Dyeing agent for dyeing keratin fibers, containing at least one chitosan, one pigment and one cellulose

Abstract

The invention relates to a method for dyeing keratin fibers, in particular human hair, comprising: (F-1) at least one chitosan and / or chitosan derivative; (F-2) at least one pigment; and (F-3) at least one cellulose and / or cellulose derivative.

Description

[0001] Dyeing agent for dyeing keratinous fibers containing at least one chitosan, one pigment and one cellulose.

[0002] The subject matter of the present application is a dye (F) for dyeing keratinous fibers, in particular human hair, comprising at least one chitosan and / or one chitosan derivative, at least one pigment and at least one cellulose and / or one cellulose derivative.

[0003] A second subject matter of the present application is a method for dyeing keratinous fibers, in particular human hair, with the dye (F) described above, comprising the steps in the specified order, the application of the dye (F) to the keratinous fibers and the drying of the keratinous fibers covered with the dye (F).

[0004] A third subject matter of the present application is the use of a cellulose and / or a cellulose derivative in the dye described above (F) to improve the wash stability of a dyeing on keratinous fibers.

[0005] 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.

[0006] 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.

[0007] 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."

[0008] Dyeing with pigments offers several significant advantages. Since the pigments adhere only to the outer surface of the keratin fibers, particularly the hair fibers, unwanted dyes can be removed quickly and easily without leaving any residue. This allows users to return to their original hair color immediately and effortlessly. This dyeing process is therefore particularly attractive for consumers who do not want to dye their hair regularly.

[0009] Despite these many advantages, the pigment-based dyeing system still has some disadvantages, stemming from the limited penetration depth of the pigments into the keratin fibers. Because the pigments do not diffuse into the keratin fiber but merely deposit on the outer surface of the fiber as 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.

[0010] 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 was intended to 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, colorations obtained with pigment and chitosan still have disadvantages regarding their wash fastness.Achieving even coloring across the entire length of the hair cannot yet be considered optimal, as the durability of the films varies on different parts of the hair, especially in the areas at the roots and tips.

[0011] The objective of the present application was therefore to disclose a pigment-based dye that enables intense coloring with improved wash fastness. The dyeing should be achieved using biopolymers, and the keratin fibers or hair dyed with this dye should not feel coated or greasy, should exhibit a healthy shine, and the elasticity of the keratin fibers should not be negatively affected. A further objective of the present application was to disclose a dye in which the application of the dye is improved by optimizing its viscosity, thereby at least reducing or preventing dripping of the dye.

[0012] Surprisingly, it has now been found that this task can be solved by using a dye containing chitosan and / or a chitosan derivative, a pigment and cellulose and / or a cellulose derivative.

[0013] A first object of the present invention is a dyeing agent for dyeing keratinous fibers, in particular human hair, comprising

[0014] (F-1) at least one chitosan and / or one chitosan derivative,

[0015] (F-2) at least one pigment and

[0016] (F-3) at least one cellulose and / or a cellulose derivative.

[0017] Hair dyed with the aforementioned dye was characterized by an intense color result with improved wash fastness. Furthermore, the dyed hair was very evenly colored and possessed a beautiful, natural shine without feeling greasy or coated. The hair was not weighed down, and its natural movement was not negatively affected. Additionally, the dye adhered better to the hair. The use of cellulose and / or a cellulose derivative resulted in the formation of a particularly homogeneous film on the hair, which was also characterized by improved flexibility. This improved flexibility led to greater pliability of the hair, and the film remained intact for longer under mechanical stress.

[0018] Keratinous fibers

[0019] Keratinous fibers include hair, wool, and fur. Human hair is particularly often considered a keratinous fiber.

[0020] dyeing agents

[0021] The term "coloring agent" is used in this invention to describe the coloring of keratin fibers, particularly hair, by the use of pigments. In this coloring process, the pigments are deposited as coloring compounds in a homogeneous, uniform, and smooth film on the surface of the keratin fibers. This film is formed by the chitosan(s) and / or chitosan derivative(s).

[0022] Dyeing agent (F) The dyeing agent (F) according to the invention is characterized by its content of the components (F-1), (F-2) and (F-3).

[0023] Chitosans and / or chitosan derivatives (F-1) in the dye (F)

[0024] The first essential component of the dye is at least chitosan and / or a chitosan derivative (F-1).

[0025] 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.

[0026] Suitable chitosans are freely available commercially under the trade names Hydagen® CMF (1 wt% active substance in aqueous solution with 0.4 wt% glycolic acid, molecular weight 500000 to 5000000 g / mol; Cognis), Hydamer® HCMF (chitosan (80% deacetylated), molecular weight 50000 to 1000000 g / mol, Chitinor, formerly Cognis), Kytamer® PC (approximately 80 wt% active substance of chitosan pyrolidone carboxylate (INCI name: Chitosan PCA), Amerchol), Chitolam® NB / 101 and Chitosan 90 / 100 / A1® (chitosan (approximately 90% deacetylated); BioLog Heppe).

[0027] 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.

[0028] Chitosan derivatives are compounds with a chitosan core structure in which at least some of the existing functional groups have been chemically modified. These chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure. A chitosan with a molecular weight of 20,000 to 800,000 g / mol is particularly 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.

[0029] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the dyeing agent (F) contains at least one chitosan and / or one chitosan derivative (F-1) 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.

[0030] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from the company Sigma Aldrich, for example.

[0031] A chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Daltons) is, for example, commercially available in pharmaceutical purity from BioLog Heppe (Kraeber). The degree of deacetylation of this chitosan is 88–95%.

[0032] 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.

[0033] Chitosan 027 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.

[0034] It has proven particularly advantageous if the dye according to the invention contains the chitosans and / or chitosan derivatives (F-1) in certain quantity ranges. Particularly good results were obtained when the dye contained one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.%, more preferably 0.1 to 1.5 wt.%, and most preferably 0.3 to 0.9 wt.%.

[0035] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.%, more preferably 0.1 to 1.5 wt.% and most preferably 0.3 to 0.9 wt.%.

[0036] Pigments (F-2) in the dye CF) As a second essential component, the dye (F) according to the invention contains at least one pigment. 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 potentially finely dispersed pigment, the mixture is filtered. If a proportion of undissolved pigment remains on the filter paper, the pigment's solubility is below 0.5 g / L.

[0037] Particularly preferred is a dye for dyeing keratinous fibers, especially human hair, comprising

[0038] (F-1) at least one chitosan and / or one chitosan derivative,

[0039] (F-2) at least one pigment which has a solubility in water at 25 °C of less than 0.5 g / L, preferably less than 0.1 g / L, more preferably less than 0.05 g / L, and

[0040] (F-3) at least one cellulose and / or a cellulose derivative.

[0041] Suitable color pigments can be of inorganic and / or organic origin.

[0042] In a preferred embodiment, a coloring agent (F) according to the invention is characterized in that it contains at least one coloring compound (F-2) from the group of inorganic and / or organic pigments.

[0043] In a preferred embodiment, a dyeing agent (F) according to the invention is characterized in that it contains at least one inorganic and / or organic pigment (F-2).

[0044] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be produced, for example, from chalk, ochre, umber, green earth, burnt sienna, or graphite. Furthermore, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments can be used as inorganic color pigments. 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.Particularly 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).

[0045] 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.

[0046] 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).

[0047] In a further preferred embodiment, a coloring agent (F) according to the invention is characterized in that the coloring agent (F) contains at least inorganic pigment (F-2), 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.

[0048] In a further preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the dyeing agent (F) 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).

[0049] 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. Particularly favored color pigments with the trade name Colorona® include, for example:

[0050] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0051] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0052] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0053] Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0054] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)

[0055] Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0056] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0057] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0058] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0059] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM

[0060] DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0061] Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0062] Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)

[0063] Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)

[0064] Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)

[0065] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510)

[0066] Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0067] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0068] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0069] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

[0070] Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0071] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0072] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0073] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0074] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0075] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

[0076] Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0077] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0078] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

[0079] Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0080] Weiterhin besonders bevorzugte Farbpigmente mit der Handelsbezeichnung Xirona® sind beispielsweise:

[0081] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0082] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0083] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0084] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0085] In addition, particularly preferred color pigments with the trade name Unipure® include, for example:

[0086] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0087] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0088] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0089] In a further embodiment, the dyeing agent (F) according to the invention can also contain one or more organic pigments.

[0090] 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.

[0091] 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.

[0092] In a further particularly preferred embodiment, a coloring agent (F) according to the invention is characterized in that it contains at least one organic pigment (F-2) 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 71 105, 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.

[0093] 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.

[0094] For example, alizarin lacquer can be used as a colored lacquer.

[0095] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the colorant (F) 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 a mean particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, and particularly of 14 to 30 pm. The mean particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0096] Pigments (F-2) 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.

[0097] In a further preferred embodiment, a means according to the invention is characterized in that it contains at least one pigment (F-2) selected from the group consisting of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0098] 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.

[0099] 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.

[0100] 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 pm, especially approximately 5 to 100 pm.

[0101] 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 Heios instrument with Quixel wet dispersion. For sample preparation, the sample to be tested was pre-dispersed in isopropanol for 3 minutes.

[0102] The substrate plates can be made from any material that can be formed into platelet form.

[0103] They can be of natural origin or synthetically produced. Materials from which the substrate plates can be made 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 made of metal (alloys).

[0104] 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 platelets being particularly preferred.

[0105] Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0110] Uncoated lamellar, lenticular and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect the incident light to a high degree and produce a light-dark flop. These have proven particularly advantageous for use in dyes.

[0111] Suitable pigments based on a lamellar substrate platelet include, for example, the VISIONAIRE series pigments from Eckart.

[0112] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH. Pigments based on a substrate platelet containing a vacuum metallized pigment are available, for example, under the names Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0113] The pigment(s) (F-2) constitute the second essential component of the dyeing agent (F) according to the invention and are preferably used in specific average quantities. Particularly good results were obtained when the dyeing agent contained one or more pigments (F-2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.%, more preferably 0.1 to 3 wt.%, and most preferably 0.2 to 1.5 wt.%.

[0114] In a further particularly 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 (F) - one or more pigments (F-2) in a total amount of 0.01 to 10.0 wt. %, preferably 0.05 to 5.0 wt. %, further preferably 0.1 to 3 wt. %, and most preferably 0.2 to 1.5 wt. %,.

[0115] Cellulose (derivatives) (F-3) in the dye

[0116] As a third essential component, the dye (F) used in the dye (F) according to the invention contains at least one cellulose and / or at least one cellulose derivative (F-3).

[0117] During the work leading to this invention, it was found that the use of cellulose or cellulose derivatives not only resulted in good thickening of the formulation, but also that the film formed on the keratin fibers was particularly homogeneous and resistant. One explanation for this effect could be the formation of the film from a mixture of chitosan and cellulose, which ensures particularly good embedding of the pigments within the film. In this way, the wash fastness of the dyed fibers could be further improved.

[0118] For the purposes of this invention, cellulose means both cellulose itself and a derivative thereof, i.e., a chemically or physically modified cellulose.

[0119] Cellulose is composed of β-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions alternate with those of lower order (amorphous regions) within cellulose. Natural and manufacturing-related impurities, such as the presence of carboxyl groups, are typically in the range of approximately 1%. According to the invention, cellulose itself is therefore considered a nonionic polysaccharide. A cellulose suitable for use according to the invention can have a degree of polymerization (DP), i.e., a chain length of glucopyranose units, of 10 to approximately 8000.

[0120] Microcrystalline cellulose, for example, can be used as a suitable cellulose. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of celluloses, in which only the amorphous regions of the semi-crystalline cellulose are attacked and completely dissolved. This initially results in microfine cellulose, which is then disaggregated into microcrystalline cellulose in aqueous suspension under mechanical stress.

[0121] The degree of polymerization remaining after hydrolysis (also called leveling-off polymerization degree = LODP) of microcrystalline cellulose is in the range of approximately 30-400. Therefore, microcrystalline celluloses with a degree of polymerization of 30 to 400 are particularly suitable.

[0122] For the purposes of this invention, cellulose (F-3) also includes any derivative of cellulose, i.e., the cellulose can be modified with substituents by reaction with a chemical agent and / or bear further chemical functional groups. Such chemically modified celluloses can be nonionic, cationic, and / or anionic.

[0123] A suitable cationic cellulose is marketed, for example, under the name Polymer JR® 400 by Amerchol and has the INCI name Polyquaternium-10. Another cationic cellulose bears the INCI name Polyquaternium-24 and is marketed under the trade name Polymer LM-200 by Amerchol or also Quatrisoft® LM 200. Other commercially available products include the compounds Celquat® H 100, Celquat®, and L 200. The aforementioned commercial products are preferred cationic celluloses.

[0124] Non-ionic celluloses are particularly preferred. These can be selected, for example, from the group consisting of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methylcellulose, hydroxyethyl ethylcellulose, ethylcellulose, methyl ethylcellulose, and methylcellulose. These are marketed, for example, under the brand names Culminal® and Benecel®, and Natrosol® types by companies such as Aqualon, Hercules, or Ashland.

[0125] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that it contains at least one non-ionic cellulose and / or one non-ionic cellulose derivative from the group consisting of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methylcellulose, hydroxyethyl ethylcellulose, ethylcellulose, methyl ethylcellulose, and methylcellulose. In a further explicitly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that it contains hydroxypropyl methyl cellulose (F-3).

[0126] The most suitable cellulose derivative is hydroxypropyl methyl cellulose, also known as cellulose hydroxypropyl methyl ether, which has the CAS number 9004-65-3 and is commercially available, for example, under the trade name Benecel E4M from Ashland. Dow Chemicals markets hydroxypropyl methyl cellulose under the trade name Methocel 267.

[0127] Another particularly suitable cellulose with a hydroxypropyl group is hydroxypropylcellulose, CAS No. 9004-64-2, which can be purchased from the company Hercules under the trade name Klucel H CS.

[0128] A hydroxypropylcellulose with a molecular weight of 30,000 to 50,000 g / mol, which is sold, for example, under the trade name Nisso Sl® by the company Lehmann & Voss, Hamburg, is also very suitable.

[0129] A particularly suitable cellulose with a 2-hydroxyethyl group is 2-hydroxyethylcellulose, CAS No. 9004-62-0, which can be obtained commercially from Ashland (Herkules) under the trade name Natrosol 250 HR.

[0130] A suitable ethylcellulose is marketed by Dow Chemical under the trade name Ethocel Standard 45 Industrial. This ethylcellulose has the CAS number 9004-57-3.

[0131] Suitable anionic celluloses include, for example, carboxymethyl cellulose, carboxymethyl hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate propionate carboxylate and / or their physiologically acceptable salts.

[0132] In the course of the work leading to this invention, it was found that improved coloring results could be achieved by using specific weight ratios of the cellulose and / or cellulose derivatives (F-3) contained in the dye (F) to the pigments (F-2). The uniform embedding of the pigments in the resulting film on the keratin fibers when using specific weight ratios of (F-3) to (F-2) further improved the optical color impression produced by the dye.

[0133] In a further preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the weight ratio of the cellulose and / or cellulose derivative (F-3) contained in the dyeing agent (F) to the pigments (F-2), i.e. the weight ratio (F-3) to (F-2), is 5 to 1 to 1 to 5, preferably 4 to 1 to 1 to 3, more preferably 3 to 1 to 1 to 2 and most preferably 2 to 1 to 1 to 1.

[0134] Acids in the dye

[0135] As an optional component, the dye according to the invention can also contain at least one organic and / or inorganic acid.

[0136] The addition of one or more acids can lower the pH of the dye (F), thereby partially or completely protonating the chitosan and 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. The formation of a particularly uniform film has thus also resulted in dyes with exceptionally good wash fastness. Furthermore, the presence of the acid(s) 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.

[0137] 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.

[0138] Formic acid and propanoic acid are also suitable acids.

[0139] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that the dyeing agent (F) contains one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0140] Acetic acid dissolves chitosan particularly well and leads to very thin and uniform films; therefore, a dye (F) containing acetic acid is particularly preferred.

[0141] In a further explicitly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that the dyeing agent (F) contains acetic acid.

[0142] 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 (F) was adjusted to a pH in the range of 2.0 to 7.5, preferably 2.25 to 7.0, more preferably 2.5 to 6.5, and most preferably 3.0 to 5.0.

[0143] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that the dyeing agent (F) has a pH value of 2.0 to 7.5, preferably of 2.25 to 7.0, more preferably of 2.5 to 6.5 and most preferably of 3.0 to 5.0.

[0144] Cosmetic carrier of the dye

[0145] The coloring agent (F) contains the components (F-1), (F-2) and (F-3), preferably in a cosmetic carrier, which may be water. Additionally or instead of water, the agent may also contain at least one organic solvent as a cosmetic carrier.

[0146] In a further particularly preferred embodiment, a coloring agent (F) according to the invention is therefore characterized in that it contains water as a cosmetic carrier.

[0147] In a further particularly preferred embodiment, a coloring agent (F) according to the invention is therefore characterized in that it contains as a cosmetic carrier at least one solvent from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol and / or polyethylene glycols.

[0148] In a further explicitly preferred embodiment, a coloring agent (F) according to the invention is characterized in that it contains as a cosmetic carrier - based on the total weight of the coloring agent -

[0149] - 10.0 to 50.0 wt.%, preferably 15.0 to 40 wt.% water and

[0150] - one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol and / or polyethylene glycols in a total amount of 40 to 90 wt.%, preferably 50 to 85 wt.%, particularly preferably 55 to 80 wt.%.

[0151] In this case, all the amounts of the components contained in the dye, expressed as weight percent, add up to a maximum of one hundred weight percent.

[0152] Viscosity of the dye (F)

[0153] The work carried out within the scope of this application has shown that the dye (F) can be applied particularly well to keratinous fibers when the dye (F) itself is more viscous and thus spreads well on the keratin material without dripping from the hair. Therefore, it is further preferred if the dye (F) has a viscosity of 10 to 10,000 mPas, preferably 10 to 5,000 mPas, more preferably 100 to 3,000 mPas, and most preferably 500 to 2,000 mPas (22 °C / Brookfield viscometer / spindle 4 / 20 rpm = revolutions per minute).

[0154] In a further particularly preferred embodiment, a method according to the invention for dyeing the keratin fibers or for improving the wash fastness of the dyed keratin fibers is characterized in that the post-treatment agent (N) has a viscosity of 10 to 10,000 mPas, preferably of 10 to 5,000 mPas, more preferably of 100 to 3,000 mPas and most preferably of 500 to 2,000 mPas (22 °C / Brookfield viscometer / spindle 4 / 20 rpm).

[0155] Methods for dyeing keratinous fibers

[0156] A second subject matter of the present application is a method for dyeing keratinous fibers, in particular human hair, with a dye (F) comprising the steps in the specified order: applying the dye (F) to the keratinous fibers and drying the keratinous fibers covered with the dye (F). The dye (F) has already been described in detail in the description of the first subject matter of the invention.

[0157] A second object of the present invention is therefore a method for dyeing keratinous fibers, in particular human hair, with a dye (F), wherein the dye has already been disclosed in detail in the description of the first object of the invention, and wherein the method comprises the following steps in the specified order:

[0158] - the application of the dye (F) to the keratinous fibers and

[0159] - the drying of the keratinous fibers covered with the dye (F).

[0160] The dye can be applied to the keratin fibers, for example, with a gloved hand or using a brush or applicator, and the keratin fibers can be wet or dry. After application, the dye can be spread over the keratin fibers and, if necessary, gently massaged in.

[0161] After application of the dye (F), the keratin fibers covered with the dye (F) are dried. During drying, the cosmetic carrier present in the dye (F), such as the ethanol / water mixture, evaporates, allowing the film comprising the pigment, chitosan (derivative), and cellulose (derivative) to form. Since the dye is not washed out before drying, the process according to the invention is a leave-on dyeing process.

[0162] The drying of the keratin fibers begins in principle immediately after the application of the dye, as the evaporation of the cosmetic carrier also starts at this time. Drying can occur at room temperature (i.e., without any further heat application), or it can be supported or accelerated by heat treatment of the keratin fibers.

[0163] Heat treatment of keratin fibers

[0164] The dye (F) can be applied, massaged in, and distributed onto the wet or dry keratinous fibers. After application of the dye (F), the keratinous fibers covered with the dye (F) are preferably heated to a temperature above 40 °C by mechanical means (combing or kneading). In this embodiment, the heating takes place after the application of the dye (F). Heating accelerates the evaporation of the water present in the dye (F), allowing the film consisting of pigment, chitosan (derivative), and cellulose (derivative) to form. Since the dye is not washed out before drying, the process according to the invention is a leave-on dyeing process.

[0165] Heating or heat treatment refers to the process of bringing the keratin material into contact with a heated device, or applying this heated device to or on the keratin material. 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.

[0166] 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.

[0167] Furthermore, it was found that it is preferred if the treatment temperature during the heat treatment is between 40 °C and 210 °C, preferably between 40 °C and 190 °C, more preferably between 45 °C and 170 °C, even more preferably between 45 °C and 100 °C, and most preferably between 50 °C and 80 °C. In other words, it has proven particularly preferred if the heat treatment is carried out with a device that is heated to a temperature of 40 °C to 210 °C, preferably between 40 °C and 190 °C, more preferably between 45 °C and 170 °C, even more preferably between 45 °C and 100 °C, and most preferably between 45 °C and 75 °C.

[0168] In a further particularly preferred embodiment, a method according to the invention is characterized by 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 75 °C.

[0169] 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.

[0170] 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.

[0171] During heat treatment or heating, the keratin fibers can also be combed or brushed.

[0172] For example, the keratin fibers or the hair, possibly under combs or brushes, can be treated with a hairdryer that blows warm or hot air onto the fibers. This air is preferably between 50 and 80 °C. Alternatively, the keratin material or the hair can be held under an infrared lamp, preferably set to a temperature of 50 to 80 °C. For heat treatment, hair can also be pressed between two appropriately heated plates of a flat iron, with the plates being moved along the hair fiber at the same time. The plates of the flat iron can, for example, be set to a temperature of up to 210 °C.

[0173] 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.

[0174] A third subject matter of the present application is the use of a cellulose and / or a cellulose derivative in the dye described above (F) to improve the wash stability of a dyeing on keratinous fibers.

[0175] Regarding the other preferred embodiments of the methods and uses according to the invention, what has been said about the dyes according to the invention applies mutatis mutantis. Examples

[0176] 1. Formulations

[0177] The following dyes were produced (all values, unless otherwise stated, are in wt.%):

[0178] 2. Viscosity measurement

[0179] The viscosity of the dyes prior to application was determined using a Brookfield viscometer with a spindle 4 at 20 rpm (revolutions per minute) and at 22 °C.

[0180] The dyes were applied to hair strands (Kerling company). For this purpose, 2.0 g of dye (F) per gram of hair strand was massaged in. The adhesion of the dye to the hair strands covered with the dye was assessed on a scale from 1 (very high adhesion) to 6 (very low adhesion).

[0181] Scale: 1 very high rating for the criterion (very high adhesion), 6 very low rating for the criterion (very low adhesion)

[0182] The strands dyed with dye (F1) showed poor dye adhesion. It was observed that dye (F1) was too thin and dripped from the strands. Improved dye adhesion was achieved to the same extent with dyes (F2) and (F3). Both dyes (F2) and (F3) contain a cellulose component. The use of cellulose and / or cellulose derivatives leads to improved dye adhesion to the strands.

[0183] 3. Measurement of color intensity and wash fastness

[0184] 3.1 Visual Assessment

[0185] The dyes were applied to hair strands (Kerling company). For this purpose, 2.0 g of dye (F) per gram of hair strand was massaged in and left to act for 1 minute. The strands, still coated with dye, were then dried with a standard hairdryer. The dyed strands were visually assessed by a trained person under a daylight lamp.

[0186] Following the coloring process, each dyed strand underwent two manual washes. For each wash, the strand was moistened, then a standard shampoo (Schwarzkopf, Schauma 7 Herbs) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). Afterward, the strand was rinsed with lukewarm tap water for 30 seconds and dried.

[0187] After the two hair washes, each strand was visually assessed again under the daylight lamp.

[0188] The hair strands were assessed for color intensity and uniformity on a scale of 1 (very high color intensity and uniformity) to 6 (very low color intensity and uniformity) after application of the dye (F). A further assessment was performed after two washes to evaluate wash stability on a scale of 1 (very high wash stability) to 6 (very low wash stability).

[0189] Scale: 1 very high rating for the criterion (good uniformity, good color intensity, good wash fastness), 6 very low rating for the criterion (poor uniformity, poor color intensity, poor wash fastness)

[0190] The hair strands dyed with dye (F2) exhibited the best wash fastness. Simultaneously, both improved intensity and uniformity were achieved compared to strands treated with dye (F1). Dyes (F1) and (F2) differ in the use of cellulose and / or a cellulose derivative in the formulation (F2). The improved optical properties and wash stability can be attributed to the use of hydroxypropyl methylcellulose in the dye formulation.

[0191] 3.2. Colorimetric Measurements

[0192] Hair strands (from the company Kerling) were colorimetrically measured. The dyes were then applied to the hair strands. For this, 2.0 g of dye (F) per gram of hair strand was massaged in and left to act for 1 minute. The strands, still coated with dye, were then dried with a standard hairdryer and subsequently colorimetrically measured again.

[0193] The dE value used to assess color intensity is derived from the L*a*b* color measurements taken on the respective strand as follows: dE = [ (Li - Lo) 2 + (ai - ao) 2 + (bi - bo) 2 ]i / 2

[0194] Lo, ao and bo = measured values ​​of the uncolored strand

[0195] Li, ai and bi = measured values ​​of the dyed strand

[0196] The lower the dE value, the smaller the color difference between the undyed and dyed hair. The higher the dE value, the greater the color intensity compared to the undyed strand. The following color results were obtained for strands dyed with dyes (F1) and (F3) without washing, compared to undyed strands.

[0197] HW = Hair washes

[0198] Both dyes produced very intense coloration, with dye (F3) exhibiting a higher color intensity (dE value of 56.6) than dye (F1). The formulations of dyes (F1) and (F3) differ due to the addition of ethylcellulose in dye (F3). The higher color intensity can be attributed to this addition.

[0199] To measure colorfastness, the hair strands were washed once, twice, and three times, respectively. For each wash, a standard shampoo (0.25 g of shampoo (Schauma 7 Herbs) per 1 g of hair) was applied to the strand and massaged in with the fingers for 30 seconds. The shampoo was then rinsed out under running, lukewarm water for one minute, and the hair strand was dried. This process constitutes one wash. The procedure was repeated for each subsequent wash. The hair washed in this way was then colorimetrically measured.

[0200] The dE value used to assess wash fastness is derived from the L*a*b* color measurements taken on the respective strand as follows: dE = [ (Li - Lo) 2 + (ai - ao) 2 + (bi - bo) 2 ]i / 2

[0201] Lo, ao and bo = measured values ​​of the dyed, unwashed strand

[0202] Li, ai and bi = measured values ​​of the dyed and defined washed strand

[0203] A low dE value indicates a small color difference between dyed, unwashed hair and dyed, washed hair. In other words, the lower the specific dE value, the greater (i.e., better) the wash stability of the dye.

[0204] HW = Hair washes

[0205]

[0206] After each hair wash, a lower dE value was observed for the strands colored with dye (F3) compared to strands colored with dye (F1). The difference in the formulation of (F1) to (F3) lies in the proportion of ethylcellulose within the dye (F3). The wash stability of the dye was significantly improved by the use of ethylcellulose compared to a dye without cellulose.

Claims

Patent claims 1. Dyeing agent (F) for dyeing keratinous fibers, especially human hair, comprising: (F-1) at least one chitosan and / or one chitosan derivative, (F-2) at least one pigment and (F-3) at least one cellulose and / or a cellulose derivative.

2. Dyeing agent (F) according to claim 1, characterized in that it contains at least one chitosan and / or one chitosan derivative (F-1) 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.

3. Dyeing agent (F) according to one of claims 1 to 2, characterized in that it contains - based on the total weight of the dyeing agent (F) - one or more chitosans and / or chitosan derivatives (F-1) in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.%, more preferably 0.1 to 1.5 wt.% and most preferably 0.3 to 0.9 wt.%.

4. Dyeing agent (F) according to one of claims 1 to 3, characterized in that it contains at least one inorganic pigment (F-2) 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.

5. Dyeing agent (F) according to any one of claims 1 to 4, characterized in that it contains at least one organic pigment (F-2) 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, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers C1 12085, CI 12120, C1 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.

6. Dyeing agent (F) according to one of claims 1 to 5, characterized in that it contains at least one pigment (F-2) selected from the group consisting of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

7. Dyeing agent (F) according to one of claims 1 to 6, characterized in that it contains - based on the total weight of the dyeing agent (F) - one or more pigments (F-2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.%, more preferably 0.1 to 3 wt.% and most preferably 0.2 to 1.5 wt.%.

8. Dyeing agent (F) according to any one of claims 1 to 7, characterized in that it comprises - based on the total weight of the dyeing agent (F) - one or more celluloses and / or cellulose derivatives (F-3) in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 7.5 wt.%, more preferably from 0.1 to 5 wt.% and most preferably from 0.2 to 3 wt.%.

9. Dyeing agent (F) according to any one of claims 1 to 8, characterized in that it contains at least one cellulose and / or one cellulose derivative (F-3) from the group consisting of non-ionic celluloses, cationic celluloses and anionic celluloses.

10. Dyeing agent (F) according to any one of claims 1 to 9, characterized in that it contains at least one non-ionic cellulose and / or one non-ionic cellulose derivative from the group consisting of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methylcellulose, hydroxyethyl ethylcellulose, ethylcellulose, methyl ethylcellulose and methylcellulose.

11. Dyeing agent (F) according to any one of claims 1 to 10, characterized in that it contains one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

12. Dyeing agent (F) according to one of claims 1 to 11, characterized in that it contains water and has a pH value of 2.0 to 7.5, preferably of 2.25 to 7.0, further preferably of 2.5 to 6.5 and especially preferably from 3.0 to 5.

0.

13. Dyeing agent (F) according to any one of claims 1 to 12, characterized in that the weight ratio of the cellulose and / or the cellulose derivative (F-3) contained in the dyeing agent (F) to the pigments (F-2), i.e. the weight ratio (F-3) to (F-2), is 5 to 1 up to 1 to 5, preferably from 4 to 1 to 1 to 3, more preferably from 3 to 1 to 1 to 2 and most preferably from 2 to 1 to 1 to 1.

14. Dyeing agent (F) according to any one of claims 1 to 13, characterized in that it has a viscosity of 10 to 10,000 mPas, preferably of 10 to 5,000 mPas, more preferably of 100 to 3,000 mPas and most preferably of 500 to 2,000 mPas (22 °C / Brookfield viscometer / spindle 4 / 20 rpm).

15. Method for dyeing keratinous fibers, in particular human hair, with a dye (F) according to any one of claims 1 to 14 comprising the steps in the specified order: - the application of the dye (F) to the keratinous fibers and - the drying of the keratinous fibers covered with the dye (F).

16. Method according to claim 15, characterized in that the drying takes place at 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 75 °C.

17. Use of a cellulose and / or a cellulose derivative in a dye (F) according to claims 1 to 14, to improve the wash stability of a dyeing on keratinous fibers.

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