Dyeing agent for keratinous fibers containing at least one coloring compound, a chitosan, an aliphatic C1-C22 monoalcohol and an aliphatic C2-C22 polyol

Abstract

The present invention relates to a means for dyeing keratinous fibers, in particular human hair, comprising (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or a chitosan derivative, and (F-3) at least one aliphatic C1-C 22 Monoalcohol, and (F-4) at least one aliphatic C2-C 22 Polyol wherein the weight ratio of the aliphatic C1-C contained in the average 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22 Polyols (F-4), i.e., the weight ratio (F-3) / (F-4), is at least 1.

Description

[0001] The subject of the present application is a dyeing agent for keratinous fibers, in particular human hair, comprising at least one coloring compound, at least one chitosan and / or chitosan derivative, and at least one aliphatic C1-C 22 Monoalcohol and at least one aliphatic C2-C 22 Contains polyol. A characteristic feature of the product is the weight ratio of the aliphatic C1-C2 components contained in the product. 22 -Monoalcohols to the aliphatic C2-C contained in the average 22 Polyols have a value of at least 1.

[0002] Another subject matter of the present application is a method for dyeing keratinous fibers, in particular human hair, in which the dye described above is applied to the keratinous fibers and, if necessary, rinsed off after an exposure time.

[0003] Altering the shape and color of keratin fibers, especially human hair, is an important area of ​​modern cosmetics. Depending on the desired color, professionals are familiar with various dyeing systems for changing hair color. For permanent, intense colorations with good colorfastness and gray coverage, oxidation dyes are typically used. These dyes contain oxidation dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidation dyes are characterized by very long-lasting color results.

[0004] When using direct dyes, pre-formed pigments diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, dyes produced with direct dyes are less durable and wash out more quickly. Dyes made with direct dyes typically remain on the hair for between 5 and 20 washes.

[0005] The use of color pigments is well-known for temporary color changes to hair and / or skin. Color pigments are generally understood to be insoluble, coloring substances. These are present in the coloring formulation in the form of small particles and are simply deposited on the hair fibers and / or skin surface. Therefore, they can usually be removed completely after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name "hair mascara."

[0006] Dyeing with pigments offers several significant advantages. Since the pigments adhere only to the keratin material, particularly the hair fibers, unwanted colors can be removed quickly, easily, and completely, allowing users to return to their original hair color immediately and effortlessly. This makes the dyeing process especially attractive for consumers who don't want to regularly dye their hair.

[0007] Despite these many advantages, the pigment-based dyeing system still has some disadvantages, which stem from the limited penetration depth of the pigments into the keratinous material. Since the pigments do not diffuse into the keratin fiber but merely deposit on the outside of the fiber in the form of a coating or film, the wash fastness of dyes produced with this system still needs improvement. Various studies have attempted to bind the pigment(s) more permanently to the hair surface using film-forming materials, mostly polymers.

[0008] For example, German patent DE 19847883 A1 deals with achieving pigment-based colorations using dyes containing at least one chitosan and one pigment. Combining the pigments with chitosan should improve the abrasion resistance of the colorations. The major advantage of chitosan as a film-forming material is that it is based on biopolymers and therefore offers improved environmental compatibility and biodegradability. As many users show increasing interest in products made with sustainable or renewable raw materials, the use of biopolymers is gaining in importance. Nevertheless, the colorations obtained with pigment and chitosan still have room for improvement.

[0009] The coloring achieved with pigments (or direct dyes, especially poorly soluble direct dyes) and chitosan is a surface coloring, meaning that the applied dyes do not diffuse into the hair but are deposited on the hair surface and embedded there in a film by the simultaneously applied chitosan. Depending on the amount of embedded dyes, this film is modified to a greater or lesser extent. The work leading to this invention revealed that the properties of a film embedding a large number of dyes are also significantly altered. In particular, the feel and rub fastness of the film are adversely affected.

[0010] The objective of this application was therefore to find a dye based on pigments and / or direct dyes that enables intense coloring with improved feel and better rub fastness. The coloring should be achieved using biopolymers, and the keratin fibers or hair colored with the dye should not feel coated, dull, rough, or greasy.

[0011] Surprisingly, it has now been found that this task can be solved if a dye is used to color the keratin fibers which contains one or more pigments and / or direct dyes, one or more chitosans and / or chitosan derivatives, and at least one aliphatic C1-C 22 Monoalcohol, and at least one aliphatic C2-C 22 Contains polyol.

[0012] It has proven to be essential to the invention that the weight ratio of the aliphatic C1-C contained in the average is 22 -Monoalcohols to the aliphatic C2-C contained in the average 22 polyols have a value of at least 1. Or, to put it another way, it has proven essential that the agent binds to the aliphatic C1-C 22 Monoalcohols in a larger defined total quantity than the aliphatic C2-C 22 Contains polyols.

[0013] A first object of the present invention is a means for dyeing keratinous fibers, in particular human hair, comprising (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or a chitosan derivative, and (F-3) at least one aliphatic C1-C 22 Monoalcohol, and (F-4) at least one aliphatic C2-C 22 Polyol wherein the weight ratio of the aliphatic C1-C contained in the average 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22 Polyols (F-4), i.e., the weight ratio (F-3) / (F-4), is at least 1.

[0014] Hair dyed with one of these products exhibited particularly high color intensity and was characterized by a pleasant, smooth, non-greasy and soft feel.

[0015] During staining, the color-imparting compounds are deposited in a homogeneous, uniform, and smooth film on the surface of the keratin fibers. This film is formed by the chitosans. It has been found that the non-volatile aliphatic C2-C 22Polyols (F-4) are integrated into the film during its formation, giving it a particularly smooth texture. This film then feels very pleasant and soft on keratin fibers. Keratinous fibers

[0016] Keratinous fibers include hair, wool, and fur. Human hair is particularly often considered a keratinous fiber. dyeing agents

[0017] The term "coloring agent" is used in this invention to describe the coloring of keratin fibers, particularly hair, by the use of pigments and / or direct dyes. The agent can alternatively be referred to as a coloring agent or dye (F). During the coloring process, the coloring compounds are deposited in a homogeneous, uniform, and smooth film on the surface of the keratin fibers. This film is formed by the chitosans. colouring compounds (F-1) in the dye

[0018] The dye according to the invention contains, as its first essential component (F-1), at least one coloring compound from the group consisting of pigments and direct dyes.

[0019] For the purposes of this invention, pigments are understood to be coloring compounds which have a solubility in water at 25 °C of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. The water solubility can be determined, for example, by the method described below: 0.5 g of the pigment is weighed into a beaker. A magnetic stir bar is added. Then one liter of distilled water is added. This mixture is heated to 25 °C for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L. If the pigment-water mixture cannot be visually assessed due to the high intensity of the pigment, which may be finely dispersed, the mixture is filtered.If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0020] In a particularly suitable embodiment, the dye contains at least one pigment. Suitable color pigments can be of inorganic and / or organic origin. Pigments with specific shapes and metallic pigments are also particularly well suited for use in the dye according to the invention.

[0021] In a particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one pigment (F-1) from the group consisting of inorganic pigments, organic pigments, pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0022] Preferred inorganic color pigments are selected from synthetic or natural sources. Naturally derived inorganic color pigments can be produced, for example, from chalk, ochre, umber, green earth, burnt sienna, or graphite. Other inorganic color pigments that can be used include black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments.

[0023] Particularly suitable are colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates. Especially preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0024] Colored pearlescent pigments are also particularly preferred according to the invention. These are typically mica- and / or micaceous and can be coated with one or more metal oxides. Mica belongs to the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0025] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as a pearlescent pigment. Particularly favored pearlescent pigments are based on natural or synthetic mica and coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by changing the thickness of the metal oxide layer(s).

[0026] In a further preferred embodiment, a coloring agent according to the invention is characterized in that it contains at least one inorganic pigment, which is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or micaceous oxide, which are coated with at least one metal oxide and / or one metal oxychloride.

[0027] In a further preferred embodiment, a coloring agent according to the invention is characterized in that it contains at least one pigment selected from mica- or micaceous-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0028] Examples of particularly suitable color pigments are available commercially under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[0029] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iron oxides), Tin oxide Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides) Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

[0030] Weiterhin besonders bevorzugte Farbpigmente mit der Handelsbezeichnung Xirona® sind beispielsweise: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0031] In addition, particularly preferred color pigments with the trade name Unipure® include, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0032] In a further embodiment, the dyes according to the invention can also contain one or more organic pigments (F-1).

[0033] The organic pigments according to the invention are correspondingly insoluble organic dyes or color lakes, which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolin, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine, and / or triarylmethane compounds.

[0034] Particularly suitable organic pigments include, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, and red pigments with the Color Index Numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0035] In a further particularly preferred embodiment, a coloring agent according to the invention is characterized in that it contains at least one organic pigment, preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, and orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0036] The organic pigment can also be a paint lake. For the purposes of this invention, the term "paint lake" refers to particles comprising a layer of absorbed dyes, wherein the particle-dye unit is insoluble under the aforementioned conditions. These particles can be, for example, inorganic substrates such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum itself.

[0037] For example, alizarin lacquer can be used as a colored lacquer.

[0038] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the dye of the process according to the invention is particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. Therefore, according to the invention, it is advantageous if the at least one pigment has an average particle size D 50 The particle size ranges from 1.0 to 50 µm, preferably from 5.0 to 45 µm, preferably from 10 to 40 µm, and particularly from 14 to 30 µm. The mean particle size D 50 can be determined, for example, using dynamic light scattering (DLS).

[0039] Pigments with a specific shape can also be used to stain keratin fibers. For example, a pigment based on a lamellar and / or lenticular substrate platelet can be used. Furthermore, staining based on a substrate platelet containing a vacuum-metallized pigment is also possible.

[0040] In a further preferred embodiment, a means according to the invention is characterized in that it contains at least one pigment selected from the group consisting of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet, and vacuum metallized pigments.

[0041] The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred thickness ranges for the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm; 2.5 to 20 nm, 5 to 20 nm, and 10 to 20 nm. Preferably, each substrate platelet has as uniform a thickness as possible. Due to the small thickness of the substrate platelets, the pigment exhibits particularly high opacity.

[0042] The substrate platelets are preferably monolithic. In this context, monolithic means consisting of a single, closed unit without fractures, layering, or inclusions, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous, meaning that no concentration gradient exists within the platelets. In particular, the substrate platelets are not layered and do not contain any particles or other distributed particles.

[0043] The size of the substrate platelet can be tailored to the specific application, particularly the desired effect on the keratinous material. Typically, the substrate platelets have a mean maximum diameter of approximately 2 to 200 µm, especially approximately 5 to 100 µm.

[0044] In a preferred embodiment, the aspect ratio, expressed as the ratio of the mean size to the mean thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The mean size of the uncoated substrate platelets is defined as the d50 value of the uncoated substrate platelets. Unless otherwise specified, the d50 value was determined using a Sympatec Helos instrument with Quixel wet dispersion. For sample preparation, the sample to be tested was pre-dispersed in isopropanol for 3 minutes.

[0045] The substrate plates can be made from any material that can be formed into platelet form.

[0046] They can be of natural origin or synthetically produced. Materials from which the substrate plates can be constructed include, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. Preferably, the substrate plates are composed of metal (alloys).

[0047] Any metal suitable for metallic luster pigments can be used. Such metals include iron and steel, as well as all air- and water-resistant (semi-)metals such as platinum, zinc, chromium, molybdenum, and silicon, and their alloys such as aluminum bronzes and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum and brass platelets, with aluminum substrate platelets being particularly preferred.

[0048] Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

[0049] Due to their irregular structure, pigments based on lamellar substrate platelets produce a high proportion of scattered light. Furthermore, these pigments do not completely mask the existing color of a keratinous material, and effects similar to natural graying can be achieved.

[0050] Lenticular (lens-shaped) substrate platelets have a generally regular, rounded edge and are also referred to as "silver dollars" due to their appearance. Because of their regular structure, pigments based on lenticular substrate platelets have a high proportion of reflected light.

[0051] Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated films. They are characterized by a particularly thin substrate platelet, ranging from 5 to 50 nm, and by a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum metallized pigment are also referred to as VMP substrate platelets within the scope of this application. Aluminum VMP substrate platelets, for example, can be obtained by releasing aluminum from metallized films.

[0052] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0053] Uncoated lamellar, lenticular, and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop. These have proven particularly advantageous for use in dyes.

[0054] Suitable pigments based on a lamellar substrate platelet include, for example, the VISIONAIRE series pigments from Eckart.

[0055] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from the company Schlenk Metallic Pigments GmbH.

[0056] Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0057] Instead of or in addition to the pigment(s), the dyes according to the invention can also contain one or more direct dyes. Direct dyes are dyes that adhere directly to the hair and do not require an oxidative process to develop the color. Typical direct dyes are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0058] The direct-acting dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 0.5 g / L and are therefore not to be considered pigments. Preferably, the direct-acting dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 1.0 g / L.

[0059] Direct-drawing dyes can be divided into anionic, cationic, and nonionic direct-drawing dyes.

[0060] Kationische direktziehende Farbstoffe sind beispielsweise Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2 und Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76.

[0061] Examples of nonionic direct-drawing dyes include nonionic nitro and quinone dyes and neutral azo dyes. Examples of nonionic direct-drawing dyes are those known by their international names.Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 bekannten Verbindungen, sowie 1,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1,4-Bis-(2-hydroxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(2-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-Hydroxyethyl)amino]-3-nitro-1-methylbenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2'-Ureidoethyl)amino-4-nitrobenzol, 2-[(4-Amino-2-nitrophenyl)amino]-benzoesäure, 6-Nitro-1,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1,4-naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chlor-6-ethylamino-4-nitrophenol.

[0062] Anionic direct-acting dyes are also known as acid dyes. Acid dyes are defined as direct-acting dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms (-COOH, -SO3H) of the carboxylic acid and sulfonic acid groups, along with their deprotonated forms (-COO), are located at different pH values. - , -SO3 - The carboxylic acid groups (carboxylic acid groups) exist in equilibrium. As the pH decreases, the proportion of protonated forms increases. When direct-acting dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0063] The acid dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 0.5 g / L and are therefore not to be considered pigments. Preferably, the acid dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 1.0 g / L.

[0064] The alkaline earth salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali salts. If the solubility of these salts in water is below 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L (each at 25 °C, 760 mmHg), they do not fall under the definition of a direct-drawing dye.

[0065] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one color-imparting compound (F-1) from the group of direct dyes, particularly preferably from the group of anionic direct dyes.

[0066] Anionic direct-acting dyes are also known as acid dyes. Acid dyes are defined as direct-acting dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H) and / or one sulfate group (-OSO3H). Depending on the pH value, the protonated forms (-COOH, -SO3H) of the carboxylic acid and sulfonic acid groups are located at different pH levels, along with their deprotonated forms (-COO). - , -SO3 - or -OSO3 -The carboxylic acid groups (carboxylic acid groups) exist in equilibrium. As the pH decreases, the proportion of protonated forms increases. When direct-acting dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0067] Alkaline earth salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali salts. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), they do not fall under the definition of a direct-drawing dye.

[0068] A key characteristic of acid dyes is their ability to form anionic charges, with the carboxylic acid or sulfonic acid groups responsible for this typically being linked to various chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes, and / or indophenol dyes.

[0069] Als Beispiele für Säurefarbstoffe können genannt werden: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403,CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n° : C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1;CI20170;KATSU201;nosodiumsalt;Brown No.201;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201;D & C Brown No.1), Acid Red 14 (C.I.14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI C.I.18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.I. 60730, COLIPA n° C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blau V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, CI 42090, C.I.Food Blue 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9 (C.I.42100), Acid Green 22 (C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, C.I. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n° B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 und / oder D&C Brown 1.

[0070] Im Rahmen einer weiteren Ausführungsform ist ein erfindungsgemäßes Färbemittel dadurch gekennzeichnet, es mindestens einen Säurefarbstoff enthält, der ausgewählt ist aus der Gruppe aus Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 und / oder D&C Brown 1.

[0071] Since the alkaline earth salts (such as calcium and magnesium salts) or aluminum salts of acid dyes have lower solubility than the corresponding alkali metal salts, an organic dye that can be considered an acid dye in the form of its alkali metal salt can also exist as a pigment if the counterion for the acid group(s) is not an alkali metal ion, but an alkaline earth metal ion or an analogous, correspondingly more highly charged counterion. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), the compounds do not fall under the definition of a direct-drawing dye.

[0072] Like pigments, acid dyes are not intended to diffuse primarily into the keratin fiber, but rather to be preferentially deposited embedded in the chitosan film on the surface of the keratin fibers. For this reason, acid dyes are particularly preferred, as they have a solubility so high that they can no longer be classified as organic pigments, but which nevertheless exhibit relatively poor solubility.

[0073] For this reason, acid dyes are particularly preferred as organic coloring compounds which have a solubility in water at 25 °C between 0.5 g / l and 20 g / l, preferably between 1.0 g / l and 17 g / l and most preferably between 2.0 g / l and 15 g / l.

[0074] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one direct dye (F-1) which has a solubility in water at 25 °C of between 0.5 g / l and 20 g / l, preferably between 1.0 g / l and 17 g / l and most preferably between 2.0 g / l and 15 g / l.

[0075] The water solubility of anionic direct-acting dyes can be determined, for example, using the following method. Place 0.1 g of the anionic direct-acting dye into a beaker. Add a magnetic stir bar. Then add 100 ml of water. Heat this mixture to 25 °C on a magnetic stirrer while stirring. Stir for 60 minutes. Afterward, visually inspect the aqueous mixture. If undissolved dye remains, increase the amount of water—for example, in 10 ml increments. Continue adding water until the dye is completely dissolved. If the dye-water mixture cannot be visually assessed due to the high intensity of the dye, filter the mixture. If some undissolved dye remains on the filter paper, repeat the solubility test with a larger amount of water.If 0.1 g of the anionic direct-drawing dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g / L.

[0076] The water solubility of nonionic direct-drawing dyes can be determined in an analogous manner.

[0077] Acid Yellow 1 is called 8-Hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25°C).

[0078] Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of 20 g / L (25 °C).

[0079] Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid; its water solubility is above 40 g / L (25 °C).

[0080] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

[0081] Acid Orange 7 is the sodium salt of 4-[(2-Hydroxy-1-naphthyl)azo]benzenesulfonate. Its water solubility is greater than 7 g / L (25 °C).

[0082] Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has a very high water solubility of more than 20 wt%. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)naphthalene-2,7-disulfonate; its water solubility is 2.5 g / L (25 °C).

[0083] Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose water solubility is given as greater than 10 g / L (25 °C).

[0084] Brilliant Blue FCF, also known as Food Blue 2 or Acid Blue 9, is known as disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl{(4Z)-4-[ethyl(3-sulfonatobenzyl)amino]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate and has the CAS number 3844-45-9. The disodium salt of Acid Blue 9 has a water solubility of more than 20% by weight (25 °C).

[0085] Acid Blue 74 is also known as Indigo Carmine, Food Blue 1, or FD&C Blue 2, and its chemical name is indigo-5,5'-disulfonic acid, disodium salt, or disodium 5,5'-(2-(1,3-dihydro-3-oxo-2H-indazol-2-ylidene)-1,2-dihydro-3H-indol-3-one)disulfonate. The disodium salt of Acid Blue 74 has a solubility of 10 g / L in water at 25 °C. Acid Blue 74 (disodium salt) has the Color Index number 73015 and can be purchased, for example, under the trade name Bleu Covalac W6504.

[0086] The dye preferably contains the coloring compound(s) in certain quantity ranges. Good results can be obtained, for example, if the dye contains one or more coloring compounds (F-1) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.%, and most preferably 0.30 to 1.00 wt.%, based on the total weight of the dye.

[0087] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains – based on the total weight of the dyeing agent – ​​one or more color-imparting compounds (F-1) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%.

[0088] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains – based on the total weight of the dyeing agent – ​​one or more pigments (F-1) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%.

[0089] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains – based on the total weight of the dyeing agent – ​​one or more direct dyes (F-1) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%. Chitosans (F-2) in the dye (F)

[0090] As a second essential component, the dye according to the invention (F) contains at least one chitosan or a derivative of chitosan (F-2).

[0091] Chitosan, also known as polyglucosamine or poly-D-glucosamine, is a naturally occurring biopolymer derived from chitin, which is composed of β-1,4-glycosidically linked N-acetylglucosamine residues (specifically, 2-acetamido-2-deoxy-β-D-glucopyranose residues). Like chitin, it is a polyaminosaccharide. Chitosan is produced by deacetylating chitin, resulting in a molecule consisting of approximately 2000 linearly linked 2-amino-2-deoxy-β-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4.

[0092] Chitosan is preferably produced from chitin, which is found in shellfish or crustaceans. Chitosan is industrially produced from chitin by deacetylation. This can be achieved, for example, using (hot) sodium hydroxide or enzymatically. Both processes are used industrially, but the alkaline method is clearly the most prevalent in terms of volume. The degree of deacetylation can vary considerably: deacetylation can be complete or partial, resulting in a distribution of strongly deacetylated areas alongside weakly deacetylated areas, or a homogeneous deacetylation distribution. Simultaneously, this chemical process can decrease the polymer chain length (depolymerization). The molecular weight of chitosan can range over a wide spectrum, for example, from 20,000 to approximately 5 million g / mol.

[0093] Chitosan derivatives are compounds with a chitosan core structure in which at least some of the existing functional groups have been chemically modified. Chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure.

[0094] A derivative of chitosan therefore has a poly-D-glucosamine or polyglucosamine structure, which has either been converted into its salt by protonation of one or more nitrogen atoms or which bears an organic substituent on at least one oxygen atom and / or at least one amino group.

[0095] For example, a chitosan with a molecular weight of 20,000 to 800,000 g / mol is very suitable, preferably 50,000 to 600,000 g / mol, more preferably 80,000 to 450,000 g / mol and most preferably 100,000 to 300,000 g / mol.

[0096] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one chitosan and / or one chitosan derivative (F-2) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

[0097] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from the company Sigma Aldrich, for example.

[0098] A chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Daltons) is commercially available in pharmaceutical purity from BioLog Heppe (Kraeber), for example. The degree of deacetylation of this chitosan is 88–95%.

[0099] Chitosan in the form of its hydrochloride can be obtained as vegan chitosan from the company Sandream Impact. The hydrochloride of chitosan is a chitosan derivative according to the invention.

[0100] Chitosan O27 is a suitable, commercially available, high-molecular-weight chitosan from the company Polymar, which has a molecular weight of 100,000 - 2,000,000 g / mol.

[0101] It has proven particularly advantageous if the dye according to the invention contains the chitosans and / or chitosane derivatives (F-2) in certain quantity ranges. Particularly good results were obtained when the dye (F) – based on the total weight of the dye (F) – contained one or more chitosans and / or chitosane derivatives in a total amount of 0.1 to 7.0 wt.%, preferably 0.2 to 4.5 wt.%, more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%.

[0102] In a further explicitly preferred embodiment, a dye according to the invention is characterized in that it contains – based on the total weight of the dye – one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 7.0 wt.%, preferably 0.2 to 4.5 wt.%, more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%.

[0103] In a further explicitly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that it contains - based on the total weight of the dyeing agent - one or more chitosans in a total amount of 0.1 to 7.0 wt.%, preferably 0.2 to 4.5 wt.%, more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%. aliphatic C1-C 22 Monoalcohols (F-3)

[0104] As a third essential component of the invention (F-3), the dye according to the invention contains at least one aliphatic C1-C 22 Monoalcohol.

[0105] Under an aliphatic C1-C 22 A monoalcohol is defined as an organic compound with one to 22 carbon atoms, possessing an OH group (hydroxyl group) bonded to one of the carbon atoms. This alcohol is aliphatic, meaning it is not an aromatic alcohol.

[0106] Particularly suitable aliphatic C1-C 22 Monoalcohols can be selected, for example, from the group consisting of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol and 1-hexanol.

[0107] In principle, aliphatic C1-C 22Monoalcohols can also be one or more longer-chain compounds from the group consisting of dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachyl alcohol (eicosan-1-ol), heneicosyl alcohol (heneicosan-1-ol), and / or behenyl alcohol (docosan-1-ol). However, the shorter-chain aliphatic C1-C6 monoalcohols are preferred.

[0108] Particularly preferred is a dyeing agent for keratinous fibers, especially human hair, containing (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or a chitosan derivative, and (F-3) at least one aliphatic C1-C6 monoalcohol, and (F-4) at least one aliphatic C2-C 22 Polyol wherein the weight ratio of the average aliphatic C1-C6 monoalcohols (F-3) to the average aliphatic C2-C 22 Polyols (F-4), i.e., the weight ratio (F-3) / (F-4), is at least 1.

[0109] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one aliphatic C1-C 22 Monoalcohol (F-3) from the group consisting of ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol and 1-hexanol.

[0110] The experiments carried out have shown that ethanol is particularly compatible with the coloring compounds (F-1) or chitosans (F-2) and also with the optionally usable acetic acid; therefore, the use of ethanol in the dye (F) is particularly preferred.

[0111] In one explicitly preferred embodiment, a dye according to the invention is characterized by containing ethanol (F-3).

[0112] Ethanol has the Cas number 64-17-5.

[0113] 1-Propanol, also known as propyl alcohol, has the CAS number 71-23-8.

[0114] Isopropanol is also alternatively called 2-propanol and has the CAS number 67-63-0. 1-Butanol can also be called n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0115] 1-Pentanol has the CAS number 71-41-0 and is also known as amyl alcohol. 2-Methyl-2-butanol has the CAS number 75-85-4 and is also known as tert-pentanol. 1-Hexanol has the CAS number 111-27-3 and is also known as hexyl alcohol or capron alcohol.

[0116] The aliphatic C1-C 22Monoalcohols are preferably used in certain quantity ranges in the dye.

[0117] Particularly uniform and resistant colorations could be achieved when the dye – based on the total weight of the dye – contained one or more aliphatic C1-C 22 containing monoalcohols (F-3) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%.

[0118] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains – based on the total weight of the dyeing agent – ​​one or more aliphatic C1-C 22 Contains monoalcohols (F-3) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%.

[0119] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains - based on the total weight of the dyeing agent - one or more aliphatic C1-C6 monoalcohols (F-3) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%.

[0120] A dyeing agent is explicitly and particularly preferred which contains 40 to 95 wt.%, preferably 50 to 90 wt.%, further preferably 55 to 85 wt.% and most preferably 60 to 80 wt.% ethanol, based on the total weight of the dyeing agent. aliphatic C2-C 22 Polyols (F-4)

[0121] As a fourth essential component of the invention (F-4), the dye according to the invention contains at least one aliphatic C2-C 22 Polyol.

[0122] Under an aliphatic C2-C22 A polyol is defined as an organic compound with two to 22 carbon atoms, possessing at least two OH groups bonded to the carbon atoms. Preferably, the aliphatic C2-C polyol possesses... 22 Polyols have at least three OH groups (hydroxyl groups) bonded to the carbon atoms. These polyols are aliphatic, meaning they are not aromatic polyols.

[0123] Particularly suitable aliphatic C2-C 22 Polyols can be selected, for example, from the group consisting of glycerol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, hexane-1,2-diol, hexane-1,6-diol, PEG-3, PEG-4, PEG-5, PEG-6, PEG-7, PEG-8, sorbitol, mannitol, xylitol and erythritol.

[0124] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains at least one aliphatic C2-C 22Polyol (F-4) from the group consisting of glycerol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, hexane-1,2-diol, hexane-1,6-diol, PEG-3, PEG-4, PEG-5, PEG-6, PEG-7, PEG-8, sorbitol, mannitol, xylitol and erythritol, most preferably glycerol.

[0125] Glycerin is also known as propane-1,2,3-triol and has the CAS number 56-81-5. The most significant improvement in hair feel and shine has been observed with the use of glycerin; therefore, glycerin is the most preferred C2-C. 22 Polyol (F-4).

[0126] Ethane-1,2-diol can also be called ethylene glycol or 1,2-dihydroxyethane and has the CAS number 107-21-1.

[0127] Propane-1,2-diol bears the alternative names 1,2-dihydroxypropane and 1,2-propylene glycol and is a chiral compound. Propane-1,2-diol has the CAS numbers 57-55-6 (racemate), 4254-14-2 ((R)-enantiomer), and 4254-15-3 ((S)-enantiomer). All these compounds are according to the invention.

[0128] Propane-1,3-diol can alternatively be called 1,3-dihydroxypropane and has the CAS number 504-63-2.

[0129] Hexane-1,2-diol possesses a chiral carbon atom and bears the CAS numbers 6920-22-5 and 84994-66-1 (R compound), and 29117-56-4 (S compound). All these compounds or stereoisomers are according to the invention.

[0130] Hexane-1,6-diol is also alternatively called 1,6-dihydroxyhexane and has the CAS number 629-11-8.

[0131] PEG-3, PEG-4, PEG-5, PEG-6, PEG-7 and PEG-8 are low molecular weight polyethylene glycols of general formula (I) HO-(CH2-CH2-O) n -H (I) where n represents an integer from 3 to 6.

[0132] PEG-3 comprises polyethylene glycols of the general formula (I) with n equal to 3.

[0133] PEG-4 comprises polyethylene glycols of the general formula (I) with n equal to 4.

[0134] PEG-5 comprises polyethylene glycols of general formula (I) with n equal to 5.

[0135] PEG-6 comprises polyethylene glycols of general formula (I) with n equal to 6.

[0136] PEG-7 comprises polyethylene glycols of general formula (I) with n equal to 7.

[0137] PEG-8 comprises polyethylene glycols of general formula (I) with n equal to 8.

[0138] PEG-6 is a polyethylene glycol with an average of 6 ethylene oxy units, is also alternatively referred to as PEG 300 and can be purchased, for example, from the company Huntsman.

[0139] PEG-8, also known as PEG-400, is a polyethylene glycol with an average of 8 ethylene oxy units. Its molecular weight ranges from 380 to 420 g / mol. PEG-400 is commercially marketed under this name by Petronas.

[0140] Sorbitol, also known as sorbitol, has the CAS number 50-70-4 and the IUPAC name (2R,3R,4R,5S)-hexane-1,2,3,4,5,6-hexol. Potential suppliers of sorbitol include companies such as ADM and Mitsubishi.

[0141] Mannitol, which can also be called mannite, has the IUPAC name (2R,3R,4R,5R)-hexane-1,2,3,4,5,6-hexol and the CAS numbers 87-78-5 (D,L mixture) and 69-65-8 (D form).

[0142] Xylitol, also called xylit or (2R,3R,4S)-pentane-1,2,3,4,5-pentol, has the CAS number 87-99-0.

[0143] Erythritol has the IUPAC name (2S,3R)-butane-1,2,3,4-tetrol and the CAS number 149-32-6.

[0144] To achieve the best possible feel when dyeing the keratinous fibers, the aliphatic C2-C ions are used. 22 Polyols are preferably used in certain quantity ranges in the composition according to the invention. A particularly good feel and also a very high gloss were observed when the colorant – based on its total weight – contained one or more aliphatic C2-C 22 contained polyols (F-4) in a total amount of 0.01 to 20 wt.%, preferably 0.1 to 10 wt.%, further preferably 0.2 to 5.0 wt.%, even more preferably 0.3 to 2.5 wt.% and most preferably 0.6 to 1.8 wt.%.

[0145] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains – based on the total weight of the dyeing agent – ​​one or more aliphatic C2-C 22containing polyols (F-4) in a total amount of 0.01 to 20 wt.%, preferably 0.1 to 10 wt.%, further preferably 0.2 to 5.0 wt.%, even more preferably 0.3 to 2.5 wt.% and most preferably 0.6 to 1.8 wt.%.

[0146] Particularly preferred is a dyeing agent for keratinous fibers, especially human hair, containing - based on its total weight - (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or one chitosan derivative, and (F-3) 40–95 wt% ethanol, and (F-4) 0.01 to 20 wt% glycerin.

[0147] Particularly preferred is a means for dyeing keratinous fibers, especially human hair, containing - based on its total weight - (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or one chitosan derivative, and (F-3) 50–90 wt% ethanol, and (F-4) 0.1 to 10 wt% glycerol,

[0148] Particularly preferred is a means for dyeing keratinous fibers, especially human hair, containing - based on its total weight - (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or one chitosan derivative, and (F-3) 55–85 wt% ethanol, and (F-4) 0.2 to 5.0 wt% glycerin.

[0149] Particularly preferred is a means for dyeing keratinous fibers, especially human hair, containing - based on its total weight - (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or one chitosan derivative, and (F-3) 60-80 wt% ethanol, and (F-4) 0.3 to 2.5 wt% glycerin.

[0150] Particularly preferred is a means for dyeing keratinous fibers, especially human hair, containing - based on its total weight - (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or one chitosan derivative, and (F-3) 60-80 wt% ethanol, and (F-4) 0.6 to 1.8 wt% glycerin.

[0151] In the aforementioned preferred and particularly preferred quantity ranges of the components ethanol (F-3) and glycerol (F-4), the requirement that the weight ratio of the average ethanol (F-3) to the average glycerol (F-4) is greater than 1 is met. Weight ratio (F-3) / (F-4)

[0152] During the work carried out, it was observed that the weight ratio of the aliphatic C1-C contained in the average 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22 The polyols (F-4), i.e., the weight ratio (F-3) / (F-4), should be at least 1 to positively influence the properties of the formed film on the keratin surface. A weight ratio (F-3) / (F-4) greater than 1 indicates that the dye contains a higher total amount of C1-C. 22 -Monoalcohols as at C2-C 22 Polyols.

[0153] In a dye containing ethanol (F-3) and glycerol (F-4), it was observed that the weight ratio of the average ethanol (F-3) to the average glycerol (F-4) must be greater than 1. If the weight ratio (F-3) / (F-4) is greater than 1, the dye contains more ethanol (F-3) than glycerol (F-4).

[0154] By further adjusting this weight ratio (F-3) / (F-4), the feel and the realism properties of the trained film can be optimized even further.

[0155] In a further particularly preferred embodiment, a dye according to the invention is characterized in that the weight ratio of the aliphatic C1-C contained in the medium is 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22polyols (F-4), i.e. the weight ratio (F-3) / (F-4), is in the range of 500 to 10, preferably from 250 to 20, more preferably from 200 to 30, even more preferably from 180 to 50 and most preferably from 150 to 60.

[0156] In the coloring agent, ethanol (F-3) acts as a component of the cosmetic carrier, which disperses the film-forming chitosan (F-2) so finely that the chitosan can be deposited evenly and in the form of a thin layer on the surface of the keratin fibers. The coloring compounds (F-1) are incorporated into this film. Since ethanol (F-3) is volatile, the cosmetic carrier can evaporate particularly well and evenly from the keratin surface after application, and the chitosan film hardens.

[0157] The addition of glycerin (F-4) allows it to distribute particularly evenly within the ethanolic cosmetic carrier and to be uniformly incorporated into the chitosan film. Glycerin is non-volatile and therefore does not evaporate during the drying of the keratin fibers.

[0158] It has been found that there is an optimal range for the incorporation of glycerin into the chitosan film. Compared to the volatile alcohol (ethanol), which is necessary for the distribution and curing of the film, the amount of glycerin used must therefore not be too high. The weight ratio of ethanol (F-3) to glycerin (F-4) is most preferably in the range of 500 to 10, more preferably from 250 to 20, further preferably from 200 to 30, even more preferably from 180 to 50, and most preferably from 150 to 60.

[0159] In a particularly preferred embodiment, a dye according to the invention is therefore characterized in that the weight ratio of the ethanol (F-3) contained in the mixture to the glycerol (F-4) contained in the mixture, i.e. the weight ratio (F-3) / (F-4), is in the range of 500 to 10, preferably from 250 to 20, more preferably from 200 to 30, even more preferably from 180 to 50 and most preferably from 150 to 60.

[0160] Example: If 100 g of a dye contains 70 g ethanol (F-3) and 0.5 g glycerol (F-4), then the weight ratio (F-3) / (F-4) is 140.

[0161] If 100 g of a dye contains 70 g ethanol (F-3) and 1.0 g glycerol (F-4), then the weight ratio (F-3) / (F-4) is 70. organic and / or inorganic acids (F-5) in the dye

[0162] As an optional component, the dye according to the invention can contain at least one organic and / or inorganic acid (F-5).

[0163] The use of one or more acids can lower the pH of the dye, thereby protonating the chitosan completely or partially, allowing it to dissolve more readily. Macroscopically, the protonation of chitosan in water is observed as swelling, from which, when the preferred or highly preferred pH is established, a particularly uniform and thin film is deposited on the keratin fibers, such as hair. It has been shown that the more uniformly the film forms on the hair, the better its durability. Forming a particularly uniform film has also resulted in dyes with exceptional wash fastness. Furthermore, the presence of the acid(s) (F-5) in the dye also enables the chitosan to form a particularly thin film on the hair.Comparative studies have shown that a uniformly thin film has better resistance to external mechanical influences.

[0164] Particularly suitable organic acids include, for example, acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0165] Formic acid and propanoic acid are also suitable acids (F-5).

[0166] In a further particularly preferred embodiment, a dye according to the invention is characterized in that it contains one or more organic acids (F-5) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, most preferably acetic acid.

[0167] Acetic acid dissolves chitosan particularly well and leads to very thin and uniform films; therefore, a dye (F) containing acetic acid is particularly preferred.

[0168] In a further explicitly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that it contains acetic acid (F-5).

[0169] By using the acid(s) in suitable quantities, the pH of the dye can be adjusted to the desired pH range. Particularly thin and uniform films were obtained when the dye contained water and was adjusted to a pH in the range of 2.0 to 7.5, preferably 2.5 to 6.5, more preferably 3.0 to 6.0, and most preferably 3.0 to 5.0.

[0170] In a further particularly preferred embodiment, a dye according to the invention is therefore characterized in that it has a pH value of 2.0 to 7.5, preferably of 2.5 to 6.5, more preferably of 3.0 to 6.0 and most preferably of 3.0 to 5.0. Water content (F-6)

[0171] The cosmetic carrier may contain water in addition to the aliphatic C1-C22 monoalcohol(s) (F-3). The cosmetic carrier is particularly preferably a mixture of aliphatic C1-C22 monoalcohols (F-3) and water (F-6).

[0172] Ethanol is the most preferred aliphatic C1-C 22 Monoalcohol (F-3), so that the cosmetic carrier particularly preferably comprises a mixture of ethanol and water.

[0173] Since the content of the C1-C 22Since the concentration of monoalcohols is particularly preferably relatively high, and most preferably in the range of 60 to 80 wt.%, it is advantageous to reduce the water content accordingly. The dye (F) therefore particularly preferably contains 5 to 70 wt.%, more preferably 10 to 60 wt.%, further preferably 15 to 50 wt.%, and most preferably 20 to 40 wt.% water (F-6). The quantities of water mentioned here are based on the total weight of the dye.

[0174] In a further particularly preferred embodiment, a dyeing agent according to the invention is characterized in that it contains - based on the total weight of the dyeing agent - 10 to 50 wt.%, preferably 15 to 45 wt.%, more preferably 20 to 40 wt.% and most preferably 25 to 35 wt.% water (F-6). Quantity fraction of components (F-1), (F-2), (F-3), (F-4), (F-5) and (F-6) in the dye

[0175] During the work leading to this invention, microscopic images were taken which showed that a thin, uniform film on the keratin fibers possesses particularly good resistance to external influences such as mechanical friction or hair washing. The smoother and more continuous the film, the less surface area it offers to external forces. Once the film is broken in one place, it can be completely removed very quickly by the constant movement of the keratin fibers.

[0176] It was found that the films produced with the dye were particularly thin, uniform, and stable when the dye consisted largely of components (F-1), (F-2), (F-3), (F-4), (F-5), and (F-6). It is suspected that other components could disrupt the uniformity of the film because they could become embedded in the film, weaken it at that point, or create a point of attack for external forces. For this reason, it is especially preferred that components (F-1), (F-2), (F-3), (F-4), (F-5), and (F-6) are present together in the dye at a proportion of at least 94.0 wt.%, preferably at least 95 wt.%, further preferably at least 96 wt.%, even more preferably at least 99 wt.%, and most preferably at least 99.7 wt.%.

[0177] If components (F-1), (F-2), (F-3), (F-4), (F-5), and (F-6) together constitute at least 99.7% by weight in the dye, then the dye—based on its total weight—consists of at least 99.7% by weight of components (F-1), (F-2), (F-3), (F-4), (F-5), and (F-6). In other words, in this case, other substances or ingredients different from (F-1) to (F-6) are present in the dye at a maximum of 0.3% by weight.

[0178] In a further preferred embodiment, a dyeing agent according to the invention is characterized in that the components (F-1), (F-2), (F-3), (F-4), (F-5) and (F-6) are together contained in the dyeing agent in a quantity of at least 94.0 wt.%, preferably at least 95 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.%.

[0179] In a further explicitly preferred embodiment, a coloring agent according to the invention is characterized in that it comprises at least 94.0 wt.%, preferably at least 95 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.% of (F-1) one or more coloring compounds from the group consisting of pigments and direct dyes, and (F-2) one or more chitosans, and (F-3) one or more aliphatic C1-C 22 Monoalcohols, and (F-4) one or more aliphatic C2-C 22 Polyols, and (F-5) one or more organic acids, and (F-6) Water wherein the weight ratio of the aliphatic C1-C contained in the average 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22Polyols (F-4), i.e., the weight ratio (F-3) / (F-4), is at least 1.

[0180] In a further explicitly preferred embodiment, a coloring agent according to the invention is characterized in that it comprises at least 94.0 wt.%, preferably at least 95 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.% of (F-1) one or more coloring compounds from the group consisting of pigments and direct dyes, and (F-2) one or more chitosans, and (F-3) Ethanol, and (F-4) Glycerol, and (F-5) one or more organic acids, and (F-6) Water wherein the weight ratio of the ethanol (F-3) contained on average to the glycerol (F-4) contained on average, i.e. the weight ratio (F-3) / (F-4), is at least 1. Methods for dyeing keratinous fibers

[0181] The dye is used in processes for dyeing keratinous fibers, especially human hair.

[0182] A second subject matter of the present application is therefore a method for dyeing keratinous fibers, in particular human hair, in which a dyeing agent, which has been disclosed in detail in the description of the first subject matter of the invention, is applied to the keratinous fibers and, if necessary, rinsed off after an exposure time.

[0183] The dye can be applied to the keratin fibers, for example, with a gloved hand or using a brush or applicator. After application, the dye can be spread over the keratin fibers and, if necessary, gently massaged in.

[0184] In one embodiment, the dye is rinsed off using a rinse-off method and, after a dwell time, is rinsed off with water or with water and the aid of shampoo. Suitable dwell times are, for example, 5 to 60 minutes, preferably 5 to 45 minutes, more preferably 5 to 30 minutes, and most preferably 5 to 15 minutes.

[0185] The uniformity of the color and its wash fastness were particularly outstanding when the dye was applied as a "leave-on" dye. In this case, the dye was not rinsed out, but rather the keratin fibers still coated with the dye were dried. Drying of the keratin fibers can take place at room temperature in the open air, or the fibers still coated with the dye can be heated to accelerate the drying process.

[0186] A method for dyeing keratinous fibers, especially human hair, is therefore particularly preferred, comprising - the application of a dye, as disclosed in detail in the description of the first subject matter of the invention, to the keratinous fibers, and - heating the keratinous fibers covered with the dye (F) to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.

[0187] Heating or heat treatment refers to the process of bringing the keratin fibers into contact with a heated device, or applying this heated device to or on the keratin fibers. Furthermore, the keratin material can also be exposed to warm / hot air for heat treatment. Examples of such devices include a hairdryer, a heat cap, a flat iron, a curling iron, or an infrared lamp.

[0188] In a particularly preferred embodiment, a method according to the invention is characterized in that the heating to more than 40 °C is carried out by using a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron or an infrared lamp, most particularly by using a hairdryer.

[0189] The duration of the heat treatment can be adjusted to the selected temperature range. For example, heat treatment can be carried out for a duration of 5 seconds to 60 minutes, preferably from 15 seconds to 45 minutes, more preferably from 15 seconds to 30 minutes, and most preferably from 15 seconds to 15 minutes.

[0190] In the process according to the invention, the keratin fibers can be completely subjected to heat treatment, but the treatment of partial areas of the keratin fibers can also be included. Complete heat treatment of the keratin fibers is preferred, i.e., preferably all keratin fibers to which the dye (F) has also been applied are treated with heat.

[0191] For example, the keratin fibers or hair can be treated with a hairdryer, possibly under combs or brushes, blowing warm or hot air onto the fibers. This air is preferably between 40 and 70 °C. Alternatively, the keratin material or hair can be held under an infrared lamp, preferably set to a temperature of 40 to 70 °C.

[0192] In a further particularly preferred embodiment, a method according to the invention is characterized in that the heat treatment is carried out by using a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron or an infrared lamp.

[0193] During heat treatment or heating, the keratin fibers can also be combed or brushed.

[0194] For example, if the hair is combed continuously or occasionally during blow-drying, the individual fibers can be separated particularly well from each other, and the feel of the dyed hair was particularly good and uncoated.

[0195] In a further particularly preferred embodiment, the method according to the invention is therefore characterized in that the keratin fibers or the hair are combed or brushed during the heat treatment.

[0196] Regarding the other preferred embodiments of the methods according to the invention, what has been said about the dyes according to the invention applies mutatis mutantis. Examples 1. Formulations

[0197] The following dyes were produced (all values, unless otherwise stated, are in wt.%): Dyeing agent (FM) FM1 (wt%)V FM2 (wt%) E FM3 (wt%) E Unipure Red LC 3079 (Pigment Red 7, Cas-Nr.5281-04-9 (CI 15850) (F-1) 0,40 0,40 0,40 Chitosan (MW = 100,000 - 300,000 g / mol, SigmaAldrich) (F-2) 0,90 0,90 0,90 Ethanol (F-3) 70 70 70 Glycerin (F-4) - 0,50 1,00 acetic acid 0,60 0,60 0,60 Water (distilled) ad 100 ad 100 ad 100 V = Comparison E = Invention Dyeing agent (FM) FM4 (wt%) FM5 (wt%) E FM6 (wt%) E Bleu Covalac W6504 (Acid Blue 74, CI 73015)(F-1) 0,40 0,40 0,40 Chitosan (MW = 100,000 - 300,000 g / mol, SigmaAldrich) (F-2) 0,90 0,90 0,90 Ethanol (F-3) 70 70 70 Glycerin (F-4) - 0,50 1,00 acetic acid 0,60 0,60 0,60 Water (distilled) ad 100 ad 100 ad 100

[0198] A swelling solution was produced from the water, acetic acid and chitosan.

[0199] Ethanol was mixed with glycerin, and the pigment was added to this mixture. This dispersion was homogenized by rapid stirring.

[0200] Afterwards, the aqueous chitosan swelling and the alcoholic pigment dispersion were mixed together and homogenized by rapid stirring. 2. Application to strands

[0201] The dyes were applied to strands of hair (Kerling brand). For this, 2.0 g of dye (FM) per gram of hair strand was massaged in and left on for 1 minute. Afterwards, the strands, still coated with dye, were dried with a standard hairdryer. During drying, the strands were combed through. 3. Measuring shine and hair feel

[0202] The strands dyed in this way were assessed by trained individuals in a blind test. To measure hair shine, the strands dyed with FM1, FM2, and FM3 were laid side by side under a daylight lamp and visually compared. Shine was rated using a school grading system (1 = very shiny, 6 = very dull, no reflections). The shine of the strands dyed with FM4, FM5, and FM6 was compared analogously.

[0203] To assess the feel of the hair, each trained person took the strand to be tested and ran their fingers through it several times. The feel of the hair strands colored with formulations FM1, FM2, and FM3 was then compared. The evaluation was based on a school grading system (1 = smooth, pleasant feel; 6 = particularly dull, rough feel). The feel of the hair strands colored with dyes FM4, FM5, and FM6 was compared in a similar manner. Dye with pigment Red 7 FM1V without glycerin FM2E 0.5 wt% glycerin FM3E 1.0 wt% glycerin shine 5 3 2 Hair feeling 5 3 2 Dye with Acid Blue 74 FM4V without glycerin FM5E 0.5 wt% glycerin FM6E 1.0 wt% glycerin shine 5 3 2 Hair feeling 5 3 2

[0204] The addition of 0.5% w / w glycerin noticeably improved the shine and feel of the colored strands. A further improvement was achieved with the addition of 1.0% w / w glycerin. These effects were observed with both Pigment Red 7 and Acid Blue 74. 2. Further examples of wording Dyeing agent (FM) FM7 (wt%) FM8 (wt%) FM9 (wt%) Unipure Red LC 3079 (Pigment Red 7, Cas No. 5281-04-9 (CI 15850) 0,20 0,80 1,20 Chitosan (MW = 100,000 - 300,000 g / mol, SigmaAldrich) (F-2) 0,80 0,90 1,00 Ethanol (F-3) 65 80 90 Glycerin (F-4) 0,8 2,5 0,4 acetic acid 0,60 0,60 0,60 Water (distilled) ad 100 ad 100 ad 100 Dyeing agent (FM) FM10 (wt%) FM11 (wt%) FM12(wt.%) Bleu Covalac W6504 (Acid Blue 74, CI 73015)(F-1) 0,30 0,50 1,40 Chitosan (MG = 100,000 - 300,000 g / mol, SigmaAldrich) (F-2) 0,70 1,50 1,10 Ethanol (F-3) 65 80 85 Glycerin (F-4) 0,7 2,0 1,7 Acetic acid 0,60 0,60 0,60 Water (dist.) to 100 to 100 to 100 QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] DE 19847883 A1

[0008]

Claims

[1] Agents for dyeing keratinous fibers, especially human hair, containing (F-1) at least one colouring compound from the group consisting of pigments and direct dyes, and (F-2) at least one chitosan and / or a chitosan derivative, and (F-3) at least one aliphatic C1-C 22 Monoalcohol, and (F-4) at least one aliphatic C2-C 22 Polyol wherein the weight ratio of the aliphatic C1-C contained in the average 22 -Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22 Polyols (F-4), i.e., the weight ratio (F-3) / (F-4), is at least 1. [2] Dyeing agent according to claim 1, characterized by, that it contains at least one pigment (F-1) from the group consisting of inorganic pigments, organic pigments, pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments. [3] Dyeing agent according to any one of claims 1 to 2, characterized by , that it contains at least one colouring compound (F-1) from the group of direct dyes, particularly preferably from the group of anionic direct dyes. [4] Dyeing agent according to any one of claims 1 to 3, characterized by that it contains at least one direct dye (F-1) which has a solubility in water at 25 °C between 0.5 g / l and 20 g / l, preferably between 1.0 g / l and 17 g / l and most preferably between 2.0 g / l and 15 g / l. [5] Dyeing agent according to any one of claims 1 to 4, characterized bythat it contains - based on the total weight of the dye - one or more coloring compounds (F-1) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%. [6] Dyeing agent according to any one of claims 1 to 5, characterized by , that it contains at least one chitosan and / or one chitosan derivative (F-2) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol. [7] Dyeing agent according to any one of claims 1 to 6, characterized bythat it contains - based on the total weight of the dye - one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 7.0 wt.%, preferably 0.2 to 4.5 wt.%, more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%. [8] Dyeing agent according to any one of claims 1 to 7, characterized by that there is at least one aliphatic C1-C 22 Monoalcohol (F-3) from the group consisting of ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol and 1-hexanol, most preferably ethanol. [9] Dyeing agent according to any one of claims 1 to 8, characterized by that, in relation to the total weight of the dye, there is one or more aliphatic C1-C 22 Contains monoalcohols (F-3) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%. [10] Dyeing agent according to any one of claims 1 to 9, characterized by that there is at least one aliphatic C2-C 22 Polyol (F-4) from the group consisting of glycerol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, hexane-1,2-diol, hexane-1,6-diol, PEG-3, PEG-4, PEG-5, PEG-6, PEG-7, PEG-8, sorbitol, mannitol, xylitol and erythritol, most preferably glycerol. [11] Dyeing agent according to any one of claims 1 to 10, characterized by that, in relation to the total weight of the dye, there is one or more aliphatic C2-C 22 contains polyols (F-4) in a total amount of 0.01 to 20 wt.%, preferably 0.1 to 10 wt.%, further preferably 0.2 to 5.0 wt.%, even more preferably 0.3 to 2.5 wt.% and most preferably 0.6 to 1.8 wt.%. [12] Dyeing agent according to any one of claims 1 to 11, characterized by , that the weight ratio of the aliphatic C1-C contained in the average 22-Monoalcohols (F-3) to the aliphatic C2-C contained in the average 22 polyols (F-4), i.e. the weight ratio (F-3) / (F-4), is in the range of 500 to 10, preferably from 250 to 20, more preferably from 200 to 30, even more preferably from 180 to 50 and most preferably from 150 to 60. [13] Dyeing agent according to any one of claims 1 to 12, characterized by that it contains one or more organic acids (F-5) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, most preferably acetic acid. [14] Dyeing agent according to any one of claims 1 to 13, characterized by that it contains - based on the total weight of the dye - 10 to 50 wt.%, preferably 15 to 45 wt.%, more preferably 20 to 40 wt.% and most preferably 25 to 35 wt.% water (F-6). [15] Dyeing agent according to any one of claims 1 to 14, characterized by, that the components (F-1), (F-2), (F-3), (F-4), (F-5) and (F-6) together are contained in the dye in a quantity of at least 94.0 wt.%, preferably at least 95 wt.%, further preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.%. [16] Method for dyeing keratinous fibers, in particular human hair, in which a dye according to one of claims 1 to 15 is applied to the keratinous fibers and optionally rinsed off after an exposure time. [17] The method of claim 16 comprising - the application of the dye to the keratinous fibers, and - heating the keratin fibers covered with the dye to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.