, characterized by a water content of 40 - 98 wt.%, preferably 50 - 97 wt.%, particularly preferably 60 - 85 wt.%, in each case based on their weight.

10. Composition or process according to one of the preceding claims, characterized in that no metabisulphite is present.

11. Composition according to one of the preceding claims, characterized in that the composition has a pH value in the range from 4 to 5.5, preferably in the range from 4.5 to 5.2, particularly preferably in the range from 4.8 to 5.0, in each case measured at 20°C.

12. Composition according to any one of the preceding claims, characterized in that the buffer system is selected from - Mixtures of citric acid and its salts, in particular the alkali metal citrates, in particular the sodium salts, in particular trisodium citrate, - 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, especially potassium hydrogen phthalate, - Mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures, - Mixtures of gluconic acid and its salts, in particular gluconic acid / sodium gluconate mixtures, - Mixtures of succinic acid and its salts, in particular the sodium salts, especially sodium hydrogen succinate and disodium succinate, and - Mixtures of malic acid and its salts, in particular the sodium salts, especially sodium hydrogen malate and disodium malate.

13. Process according to one of the preceding claims, characterized in that the dyeing composition has a pH value in the range from 4.0 to 10.0, preferably in the range from 5.5 to 9.5, particularly preferably in the range from 7.0 to 8.0, in each case measured at 20°C.

14. Method according to one of the preceding claims, characterized in that the buffer system is selected from - Mixtures of phosphate and hydrogen phosphate salts, in particular the alkali metal salts, in particular the sodium salts, in particular trisodium phosphate / disodium hydrogen phosphate mixtures and disodium hydrogen phosphate / sodium dihydrogen phosphate mixtures, - Mixtures of carbonate and hydrogen carbonate salts, in particular the alkali metal salts, in particular the sodium salts, in particular disodium carbonate / sodium hydrogen carbonate mixtures, - Mixtures of citric acid and its salts, in particular the alkali metal citrates, in particular the sodium salts, in particular trisodium citrate, - 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, especially potassium hydrogen phthalate, - Mixtures of lactic acid and its salts, in particular lactic acid / sodium lactate mixtures, - Mixtures of gluconic acid and its salts, in particular gluconic acid / sodium gluconate mixtures, - Mixtures of succinic acid and its salts, in particular the sodium salts, especially sodium hydrogen succinate and disodium succinate, and - Mixtures of malic acid and its salts, in particular the sodium salts, especially sodium hydrogen malate and disodium malate,15. Process for the non-oxidative dyeing of keratinous fibres, in particular human hair, according to one of the preceding claims, characterized in that the keratinous fibres have not been treated with an oxidizing agent and not with a keratin-reducing agent for a period of up to 7 days prior to the application of the dyeing composition.