Agent for dyeing keratin fibers, containing pigment and chitosan in certain weight ratios

Abstract

The invention relates to an agent (F) for dyeing keratin fibers, in particular human hair, containing (F-1) at least one pigment and (F-2) at least one chitosan and / or chitosan derivative, characterized in that the weight ratio of all pigments (F-1) contained in the agent to all chitosan (derivatives) (F-2) contained in the agent, i.e. the weight ratio (F-1) / (F-2), is in the range of 1.00:1.05 to 1.00:2.45.

Description

[0001] Dyeing agent for keratinous fibers containing pigment and chitosan in specific weight ratios

[0002] The subject of the present application is a dyeing agent for keratinous fibers, in particular human hair, which contains at least one pigment and at least one chitosan and / or chitosan derivative in certain weight ratios.

[0003] 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.

[0004] Altering the shape and color of keratinous 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.

[0005] 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.

[0006] For temporary color changes to hair and / or skin, the use of color pigments is well-known. 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 surface of the hair fibers and / or skin. Therefore, they can usually be removed completely without residue after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name "hair mascara." Coloring with pigments offers several significant advantages. Since the pigments only adhere to the keratin material, especially the hair fibers, unwanted colorations can be removed quickly and easily without leaving any residue, thus allowing the user to return to their original hair color immediately and without much effort.This coloring process is therefore particularly attractive for consumers who do not want to regularly re-dye their hair.

[0007] Despite these many advantages, the pigment-based dyeing system still has some disadvantages, stemming 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 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.

[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 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.

[0009] The objective of this application was therefore to discover a pigment-based dyeing process that achieves intense colorations with improved wash fastness and greater uniformity or evenness. The dyeing process should utilize biopolymers, and the keratin fibers or hair dyed using this method should not feel coated or greasy, should exhibit a healthy shine, and the elasticity of the keratin fibers should not be negatively affected.

[0010] Surprisingly, it has now been found that this problem can be solved by using a dye for coloring the keratin fibers which contains one or more pigments and one or more chitosans and / or chitosan derivatives in very specific, optimized, and coordinated weight ratios. A first object of the present invention is an agent (F) for dyeing keratinous fibers, in particular human hair, containing

[0011] (F-1) at least one pigment, and

[0012] (F-2) at least one chitosan and / or one chitosan derivative, characterized in that the weight ratio of all pigments (F-1) contained in the average to all chitosan (derivatives) (F-2) contained in the average, i.e. the weight ratio (F-1) / (F-2) is in the range of 1.00:1.05 to 1.00:2.45.

[0013] A preferred agent (F) for dyeing keratinous fibers, in particular human hair, containing

[0014] (F-1) at least one pigment, and

[0015] (F-2) at least one chitosan, characterized in that the weight ratio of all pigments (F-1) contained in the average to all chitosanes (F-2) contained in the average, i.e. the weight ratio (F-1) / (F-2) is in the range of 1.00:1.05 to 1.00:2.45.

[0016] Hair dyed with one of these agents exhibited colorations with particularly high color intensity, characterized by improved wash fastness and also by a particularly even color result.

[0017] Keratinous fibers

[0018] Keratinous fibers include hair, wool, and fur. Human hair is particularly often considered a keratinous fiber.

[0019] dyeing agents

[0020] The term "coloring agent" is used in this invention to refer to the coloring of keratin fibers, particularly hair, by the use of pigments. The agent (F) can alternatively also be referred to as a dye or coloring agent (F). During the coloring process, the pigments are deposited as color-imparting compounds in a homogeneous, uniform, and smooth film on the surface of the keratin fibers. This film is formed by the chitosans.

[0021] Pigments (F-1) in the dye (F)

[0022] The dyeing agent (F) according to the invention contains at least one pigment as its first essential component.

[0023] 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.

[0024] Particularly preferred is a composition (F) for dyeing keratinous fibers, especially human hair, comprising

[0025] (F-1) at least one pigment having a solubility in water of less than 0.5 g / L, preferably less than 0.1 g / L and particularly preferably less than 0.05 g / L and

[0026] (F-2) at least one chitosan and / or one chitosan derivative, characterized in that the weight ratio of all pigments (F-1) contained in the average to all chitosan (derivatives) (F-2) contained in the average, i.e. the weight ratio (F-1) / (F-2) is in the range of 1.00:1.05 to 1.00:2.45.

[0027] 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 coloring agent according to the invention.

[0028] In a preferred embodiment, a coloring agent (F) 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.

[0029] In a particularly 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-1).

[0030] 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.

[0031] 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).

[0032] 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.

[0033] 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).

[0034] In a further preferred embodiment, a composition according to the invention is characterized in that it contains at least one inorganic pigment (F-1) 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.

[0035] In a further preferred embodiment, a coloring agent (F) 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). 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.

[0036] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise:

[0037] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0038] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0039] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0040] Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0041] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0042] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0043] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0044] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0045] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0046] Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0047] Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)

[0048] Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)

[0049] Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)

[0050] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510)

[0051] Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0052] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0053] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0054] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

[0055] Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0056] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0057] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0058] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0059] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0060] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0061] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0062] 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) Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0063] Other particularly preferred color pigments with the trade name Xirona® include, for example:

[0064] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0065] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0066] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0067] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0068] In addition, particularly preferred color pigments with the trade name Unipure® include, for example:

[0069] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0070] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0071] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0072] In a further embodiment, the dyeing agent (F) according to the invention can also contain one or more organic pigments.

[0073] 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.

[0074] 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.In a further particularly preferred embodiment, a composition (F) according to the invention is characterized in that it contains at least one organic pigment (F-1) 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.

[0075] 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.

[0076] For example, alizarin lacquer can be used as a colored lacquer.

[0077] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the colorant (F) 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 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).

[0078] 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.

[0079] In a further preferred embodiment, a composition 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. 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 ranges for the thickness of 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 a thickness that is as uniform as possible. Due to the thinness of the substrate platelets, the pigment exhibits particularly high opacity.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] The substrate plates can be made from any material that can be formed into platelet form.

[0084] They can be of natural origin or synthetically produced. Materials from which the substrate platelets can be composed 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 platelets are composed of metal (alloys). Any metal suitable for metallic luster pigments is suitable. 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 platelets and brass platelets, with aluminum substrate platelets being particularly preferred.

[0085] Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0090] 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 colorants. Suitable pigments based on a lamellar substrate platelet include, for example, the VISIONAIRE series pigments from Eckart.

[0091] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from the company Schlenk Metallic Pigments GmbH.

[0092] 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.

[0093] The pigment(s) (F-1) constitute the first essential component of the dye (F) according to the invention and are preferably used in specific average quantities. Particularly good results were obtained when the dye (F) contained 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.%.

[0094] 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-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.%.

[0095] Chitosans (F-2) in the dye (F)

[0096] As a second essential component, the dye according to the invention (F) contains at least one chitosan or a derivative of chitosan (F-2).

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] In a further particularly preferred embodiment, a dyeing agent (F) 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.

[0102] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from the company Sigma Aldrich, for example.

[0103] 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%.

[0104] 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.

[0105] Chitosan 027 is a suitable, commercially available, high-molecular-weight chitosan from Polymar, possessing a molecular weight of 100,000 to 2,000,000 g / mol. It has proven particularly advantageous when the dye according to the invention contains the chitosans and / or chitosane derivatives (F-2) in specific 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 0.11 to 7.35 wt.%, preferably 0.16 to 4.90 wt.%, more preferably 0.21 to 3.70 wt.%, and most preferably 0.27 to 1.20 wt.%.

[0106] 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 (F) – one or more chitosans and / or chitosan derivatives (F-2) in a total amount of 0.11 to 7.35 wt.%, preferably 0.16 to 4.90 wt.%, more preferably 0.21 to 3.70 wt.%, and most preferably 0.27 to 1.20 wt.%.

[0107] Weight ratio (F-1) / (F-2)

[0108] Particularly important with regard to achieving improved wash fastness and a particularly uniform coloring is the optimally adjusted weight ratio of pigment(s) (F-1) to chitosan(derivatives) (F-2) in the dye.

[0109] In other words, it is essential to the invention that the total amount of all pigments (F-1) contained in the dye is in a specific weight ratio to the total amount of chitosans and chitosan derivatives (F-2) contained in the dye.

[0110] The theory developed based on the experiments conducted suggests that the pigments used, due to their insolubility, do not diffuse into the keratin fiber, but rather accumulate on the fiber's surface and are incorporated there into the film formed by the chitosan (and / or chitosan derivatives). When the pigments and chitosans were used in the optimal weight ratio, the film was particularly intensely colored, yet still resistant to external influences.

[0111] In principle, the more pigments are incorporated into the chitosan film, the more intensely colored it is. However, it has also been found that an excessive amount of pigment in the film can impair its elasticity and adhesion to the fiber surface, resulting in either brittleness or poorer adhesion to the fiber, leading to faster washing off. Due to the partial detachment of the film, an uneven color result was also observed.

[0112] It was particularly surprising that, with the optimal adjustment of the weight ratio (F-1) / (F-2), improved color intensity, greater homogeneity of the dyeing, and better wash fastness were observed. It was found that the chitosan derivatives (F-2) must be used in a slight excess by weight compared to the pigments (F-1) to achieve these results. However, the excess of chitosan must not be too large.

[0113] The composition according to the invention is therefore characterized in that the weight ratio of all pigments (F-1) contained in the composition to all chitosan (derivatives) (F-2) contained in the composition, i.e. the weight ratio (F-1) / (F-2), is in the range of 1.00:1.05 to 1.00:2.45.

[0114] With a weight ratio (F-1) / (F-2) of 1.00:1.05, the chitosans (F-2) are used in a 1.05-fold weight excess compared to the pigments (F-1). A colorant with a pigment content (F-1) of 1.00 wt% then contains 1.05 wt% chitosan(s) (F-2).

[0115] With a weight ratio (F-1) / (F-2) of 1.00:2.45, the chitosans (F-2) are used in a 2.45-fold excess weight compared to the pigments (F-1). A dye with a pigment content (F-1) of 1.00 wt% therefore contains 2.45 wt% chitosans (F-2). Similarly, a dye with a pigment content (F-1) of 0.4 wt% contains the chitosans (F-2) in an amount of 0.98 wt%.

[0116] Furthermore, it was found that the application-related properties improved continuously as the weight ratio (F-1) / (F-2) approached a value in the range of 1.00:1.40 to 1.00:2.30.

[0117] When the dye (F) contained the pigment(s) (F-1) and chitosans (F-2) in a weight ratio of 1.00:1.40 to 1.00:2.30, the observed color intensity, wash fastness, and uniformity of coloration were at their best.

[0118] For these reasons, the weight ratio of all pigments (F-1) contained in the average to all chitosan (derivatives) contained in the average (F-2), i.e., the weight ratio (F-1) / (F-2), is preferably in the range of 1.00:1.10 to 1.00:2.35, more preferably from 1.00:1.20 to 1.00:2.35, even more preferably from 1.00:1.30 to 1.00:2.30 and most preferably from 1.00:1.40 to 1.00:2.30.

[0119] In a further explicitly preferred embodiment, the dyeing agent (F) according to the invention is characterized in that the weight ratio of all pigments (F-1) contained in the mixture to all chitosan (derivatives) (F-2) contained in the mixture, i.e. the weight ratio (F-1) / (F-2), is in the range of 1.00:1.10 to 1.00:2.35, preferably from 1.00:1.20 to 1.00:2.35, more preferably from 1.00:1.30 to 1.00:2.30 and most preferably from 1.00:1.40 to 1.00:2.30. In a further explicitly preferred embodiment, the dyeing agent (F) according to the invention is characterized in that the weight ratio of all pigments (F-1) contained in the agent to all chitosans (F-2) contained in the agent, i.e.the weight ratio (F-1) / (F-2) is in the range of 1.00:1.10 to 1.00:2.35, preferably from 1.00:1.20 to 1.00:2.35, more preferably from 1.00:1.30 to 1.00:2.30 and most preferably from 1.00:1.40 to 1.00:2.30.

[0120] With a weight ratio (F-1) / (F-2) of 1.00:1.40, the chitosans (F-2) are used in a 1.40-fold excess by weight compared to the pigments (F-1). A colorant with a pigment content (F-1) of 1.00 wt% therefore contains 1.40 wt% chitosan(s) (F-2).

[0121] With a weight ratio (F-1) / (F-2) of 1.00:2.30, the chitosans (F-2) are used in a 2.30-fold excess weight compared to the pigments (F-1). A colorant with a pigment content (F-1) of 1.00 wt% therefore contains 2.30 wt% chitosan(s) (F-2).

[0122] It is most preferred if the chitosans (F-2) in the dye (F) are used in a 1.4- to 2.3-fold excess by weight compared to the pigments (F-1). Organic and / or inorganic acids (F-3) in the dye

[0123] As an optional component, the dyeing agent (F) according to the invention may contain at least one organic and / or inorganic acid (F-3).

[0124] The use 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) (F-3) 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.

[0125] 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.

[0126] Formic acid and propanoic acid are also suitable acids (F-3). In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that it contains one or more organic acids (F-3) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0127] Acetic acid dissolves chitosan particularly well and leads to very thin and uniform films; therefore, a dye (F) containing acetic acid is particularly preferred.

[0128] In a further explicitly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that it contains acetic acid (F-3).

[0129] 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) 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.

[0130] In a further particularly preferred embodiment, a dyeing agent (F) 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.

[0131] Cosmetic carrier of the dye (F)

[0132] The coloring agent (F) contains the essential ingredients (F-1) and (F-2) as well as the optionally present acids (F-3) in a cosmetic carrier, particularly preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. Such carriers can be, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations suitable for application to the hair.

[0133] Particularly good results were obtained when the cosmetic carrier was a solvent-based system. Solvents selected from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol, and polyethylene glycol, particularly preferably ethanol, are especially suitable for solving the problem described in the invention.

[0134] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is therefore characterized in that it contains at least one solvent (F-4) other than water from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, particularly preferably ethanol.

[0135] The experiments carried out have shown that ethanol is particularly compatible with pigments or chitosans and also with acetic acid; therefore, the use of ethanol in the dye (F) is particularly preferred.

[0136] Ethanol has the Cas number 64-17-5.

[0137] Isopropanol is also alternatively called 2-propanol and has the CAS number 67-63-0.

[0138] 1,2-Propylene glycol is also alternatively referred to as 1,2-propanediol and bears the CAS numbers 57-55-6 [(RS)-1,2-Dihydroxypropane], 4254-14-2 [(R)-1,2-Dihydroxypropane] and 4254-15-3 [(S)-1,2-Dihydroxypropane],

[0139] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0140] Glycerin is also alternatively known as 1,2,3-propanetriol and has the CAS number 56-81-5. 1-Butanol can also be called n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0141] Phenoxyethanol has the Cas number 122-99-6.

[0142] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0143] Polyethylene glycols according to the present invention are preferably polymers of the general molecular formula C2nH4n+2O that are liquid at room temperature (25 °C). n +i . The repeating unit of the linearly structured polymer is (-CH2-CH2-O-), with a molar mass of approximately 44 g mol -1 Chemically, it is a polyether. Polyethylene glycols are therefore understood to be ethylene glycols of the formula (EG). where x represents an integer from 2 to 10000, preferably an integer from 2 to 1000, and most preferably an integer from 2 to 200.

[0144] The solvent(s) are preferably used in certain quantity ranges in the dye (F).

[0145] Particularly uniform and resistant colorations could be achieved when the dye – based on its total weight – contained one or more solvents other than water (F-4) in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0146] 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 solvents (F-4) other than water in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0147] 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 solvents (F-4) other than water from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0148] In a further 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) - 20 to 95 wt. %, preferably 30 to 90 wt. %, further preferably 40 to 85 wt. %, and most preferably 50 to 80 wt. %, ethanol.

[0149] Another preferred dye (F) is also characterized in that it contains - based on the total weight of the dye (F) - 20 to 95 wt.%, preferably 30 to 90 wt.%, further preferably 40 to 85 wt.% and most preferably 50 to 80 wt.% isopropanol.

[0150] In another particularly suitable embodiment, the solvent(s) (F-4) together with water form the cosmetic carrier. Since the solvent content is particularly preferably relatively high, in the range of 50 to 80 wt.%, it is advantageous to reduce the water content accordingly. The coloring agent (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-5). The quantities of water given here are based on the total weight of the coloring agent.

[0151] 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 – ​​5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.%, and most preferably 20 to 40 wt.% water (F-5). The proportion of components (F-1), (F-2), (F-3), (F-4), and (F-5) in the dyeing agent is shown below.

[0152] 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.

[0153] It was found that the films produced with the dye (F) were particularly thin, uniform, and stable when the dye consisted largely of components (F-1), (F-2), (F-3), (F-4), and (F-5). 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), and (F-5) are present together in the dye (F) in a proportion of at least 90.0 wt.%, preferably at least 93 wt.%, further preferably at least 96 wt.%, even more preferably at least 99 wt.%, and most preferably at least 99.7 wt.%.

[0154] If components (F-1), (F-2), (F-3), (F-4) and (F-5) together constitute at least 90.0% by weight in the dye, then the dye consists – based on its total weight – of at least 90% by weight of components (F-1), (F-2), (F-3), (F-4) and (F-5). In other words, in this case, other substances or ingredients different from (F-1) to (F-5) are present in the dye (F) only in a maximum quantity of 10% by weight, most preferably a maximum of 0.3% by weight.

[0155] Particularly preferably, the coloring agent (F) consists essentially of pigments (F-1), chitosan (F-2), acids (F-3), a solvent other than water (F-4) (most preferably ethanol) and water (F-5).

[0156] In a further preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the components (F-1), (F-2), (F-3), (F-4) and (F-5) are together contained in the dyeing agent (F) in a quantity of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.%.

[0157] In a further explicitly preferred embodiment, a coloring agent (F) according to the invention is characterized in that it comprises at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.% of

[0158] (F-1) one or more pigments,

[0159] (F-2) one or more chitosans and / or chitosane derivatives,

[0160] (F-3) one or more 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,

[0161] (F-4) one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, and

[0162] (F-5) Water exists.

[0163] In a further explicitly preferred embodiment, a coloring agent (F) according to the invention is characterized in that it comprises at least 90.0 wt.%, preferably at least 93 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 pigments, (F-2) one or more chitosans,

[0164] (F-3) one or more 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,

[0165] (F-4) one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, and

[0166] (F-5) Water exists.

[0167] Direct dyes in the dyeing agent (F)

[0168] In principle, the colorants (F) used in the process according to the invention can also contain one or more direct dyes as optional components. Direct dyes are dyes that adhere directly to the hair and do not require an oxidative process to form the color. Typical direct dyes are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0169] The direct 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 dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 1.0 g / L. It may be preferred if the dye (F) does not contain any direct dyes or contains them only in very small amounts.

[0170] In a further, particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the total amount of direct dyes contained in the dyeing agent (F) - based on the total weight of the dyeing agent (F) - is below 0.1 wt.%, preferably below 0.05 wt.%, more preferably below 0.01 wt.% and most preferably below 0.001 wt.%.

[0171] In other words, in a further particularly preferred embodiment, a dyeing agent (F) according to the invention is characterized in that the total amount of the direct dyes contained in the dyeing agent (F) – based on the total weight of the dyeing agent (F) – is below 0.1 wt.%, preferably below 0.05 wt.%, more preferably below 0.01 wt.% and most preferably below 0.001 wt.%, wherein the direct dyes are characterized in that they have a solubility in water (760 mmHg) at 25 °C of more than 0.5 g / L.

[0172] In a further, particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) is free of direct dyes.

[0173] Direct-drawing dyes can be divided into anionic, cationic, and nonionic direct-drawing dyes.

[0174] 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.

[0175] 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-dinitro- phenol, 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-naphtho- chinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitro- benzoesäure und 2-Chlor-6-ethylamino-4-nitrophenol.

[0176] Anionic direct-drawing dyes are also known as acid dyes. Acid dyes are defined as direct-drawing dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH, the rudimentary forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups exist in equilibrium with their deprotonated forms (-COO-, -SCh). The proportion of rudimentary forms increases with decreasing pH. When direct-drawing dyes are used in the form of their salts, the carboxylic acid or sulfonic acid groups exist 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 potassium salts.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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, Cl 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (C.l. 16230; Orange G sodium salt), Acid Orange 11 (Cl 45370), Acid Orange 15 (Cl 50120), Acid Orange 20 (Cl 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.1.14720), Acid Red 18 (E124, Red 18; Cl 16255), Acid Red 27 (E 123, Cl 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, Cl 17200), Acid Red 35 (Cl C.l.18065), Acid Red 51 (Cl 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (Cl 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (Cl 27290), Acid Red 87 (Eosin, Cl 45380), Acid Red 92 (COLIPA n° C53, Cl 45410), Acid Red 95 (Cl 45425, Erythtosine.Simacid Erythrosine Y), Acid Red 184 (Cl 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.l. 60730, COLIPA n° C063), Acid Violet 49 (Cl 42640), Acid Violet 50 (Cl 50325), Acid Blue 1 (Patent Blue, Cl 42045), Acid Blue 3 (Patent Blau V, Cl 42051), Acid Blue 7 (Cl 42080), Acid Blue 104 (Cl 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, Cl 42090, C.l.Food Blue 2), Acid Blue 62 (Cl 62045), Acid Blue 74 (E 132, Cl 73015), Acid Blue 80 (Cl 61585), Acid Green 3 (Cl 42085, Foodgreenl), Acid Green 5 (Cl 42095), Acid Green 9 (C.1.42100), Acid Green 22 (C.1.42170), Acid Green 25 (Cl 61570, Japan Green 201 , D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, C.l. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401 , Naphthalene Black 10B, Amido Black 10B, Cl 20 470, COLIPA n° B15), Acid Black 52 (Cl 15711), Food Yellow 8 (Cl 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 .

[0181] The water solubility of anionic direct-acting dyes can be determined, for example, as follows. 0.1 g of the anionic direct-acting dye is placed in a beaker. A magnetic stir bar is added. Then, 100 ml of water is added. This mixture is heated to 25 °C on a magnetic stirrer while stirring. Stirring continues for 60 minutes. The aqueous mixture is then visually inspected. If undissolved dye remains, the amount of water is increased—for example, in 10 ml increments. Water is added until the dye is completely dissolved. If the dye-water mixture cannot be visually inspected due to the high intensity of the dye, the mixture is filtered. If some undissolved dye remains on the filter paper, the solubility test is repeated 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.

[0182] 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).

[0183] 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). 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).

[0184] 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.

[0185] 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).

[0186] 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.%.

[0187] 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).

[0188] 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).

[0189] Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a water solubility of more than 20 wt% (25 °C).

[0190] Viscosity of the dye (F)

[0191] The work carried out within the scope of this application has shown that particularly thin films could be formed even when the dye (F) itself was low in viscosity and spread quickly and with good spreading properties on the keratin material. Therefore, it is further preferred that 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 100 to 2,000 mPas (22 °C / Brookfield viscometer / spindle 4 / 20 rpm = revolutions per minute).

[0192] In a further particularly preferred embodiment, a dyeing agent (F) according to the invention is 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).

[0193] Methods for dyeing keratinous fibers

[0194] The dye (F) is used in processes for dyeing keratinous fibers, especially human hair.

[0195] A second subject matter of the present application is therefore a method for dyeing keratinous fibers, in particular human hair, in which a dye (F), disclosed in detail in the description of the first subject matter of the invention, is applied to the keratinous fibers and optionally rinsed off after a reaction time. The application of the dye to the keratin fibers can be carried out, for example, with a gloved hand or using a brush or applicator. After application, the dye can be spread over the keratin fibers and optionally lightly massaged in.

[0196] 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.

[0197] 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.

[0198] A method for dyeing keratinous fibers, especially human hair, is therefore particularly preferred, comprising

[0199] - the application of a dye (F), as disclosed in detail in the description of the first subject matter of the invention, to the keratinous fibers, and

[0200] - 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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 particularly preferred at a temperature of 40 to 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.

[0206] 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.

[0207] During heat treatment or heating, the keratin fibers can also be combed or brushed.

[0208] 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.

[0209] 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.

[0210] 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

[0211] 1. Formulations

[0212] The following dyes were produced (all values, unless otherwise stated, are in wt.%):

[0213] V = Comparison E = Invention

[0214] 2. Application to strands

[0215] The dyes were applied to strands of hair (Kerling brand). For this, 2.0 g of dye (F) 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.

[0216] 3. Measurement of color intensity, homogeneity and wash fastness

[0217] The strands dried in this way were visually assessed by a trained person under a daylight lamp. The color intensity and the evenness of the coloring were rated using school grades (1 = very high color intensity or very even coloring; 6 = very weak color intensity or very uneven coloring).

[0218] Following this, each dyed strand underwent three 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). Afterwards, the strand was rinsed with lukewarm tap water for 30 seconds and dried.

[0219] After three washes, each strand was visually assessed again under a daylight lamp. The washed hair strands were then evaluated for color intensity on a scale from 1 (very good wash fastness) to 6 (very poor wash fastness).

[0220] 1 = very high intensity 6 = very low intensity

[0221] 1 = very good homogeneity 6 = very low homogeneity

[0222] 1 = very good wash fastness 6 = very poor wash fastness

[0223] The hair strands that were dyed with the dyes (F4), (F5) and (F6) had the highest color intensity and possessed the greatest homogeneity and the best wash fastness.

Claims

Patent claims 1. Agent (F) for dyeing keratinous fibers, especially human hair, containing (F-1) at least one pigment, and (F-2) at least one chitosan and / or one chitosan derivative, characterized in that the weight ratio of all pigments (F-1) contained in the mixture to all chitosan (derivatives) (F-2) contained in the mixture, i.e. the weight ratio (F-1) / (F-2), is in the range of 1.00:1.05 to 1.00:2.

45.

2. Dyeing agent (F) according to claim 1, 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.

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 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.%.

4. Dyeing agent (F) according to any one of claims 1 to 3, 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.

5. Dyeing agent (F) according to one of claims 1 to 4, characterized in that it contains - based on the total weight of the dyeing agent (F) - one or more chitosans and / or chitosan derivatives in a total amount of 0.11 to 7.35 wt.%, preferably 0.16 to 4.9 wt.%, more preferably 0.21 to 3.7 wt.%, and most preferably 0.27 to 1.20 wt.%.

6. Dyeing agent (F) according to any one of claims 1 to 5, characterized in that the weight ratio of all pigments (F-1) contained in the mixture to all chitosan (derivatives) (F-2) contained in the mixture, i.e. the weight ratio (F-1) / (F-2), is in the range of 1.00:1.10 to 1.00:2.35, preferably from 1.00:1.20 to 1.00:2.35, more preferably from 1.00:1.30 to 1.00:2.30 and most preferably from 1.00:1.40 to 1.00:2.

30.

7. Dyeing agent (F) according to one of claims 1 to 6, characterized in that it contains one or more organic acids (F-3) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

8. Dyeing agent (F) according to any one of claims 1 to 7, 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.

9. Dyeing agent (F) according to any one of claims 1 to 8, characterized in that it contains at least one solvent (F-4) other than water from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, particularly preferably ethanol.

10. Dyeing agent (F) according to one of claims 1 to 9, characterized in that it contains - based on the total weight of the dyeing agent - one or more solvents (F-4) other than water in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

11. Dyeing agent (F) according to one of claims 1 to 10, characterized in that it contains - based on the total weight of the dyeing agent - 5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water (F-5).

12. Dyeing agent (F) according to any one of claims 1 to 11, characterized in that the components (F-1), (F-2), (F-3), (F-4) and (F-5) are together contained in the dyeing agent (F) in a quantity of at least 90.0 wt.%, preferably at least 93 wt.%, further preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.7 wt.%.

13. Dyeing agent (F) according to any one of claims 1 to 12, 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).

14. Method for dyeing keratinous fibers, in particular human hair, in which a dye (F) according to one of claims 1 to 13 is applied to the keratinous fibers and optionally rinsed off after an exposure time.

15. The method according to claim 14 comprising - the application of a dye (F) 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.

16. Method according to one of claims 14 to 15, characterized in that the keratin fibers are combed or brushed during the heat treatment.

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