Method for dyeing keratin fibers, comprising the use of a dye containing chitosane and a dyeing compound, and the use of an aftertreatment agent containing protein hydrolysate and / or amino acid

Abstract

The present invention relates to a method for dyeing keratin fibers, in particular human hair, comprising (1) the use of a dye (F) on the keratin fibers, at least containing (F-1) a chitosane and / or a chitosane derivative, and (F-2) at least a dyeing compound of the group of pigments and direct dyes, and (2) the use of an aftertreatment agent (N) on the keratin fibers, containing (N-1) at least a protein hydrolysate and / or an amino acid.

Description

[0001] A method for coloring keratin fibers, comprising the application of a colorant containing chitosan and color-providing compound and the application of a post-treatment agent containing protein hydrolysate and / or amino acid

[0002] The present application relates to a method for dyeing keratin fibers, in particular human hair, which comprises the application of a dye (F) and the application of a post-treatment agent (N). The dye (F) contains at least one chitosan (F-1) and at least one colorant compound (F-2) from the group of pigments and direct dyes. The post-treatment agent (N) contains at least one protein hydrolysate and / or at least one amino acid.

[0003] A second subject matter of the present application is a multi-component packaging unit (kit-of-parts) which contains the previously described colorant (F) and the aftertreatment agent (N) in separately packaged containers.

[0004] A third subject matter of this application is the use of the above-described after-treatment agent (N) for improving the color retention of a colorant (F) on keratin fibers.

[0005] Altering the shape and color of keratin fibers, especially human hair, represents an important area of ​​modern cosmetics. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intense colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by very long-lasting coloring results.

[0006] When using direct dyes, the fully formed pigments diffuse from the dyeing agent into the hair fiber. Compared to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. Colorations with direct dyes typically remain on the hair for between 5 and 20 washes. Color pigments are known to be used for short-term color changes on the hair and / or skin. Pigments or color pigments are generally understood to be insoluble, color-imparting substances. These are present undissolved in the form of small particles in the coloring formulation and are merely deposited externally on the hair fibers and / or the skin surface. Therefore, they can usually be removed completely after several washes with detergents containing surfactants.Various products of this type are available on the market under the name hair mascara.

[0007] Coloring with pigments offers several significant advantages. Because the pigments only attach to the keratin material, especially the hair fibers, from the outside, unwanted coloring can be removed quickly and easily without leaving any residue, thus offering the user the opportunity 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 touch up their hair regularly.

[0008] Despite these many advantages, the pigment-based coloring system also has some disadvantages, which are due to the pigments' limited penetration into the keratin material. Since the pigments do not diffuse into the keratin fibers, but rather merely deposit themselves on the outer surface of the fiber in the form of a shell or film, the washfastness of the colorations produced with this system still requires improvement. Various studies have attempted to bond the pigment(s) more permanently to the hair surface using film-forming materials, usually polymers.

[0009] For example, DE 19847883 A1 deals with the realization of pigment-based colorings using colorants containing at least one chitosan and one pigment. Combining the pigments with chitosan is intended to improve the abrasion resistance of the colorings. The major advantage of chitosans as film-forming materials is that they are based on biopolymers and therefore have improved ecological compatibility and degradability. As many users show increasing interest in products made from sustainable or renewable raw materials, the use of biopolymers is increasingly gaining attention.

[0010] In further studies described in JP2001089335 A, hair was dyed with a combination of polysaccharides, chitosans, and coloring compounds. In this case, acid dyes were used as the coloring compounds, not pigments. Acid dyes are typically used in combination with solvents to achieve sufficiently high color intensity, as the solvents enhance the penetration of the acid dyes into the hair fiber. However, acid dyes are also known to have a very strong skin coloring effect. In the presence of solvents, this skin coloring is often further intensified. The colorations obtained with pigment / dye and chitosan still have disadvantages with regard to their washfastness.Achieving even coloring over the entire length of the hair cannot yet be described as optimal, since the durability of the films can vary on different sections of the hair, especially in the areas at the roots and tips.

[0011] The object of the present application was therefore to provide a dye that binds color-imparting compounds to the surface of keratin fibers via a film, allowing for intensive colorings with improved washfastness. The dyeing should be achieved with the aid of biopolymers, and the keratin fibers or hair colored in this way should not feel coated or greasy and should exhibit a well-groomed shine. The curl behavior of the keratin fibers should also not be negatively affected.

[0012] At the same time, the dyes should have as little skin staining as possible. When used in a dyeing process, they should achieve intensive dyeing results with good fastness properties, especially good washfastness, and good color retention.

[0013] Surprisingly, it has now been found that keratin fibers that were colored in a first step by applying a colorant containing chitosan and pigment or dye are characterized by improved wash fastness, especially when a post-treatment agent containing at least one protein hydrolysate and / or one amino acid is applied in a subsequent step.

[0014] A first subject of the present invention is a process for dyeing keratin fibers, in particular human hair, comprising the

[0015] (1) Application of a coloring agent (F) on the keratin fibers, which contains

[0016] (F-1) at least one chitosan and / or a chitosan derivative, and

[0017] (F-2) at least one coloring compound from the group of pigments and direct dyes,

[0018] (2) Application of a post-treatment agent (N) to the keratin fibers, which contains

[0019] (N-1) at least one protein hydrolysate and / or at least one amino acid.

[0020] In step (1) of the method according to the invention, the colorant containing chitosan (F-1) and the color-imparting compound (F-2) is applied to the keratin fibers. The subsequent application (2) following step (1) comprises the application of the after-treatment agent (N), which contains at least one protein hydrolysate and / or one amino acid (N-1). If the colorant is applied as a rinse-off product and is washed out again after coloring, the after-treatment agent (N) according to the invention can be used to wash out the colorant. In this case, only a period of minutes to a few hours elapses between steps (1) and (2). If the after-treatment agent also contains one or more surfactants in addition to the amino acid or protein hydrolysate, the user can also perform subsequent hair washes with this after-treatment agent.

[0021] If the colorant (F) is applied as a leave-on product, the aftertreatment agent (N) can be used directly after coloring. In this case, the aftertreatment agent (N) is preferably applied to the keratin fibers still covered with the colorant, and both agents are then dried together. In another embodiment, the aftertreatment agent (N) can also be applied several hours or days after the application of the colorant (F) to the keratin fibers, for example when the hair is to be washed for the first time after coloring. In this embodiment, the aftertreatment agent (N) then preferably also contains at least one surfactant. The hair colored or colored and washed using this process is characterized by colorations with particularly good washfastness, a soft feel and shine.

[0022] Keratin fibers

[0023] Keratin fibers include wool, fur, and feathers, and especially human hair. Human hair is particularly preferred as a keratin fiber.

[0024] Coloring agents

[0025] In the context of this invention, the term "coloring agent" refers to the coloring of keratin material, particularly hair, achieved through the use of pigments and / or direct dyes. In this coloring process, the coloring compounds are integrated into the chitosan, which is deposited on the surface of the keratin material or surrounds the keratin fiber in the form of a particularly homogeneous, thin, uniform, and smooth film.

[0026] Application of the colorant (F) to keratin fibers

[0027] In step (1) of the dyeing process according to the invention, a dyeing agent (F) is applied to the keratin fibers or the human hair, which contains at least one

[0028] Chitosan and / or a chitosan derivative (F-1) and at least one colorant (F-2) from the group of pigments and direct dyes. The colorant (F) is a ready-to-use colorant.

[0029] When applying the colorant (F), it can be applied to the keratin fibers, for example, with a gloved hand or with the aid of a brush or applicator, and gently massaged in if necessary. Chitosans (F-1) in the colorant (F)

[0030] As a first essential component, the colorant (F) used in the process according to the invention contains at least one chitosan or a derivative of chitosan (F-1).

[0031] Chitosan, also known as polyglusam, poly-D-glucosamine, or polyglucosamine, is a naturally occurring biopolymer derived from chitin, which is composed of ß-1,4-glycosidically linked N-acetylglucosamine residues (more precisely, 2-acetamido-2-deoxy-ß-D-glucopyranose residues), and is thus, like chitin, a polyaminosaccharide. To produce chitosan, chitin is deacetylated, so that the molecule ultimately consists only of linearly linked 2-amino-2-deoxy-ß-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4.

[0032] Chitosan is preferably produced from the chitin found in shellfish or crustaceans. Chitosan is obtained industrially from chitin by deacetylation. This can be achieved, for example, using (hot) sodium hydroxide solution or enzymatically. Both processes are used industrially, but the alkaline procedure is clearly the most widely used. The degree of resulting deacetylation can vary: deacetylation can be complete or partial, resulting in a distribution of highly deacetylated regions alongside less deacetylated regions, or a homogeneous deacetylation distribution. At the same time, this chemical intervention can decrease the chain length of the polymer (depolymerization). The molecular weight of chitosan can vary over a wide range, for example, from 20,000 to approximately 5 million g / mol.

[0033] Chitosan derivatives are compounds with a chitosan base structure in which at least some of the functional groups present have been chemically modified. Chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure.

[0034] For example, a chitosan with a molecular weight of 20,000 to 800,000 g / mol, 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 is very suitable.

[0035] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan and / or a 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 very particularly preferably of 100,000 to 300,000 g / mol. In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan (F-1) having 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 very particularly preferably of 100,000 to 300,000 g / mol.

[0036] A chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially, for example, from Sigma Aldrich.

[0037] A chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Daltons) is commercially available in pharmaceutical grade from BioLog Heppe (Kraeber), for example. The degree of deacetylation of this chitosan is 88-95%.

[0038] Another low-molecular chitosan with a molecular weight of approximately 70,000 g / mol, which also bears the CAS number 9012-76-4, can be purchased commercially from Fluka as deacetylated chitin in the form of a white solid.

[0039] Chitosan in the form of its hydrochloride can be purchased as vegan chitosan from Sandream Impact. The chitosan hydrochloride is a chitosan derivative according to the invention.

[0040] Chitosan 027 is a suitable, commercially available, high-molecular chitosan from Polymar, which has a molecular weight of 100,000 - 2,000,000 g / mol.

[0041] It has proven particularly advantageous if the colorant (F) according to the invention contains the chitosans and / or chitosan derivatives (F-1) in specific amounts. Particularly good results were obtained when the colorant—based on the total weight of the colorant—contained one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.2 to 8.0 wt.%, more preferably 0.5 to 6.0 wt.%, and most preferably 0.7 to 2.5 wt.%.

[0042] In a further particularly preferred embodiment, an inventive

[0043] A process characterized in that the colorant (F) contains - based on the total weight of the colorant (F) - one or more chitosans and / or chitosan derivatives (F-1) in a total amount of 0.1 to 10.0 wt. %, preferably 0.2 to 8.0 wt. %, more preferably 0.5 to 6.0 wt. % and most preferably 0.7 to 2.5 wt. %. Color-providing compounds (F-2) in the colorant (F) As a second essential constituent, the colorant (F) used in step (1) of the process according to the invention contains at least one color-providing compound (F-2) from the group of pigments and direct dyes.

[0044] Pigments in the sense of the present invention are understood to be color-imparting compounds which have a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0.05 g / L. The water solubility can be determined, for example, using the method described below: 0.5 g of the pigment is weighed into a beaker. A stirring 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 present in finely dispersed form, the mixture is filtered.If a portion of undissolved pigment remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0045] Suitable color pigments can be of inorganic and / or organic origin. In a preferred embodiment, a method according to the invention is characterized in that the aftertreatment agent is applied to keratin material that has been colored by applying at least one inorganic and / or organic pigment.

[0046] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ochre, umber, green earth, burnt sienna, or graphite, for example. 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.

[0047] 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), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), and / or carmine (cochineal).

[0048] Also particularly preferred color pigments according to the invention are colored pearlescent pigments. These are typically based on mica and / or mica and can be coated with one or more metal oxides. Mica belongs to the class of layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0049] As an alternative to natural mica, synthetic mica, optionally coated with one or more metal oxides, can also be used as a pearlescent pigment. Particularly preferred 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 varying the layer thickness of the metal oxide(s).

[0050] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least inorganic pigment (F-2), which is preferably selected from the group 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 mica, which are coated with at least one metal oxide and / or one metal oxychloride.

[0051] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment which is selected from mica- or mica-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), ultramarines (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).

[0052] Examples of particularly suitable color pigments are commercially available 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.

[0053] Particularly preferred color pigments with the trade name Colorona® are, for example:

[0054] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0055] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0056] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0057] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0058] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, Cl 77499 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE)

[0059] Colorona Blackstar Blue, Merck, Cl 77499 (IRON OXIDES), MICA

[0060] Colorona Patagonian Purple, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE), Cl 77510 (FERRIC FERROCYANIDE)

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

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

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

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

[0065] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 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)

[0079] Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

[0080] Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0081] Weiterhin besonders bevorzugte Farbpigmente mit der Handelsbezeichnung Xirona® sind beispielsweise:

[0082] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0083] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0084] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0085] Xirona Magie Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide. Other particularly preferred color pigments with the trade name Unipure® include:

[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 applied colorant may also contain one or more organic pigments.

[0090] The organic pigments according to the invention are correspondingly insoluble, organic dyes or lakes which can be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0091] Particularly suitable organic pigments are, 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 1 1725, 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.

[0092] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic pigment (F-2) which is 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 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.

[0093] The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles comprising a layer of absorbed dyes, the particle-dye unit being insoluble under the aforementioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0094] Alizarin lake, for example, can be used as a colored varnish.

[0095] Pigments with a specific shape can also be used to color the keratin fibers. For example, a pigment based on a lamellar and / or lenticular substrate plate can be used. Furthermore, coloring based on a substrate plate containing a vacuum-metallized pigment is also possible.

[0096] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (F-2) which is selected from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0097] The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, more 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, more 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. Each substrate platelet preferably has a thickness that is as uniform as possible. Due to the low thickness of the substrate platelets, the pigment has particularly high hiding power.

[0098] The substrate platelets are preferably monolithic in structure. Monolithic in this context means consisting of a single, closed unit without fractures, stratification, or inclusions, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous in structure, meaning that no concentration gradient occurs within the platelets. In particular, the substrate platelets are not layered and do not contain any particles or particles distributed within them.

[0099] The size of the substrate platelet can be tailored to the respective application, in particular the desired effect on the keratinic material. As a rule, the substrate platelets have an average largest diameter of approximately 2 to 200 μm, in particular approximately 5 to 100 μm. In a preferred embodiment, the aspect ratio, expressed as the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The average size of the uncoated substrate platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Heios device with Quixel wet dispersion. For sample preparation, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.

[0100] The substrate platelets can be made of any material that can be formed into platelets.

[0101] They can be of natural origin or synthetically produced. Materials from which the substrate platelets can be constructed include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. The substrate platelets are preferably made of metal (or metal alloys).

[0102] Any metal suitable for metallic luster pigments can be considered. Such metals include iron and steel, as well as all air- and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum, and silicon, as well as their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum platelets and brass platelets, with aluminum platelets being particularly preferred.

[0103] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance.

[0104] Due to their irregular structure, pigments based on lamellar substrate platelets generate a high degree of scattered light. Furthermore, pigments based on lamellar substrate platelets do not completely cover the existing color of a keratinous material, and effects similar to natural graying can be achieved, for example.

[0105] Lenticular (= lens-shaped) substrate platelets have a substantially regular, round edge and are also referred to as "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light predominates in pigments based on lenticular substrate platelets. Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated foils. They are characterized by a particularly low thickness of the substrate platelets in the range of 5 to 50 nm and by a particularly smooth surface with increased reflectivity. Substrate platelets comprising a pigment metallized in a vacuum are also referred to as VMP substrate platelets in this application. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized foils.

[0106] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0107] Uncoated lamellar, lenticular, and / or VPM substrate plates, 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 preferred for use in the colorant.

[0108] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0109] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

[0110] 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.

[0111] Due to their excellent light and temperature stability, the use of the aforementioned pigments in the agent according to the invention is very particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, in particular of 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0112] The coloring agent (F) can also contain at least one direct dye as the coloring compound (F-2). Direct dyes are dyes that are absorbed directly into the hair and do not require an oxidative process to develop the color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols. Direct dyes can be nonionic, cationic, or anionic. It is particularly preferred if the coloring agent (F) contains at least one anionic direct dye, which can alternatively be referred to as an acid dye.

[0113] Acid dyes are understood to be direct dyes that contain at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H) and / or one sulfate group (-OSO3H). Depending on the pH, the profaned forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO; -SO3- or -OSO3"). As the pH decreases, the proportion of the profaned forms increases. If direct dyes are used in the form of their salts, the carboxylic acid or sulfonic acid groups are in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0114] The alkaline earth metal salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali metal salts. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), they do not fall under the definition of a direct dye.

[0115] A key feature of acid dyes is their ability to form anionic charges, with the carboxylic acid or sulfonic acid groups responsible for this being typically 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.

[0116] Als Beispiele für Säurefarbstoffe können 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 (C1 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1 100 (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, C1 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.1.18065), 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 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 .

[0117] In a further embodiment, an inventive method is characterized in that the dye (F) contains at least one acid dye (F-2), which is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51 , Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1 , Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1 , Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33,D&C Violet 2 and / or D&C Brown 1 .,

[0118] Since alkaline earth metal salts (such as calcium salts and magnesium salts) or aluminum salts of acid dyes generally have lower solubility than the corresponding alkali metal salts, an organic dye that is considered an acid dye in the form of its alkali metal salt can also exist in the form of a pigment if the counterion is not an alkali metal ion, but rather an alkaline earth metal or an analogous, correspondingly more highly charged counterion. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), the compounds do not fall under the definition of a direct dye but are to be considered pigments. Like pigments, acid dyes are not primarily intended to diffuse into the keratin fibers, but rather to deposit on the surface of the keratin fibers, embedded in the chitosan film.For this reason, acid dyes are particularly preferred whose solubility is so high that they can no longer be assigned to the group of organic pigments, but which nevertheless have relatively poor solubility.

[0119] For this reason, acid dyes which have a solubility in water at 25 °C of less than 20 g / L, preferably less than 18 g / L, even more preferably less than 15 g / L and very particularly preferably less than 12 g / L are very particularly preferably used as organic coloring compounds (F-2).

[0120] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) contains as color-providing compound (F-2) at least one acid dye which has a solubility in water at 25 °C of less than 20 g / L, preferably less than 18 g / L, even more preferably less than 15 g / L and very particularly preferably less than 12 g / L.

[0121] The water solubility of anionic direct dyes can be determined, for example, as follows: 0.1 g of the anionic direct dye is placed in a beaker. A stir bar is added. Then, 100 ml of water is added. This mixture is heated to 25 °C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then visually assessed. If undissolved residues remain, the amount of water is increased—for example, in 10 ml increments. Water is added until the added amount of dye has completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dye remains on the filter paper, the solubility test is repeated using a larger amount of water.If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g / L.

[0122] 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).

[0123] 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).

[0124] 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).

[0125] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazol-3-carboxylic acid and is readily soluble in water at 25 °C. 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).

[0126] 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%.

[0127] 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).

[0128] 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 stated to be greater than 10 g / L (25 °C).

[0129] Brilliant Blue FCF, alternatively known as Food Blue 2 or Acid Blue 9, is known as disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl}{(4Z)-4-[ethyl(3-sulfonatobenzyl)iminio]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate in its disodium salt and has the CAS number 3844-45-9. The disodium salt of Acid Blue 9 has a water solubility of more than 20 wt.% (25 °C).

[0130] Acid Blue 74 is also known as Indigo Carmine, Food Blue 1, or FD&C Blue 2 and has the chemical name indigo-5,5'-disulfonic acid, disodium salt, or disodium 5,5'-(2-(1,3-dihydro-3-oxo-2H-indazol-2-ylidene)-1,2-dihydro-3H-indol-3-one)disulfonate. Acid Blue 74 in the form of the disodium salt has a solubility in water of 10 g / L at 25 °C.

[0131] The color-providing compound(s) (F-2) represent(s) the second essential constituent of the colorant (F) according to the invention and are preferably used in the composition in specific quantity ranges. Particularly good results were obtained when the colorant (F) contained one or more color-providing compounds (F-2) in a total amount of 0.01 to 10.0 wt. %, preferably 0.1 to 5.0 wt. %, more preferably 0.2 to 2.5 wt. %, and most preferably 0.25 to 1.5 wt. %, based on the total weight of the colorant.

[0132] In a further very particularly preferred embodiment, a process (F) according to the invention is characterized in that the colorant (F) - based on the total weight of the agent (F) - contains one or more color-providing compounds (F-2) in a total amount of 0.01 to 10.0 wt. %, preferably 0.1 to 5.0 wt. %, more preferably 0.2 to 2.5 wt. % and very particularly preferably 0.25 to 1.5 wt. % organic and / or inorganic acids (F-3) in the colorant

[0133] As an optional ingredient, the agent (F) or the colorant (F) can contain at least one organic and / or inorganic acid (F-3). By using one or more acids, the pH of the colorant (F) can be lowered, whereby the chitosan is completely or partially profaned and dissolves more easily. Macroscopically, the protonation of the chitosan in water is perceived as swelling, from which, when the preferred or particularly preferred pH is adjusted, a particularly uniform and thin film is deposited on the keratin fibers. It has been shown that the durability of the film is better the more uniform the film forms on the hair. By forming a particularly uniform film, colorations with particularly good washfastness could also be achieved. Furthermore, the presence of the acid(s) (F-3) in the colorant also leads to the chitosan being able 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.

[0134] Particularly suitable organic acids include acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0135] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic acid (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.

[0136] Acetic acid dissolves chitosan particularly well and leads to particularly thin and uniform films, therefore a dye (F) containing acetic acid is particularly preferred.

[0137] In a further explicitly particularly preferred embodiment, a colorant (F) according to the invention is therefore characterized in that it contains acetic acid (F-3).

[0138] By using the acid(s) in appropriate amounts, the pH of the colorant can be adjusted to the desired pH range. In this context, it has also proven particularly preferable to adjust the pH of the agent (F) to a range from 1.0 to 7.5, preferably from 1.5 to 7.0, more preferably from 2.0 to 6.5, and most preferably from 2.0 to 6.0. To enable the pH of the agent (F) to be measured, the agent additionally contains water (F-4).

[0139] It is assumed that lowering the pH shifts the equilibrium reaction in the coloring compounds (F-2), which contain at least one acid group, more strongly toward the profaned acid side, thereby further reducing the solubility of the acid dyes and allowing the coloring compounds to integrate even better into the chitosan film. Therefore, the lower the pH of the colorant, the better the color absorption and washfastness of the dyes. However, for reasons of skin compatibility, the pH should not be lowered too much. Even if the colorant is designed as a leave-on product, for example, and is intended to remain on the hair without being washed out, the pH values ​​should not be chosen too low.

[0140] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) contains water (F-4) and has a pH of 1.0 to 7.5, preferably of 1.5 to 7.0, more preferably of 2.0 to 6.5 and most preferably of 2.0 to 6.0.

[0141] Amount of components (F-1), (F-2), (F-3) and (F-4) in the dye

[0142] As part of the work leading to this invention, microscopic images were taken that showed that a thin, uniform film on the keratin fibers exhibits particularly good resistance to external influences such as mechanical friction or hair washing. The smoother and more cohesive the film, the less surface area it has to resist external forces. Once the film is broken at one point, it is quickly and completely detached due to the constant movement of the keratin fibers.

[0143] It was found that the films produced with the dye (F) were particularly thin, uniform, and stable when the dye consisted largely of the components (F-1), (F-2), (F-3), and (F-4). It is suspected that other components could disrupt the uniformity of the film by embedding themselves in the film, weakening it at that point, or forming a surface vulnerable to external forces. For this reason, it is particularly preferred when the components (F-1), (F-2), (F-

[0144] 3) and (F-4) together are present in the colorant (F) in a proportion of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.% and most preferably at least 99 wt.%.

[0145] If the components (F-1), (F-2), (F-3) and (F-4) are contained together in a proportion of at least 90.0 wt.% in the colorant, then the colorant consists of at least 90 wt.% of the components (F-1), (F-2), (F-3) and (F-4) based on its total weight. In other words, in this case, other substances or ingredients that are listed from (F-1) to (F-

[0146] 4) are different, are contained in the colorant (F) only in a maximum proportion of 10 wt.%, but preferably in even smaller proportions.

[0147] In a further particularly preferred embodiment, a process according to the invention is characterized in that the components (F-1), (F-2), (F-3) and (F-4) are contained together in the colorant (F) in a proportion of at least 90.0 wt.%, preferably of at least 93 wt.%, more preferably of at least 96 wt.% and most preferably of at least 99 wt.%.

[0148] Furthermore, it has also proven preferable if no solvents other than water are used in the colorant (F). Here, too, it was observed that the film produced on the keratin fibers was very thin and uniform when the colorant contained virtually no solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, and / or polyethylene glycols.

[0149] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) is substantially free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and / or polyethylene glycols.

[0150] In this embodiment, the colorant (F) is characterized in that it is substantially free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, phenoxyethanol, and benzyl alcohol. This means that none of the solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, phenoxyethanol, and benzyl alcohol are intentionally added to the agent.

[0151] Some raw materials may contain one or more of the above-mentioned solvents in small amounts as a minor component, so that when this raw material is used, marginal amounts of this solvent are introduced. However, it has been found that the presence of such small amounts of solvent does not unduly increase skin staining.

[0152] In summary, an agent which is substantially free of the solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol and benzyl alcohol is understood to mean an agent which - based on its total weight - contains the above-mentioned solvents in a total amount of less than 0.2% by weight, preferably less than 0.1% by weight, even more preferably less than 0.05% by weight and most preferably less than 0.01% by weight.

[0153] The colorant (F) is very particularly preferably free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, and benzyl alcohol, ie the agent contains these solvents in a total amount of 0 wt.%. In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) is free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol, and polyethylene glycols.

[0154] Ethanol has the Cas number 64-17-5.

[0155] Isopropanol is also known as 2-propanol and has the CAS number 67-63-0.

[0156] 1,2-Propylene glycol is alternatively also called 1,2-propanediol and has 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],

[0157] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0158] Glycerin is also known as 1,2,3-propanetriol and has the CAS number 56-81-5. 1-Butanol can also be known as n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0159] Phenoxyethanol has the Cas number 122-99-6.

[0160] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0161] Polyethylene glycols in the sense of the present invention are liquid polymers at room temperature (25 °C) of the general molecular formula C2nH4n+2O n+i. The repeating unit of the linear polymer is (-CH2-CH2-O-), with a molar mass of about 44 g mol -1 Chemically, it is a polyether. Polyethylene glycols are therefore ethylene glycols of the formula (EG) where x is an integer from 2 to 10000.

[0162] Aftertreatment agent (N)

[0163] In step (2) of the method according to the invention, a post-treatment agent (N) is applied to the keratin fibers, in particular the human hair, which contains at least one protein hydrolysate and / or at least one amino acid (N-1).

[0164] According to the invention, protein hydrolysates are degradation products of proteins produced by acidic, basic, or enzymatic reactions. Due to the production process, protein hydrolysates exhibit a molecular weight distribution. The protein hydrolysates according to the invention also include oligopeptides, as these can also be produced from proteins through corresponding reactions. Individual amino acids, which exist as discrete individual compounds, are not considered protein hydrolysates within the meaning of this invention. According to the invention, protein hydrolysates of plant, animal, marine, or synthetic origin can be used.

[0165] Animal protein hydrolysates include elastin, collagen, keratin, silk, and milk protein hydrolysates, which can also be present in the form of salts. Such products are marketed under the trademarks Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), ProSina® (Croda), and Kerasol® (Croda).

[0166] With post-treatment agents (N) containing at least one keratin hydrolysate, a particularly pronounced improvement in the washfastness of the previously applied colorant (F) could be achieved.

[0167] A particularly suitable hydrolyzed keratin, for example, is commercially available under the trade name Keliwool from the company Kelisame. Keliwool is a keratin hydrolysate produced by gentle enzymatic hydrolysis of Merino wool using food-grade proteases at low temperatures and a neutral pH. Keliwool has an average molecular weight of 3000 Daltons. In Keliwool, the hydrolyzed keratin has the CAS number 69430-36-0 and is dissolved in water as a 20 to 23% solution.

[0168] Also preferred according to the invention are plant protein hydrolysates such as soy, almond, pea, moringa, potato, and wheat protein hydrolysates. Such products are available, for example, under the trademarks Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), Hydrosoy® (Croda), Hydrolupin® (Croda), Hydrosesame® (Croda), Hydrotritium® (Croda), Crotein® (Croda), and Puricare® LS 9658 from Laboratoires Serobiologiques.

[0169] As a suitable vegetable protein hydrolysate, the raw material Gluadin®Kera-P LM, which is a “hydrolyzed vegetable protein” and is distributed, for example, by BASF, can be used.

[0170] Other protein hydrolysates preferred according to the invention are of marine origin. These include, for example, collagen hydrolysates from fish or algae, as well as protein hydrolysates from mussels or pearl hydrolysates. Examples of pearl extracts according to the invention are the commercial products Pearl Protein Extract BG® or Crodarom® Pearl.

[0171] Furthermore, cationized protein hydrolysates are also included among the protein hydrolysates, whereby the underlying protein hydrolysate can be derived from animals, for example from collagen, milk or keratin; from plants, for example from wheat, corn, rice, potatoes, soy or almonds; from marine life forms, for example from fish collagen or algae; or from biotechnologically obtained protein hydrolysates. Typical examples of the cationic protein hydrolysates and derivatives according to the invention are those listed under the INCI designations in the “International Cosmetic Ingredient Dictionary and Handbook” (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17). th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products.

[0172] Good results were observed when the after-treatment agent (N) contained at least one protein hydrolysate (N-1) from the group of keratin, elastin, collagen, silk and milk protein hydrolysates, soy, almond, pea, moringa, potato and wheat protein hydrolysates, protein hydrolysates from mussels, pearl hydrolysates and / or their salts.

[0173] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the aftertreatment agent

[0174] (N-1) contains at least one protein hydrolysate from the group consisting of keratin, elastin, collagen, silk and milk protein hydrolysates, soy, almond, pea, moringa, potato and wheat protein hydrolysates, protein hydrolysates from mussels, pearl hydrolysates and / or their salts.

[0175] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the aftertreatment agent

[0176] (N-1) contains at least one keratin hydrolysate and / or its salts.

[0177] In the salts of protein hydrolysates, at least a portion of the amino groups present therein is in profaned form and is neutralized by corresponding negatively charged counterions (such as chloride, bromide, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, etc.), and / or the carboxy groups are deprotonated and have a cationic counterion (such as sodium, potassium or ammonium) to maintain their electroneutrality.

[0178] Further protein hydrolysates according to the invention are oligopeptides. Oligopeptides may be preferred in the hair treatment compositions according to the invention due to their defined amino acid sequence. Oligopeptides within the meaning of the present application are condensation products of amino acids linked by peptide bonds in an acid amide-like manner, comprising at least 3 and a maximum of 25 amino acids.

[0179] Furthermore, good results were obtained when, on average, at least one amino acid was used in addition to or instead of the protein hydrolysate(s). An amino acid is a chemical compound with an amino group and a carboxylic acid group. The class of amino acids includes organic compounds that contain at least one amino group (-NH2 or substituted -NR2) and one carboxyl group (-COOH) as functional groups, thus exhibiting structural features of amines and carboxylic acids. Chemically, they can be differentiated according to the position of their amino group relative to the carboxyl group. If the amino group on the calcium atom is directly adjacent to the terminal carboxyl group, this is called the α-position and is referred to as α-amino acids. Carboxylic acids with a total number of C atoms from C2 to C20, more preferably from C2 to C15, and particularly preferably from C2 to C10 are preferred.

[0180] Preferred amino acids are selected from arginine, glutamic acid, serine, lysine, histidine, asparagine, glutamine, cysteine, methionine, tryptophan, serine, alanine, aspartic acid, glycine, isoleucine, leucine, phenylalanine, proline, threonine, tyrosine and valine as well as mixtures of these amino acids.

[0181] In a further particularly preferred embodiment, a method according to the invention is characterized in that the aftertreatment agent

[0182] (N-1) contains at least one amino acid from the group consisting of L-aspartic acid, L-leucine, L-tyrosine, L-proline, L-histidine, L-serine, L-arginine, L-glutamic acid, L-lysine, L-asparagine, L-glutamine, L-cysteine, L-methionine, L-tryptophan, L-serine, L-alanine, glycine, L-isoleucine, L-phenylalanine, L-threonine and L-valine.

[0183] Chiral amino acids possess a stereogenic center and can occur in mirror-image forms. For example, arginine occurs in the form of L-arginine and D-arginine. Both the L-form of an amino acid and its D-form, as well as mixtures thereof, are encompassed by the present invention. Within the scope of the present invention, both possible enantiomers can be used equally as a specific compound or as mixtures thereof, particularly as racemates. However, it is particularly advantageous to use the naturally occurring isomer form, usually in the L-configuration.

[0184] Accordingly, a particularly preferred method according to the invention is characterized in that the aftertreatment agent (N) contains at least one amino acid (N-1)) from the group consisting of L-arginine, L-glutamic acid, L-serine, L-lysine, L-histidine, L-asparagine, L-glutamine, L-cysteine, L-methionine, L-tryptophan, L-serine, L-alanine, L-aspartic acid, glycine, L-isoleucine, L-leucine, L-phenylalanine, L-proline, L-threonine, L-tyrosine and L-valine.

[0185] To achieve the best possible results, the protein hydrolysates and / or amino acids are preferably used in specific amounts. It has proven particularly advantageous if the post-treatment agent (N) contains one or more protein hydrolysates and / or amino acids (N-1) in a total amount of 0.1 to 20 wt.%, preferably 0.2 to 10 wt.%, more preferably 0.3 to 7.5 wt.%, and most preferably 0.4 to 3.0 wt.%, based on its total weight.

[0186] In a further particularly preferred embodiment, a process according to the invention is characterized in that the aftertreatment agent (N) - based on the total weight of the aftertreatment agent (N) - contains one or more protein hydrolysates and / or amino acids (N-1) in a total amount of 0.1 to 20 wt.%, preferably 0.2 to 10 wt.%, more preferably 0.3 to 7.5 wt.% and most preferably 0.4 to 3.0 wt.%.

[0187] Dyes (F) and aftertreatment agents (N)

[0188] In the process according to the invention, in steps (1) and (2), a colorant (F) and a post-treatment agent (N) are applied to the keratin fibers, wherein the colorant (F) and the post-treatment agent (N) are different formulations.

[0189] Dyes (F) and after-treatment agents (N) are used for different purposes and, due to their different intended uses, contain different ingredients. Dye (F) is intended to color the keratin fibers, so the dye contains the chitosans (F-1) responsible for film formation and the pigments or direct dyes (F-2) responsible for coloring. Dye (F) preferably contains no protein hydrolysates or amino acids.

[0190] The aftertreatment agent (N) is intended to improve the color retention or washfastness of the dyeings and contains protein hydrolysate(s) and / or amino acid(s) for this purpose, but is not intended to dye itself. The aftertreatment agent (N) is therefore preferably characterized by not containing pigments or direct dyes.

[0191] Application of dye (F) and aftertreatment agent (N)

[0192] As already described, the aftertreatment agent (N) can be applied to the keratin fibers directly after the colorant (F). This can be the case, for example, if the colorant is to be washed out of the keratin fibers with the aid of the aftertreatment agent (N), which then preferably contains a surfactant. In this embodiment, the aftertreatment agent can then be applied directly to the keratin fibers still coated with the colorant.

[0193] However, it is also possible for the user not to rinse out the colorant (F) after coloring, but rather to leave the colorant on the keratin fibers in the form of a leave-on product. In this case, the after-treatment product can be applied, for example, to the keratin fibers still coated with the colorant. In a subsequent drying step, the colorant (F) and after-treatment product (N) can then be dried together.

[0194] The after-treatment product (N) can also be applied to the hair later, for example, at a time when the next hair wash is due. In this case, the after-treatment product (N) also contains at least one surfactant. Depending on the user's habits, the time between applying both products (F) and (N) can be several hours, but also one to several days.

[0195] If the after-treatment agent (N) is to be used as a shampoo, it preferably contains one or more surfactants, particularly preferably one or more anionic surfactants, to ensure a sufficiently high cleaning performance.

[0196] In principle, any anionic surface-active substance suitable for use on the human body is suitable as anionic surfactants. These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups.Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, a-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, acyl tartrates, acyl glutamates, acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrowed homolog distribution.Examples of particularly suitable anionic surfactants are, in the form of sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts with 2 to 4 C atoms in the alkanol group, linear and branched fatty acids with 8 to 30 C atoms (soaps).

[0197] Ethercarboxylic acids of the formula RO-(CH2-CH2O)x-CH2-COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,

[0198] Acylsarcosides with 8 to 24 C atoms in the acyl group,

[0199] Acyltaurides with 8 to 24 C atoms in the acyl group,

[0200] Acyl isethionates with 8 to 24 carbon atoms in the acyl group are long-known, skin-friendly surfactants that are obtainable by esterifying fatty acids with the sodium salt of 2-hydroxyethanesulfonic acid (isethionic acid). If fatty acids with 8 to 24 carbon atoms, such as lauric, myristic, palimitic, or stearic acid, or even technical fatty acid fractions, such as the C12-cis fatty acid fraction obtainable from coconut fatty acid, are used for this esterification, the C12-cis acyl isethionates that are preferably suitable according to the invention are obtained. It is known that the sodium salts of C12-cis acyl isethionates can be formed into a suitable form for transport and application by kneading, piling, extruding, cutting, and bar pressing, similar to fatty acid-based soaps. In this way, needles, granules, noodles, or bars can be produced. One application of acyl isethionates is toilet soap bars and syndets.

[0201] Sulfosuccinic acid mono- and dialkyl esters with 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters with 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups. The sulfosuccinic acid monoalkyl (C8-C24) ester disodium salts are produced by known processes, e.g., by reacting maleic anhydride with a fatty alcohol with 8-24 C atoms to form the maleic acid monoester of the fatty alcohol, and then sulfiting this with sodium sulfite to form the sulfosuccinic acid ester. Particularly suitable sulfosuccinic acid esters are derived from fatty alcohol fractions with 12-18 C atoms, such as those found, for example, in fatty alcohols. B. from coconut fatty acid or coconut fatty acid methyl ester by hydrogenation, linear alkanesulfonates with 8 to 24 C atoms, linear alpha-olefinsulfonates with 8 to 24 C atoms,

[0202] Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms,

[0203] Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO(CH2-CH2O)x-OSC>3H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12, hydroxysulfonates essentially corresponding to at least one of the two following formulas or mixtures thereof and salts thereof, CH3-(CH2)y-CHOH-(CH2)p-(CH-SO3M)-(CH2)z-CH2-O-(CnH2nO)xH, and / or

[0204] CH3-(CH2)y-(CH-SO3M)-(CH2)p-CHOH-(CH2)z- CH2-O-(CnH2nO)xH where in both formulas y and z = 0 or integers from 1 to 18, p = 0, 1 or 2 and the sum (y+z+p) is a number from 12 to 18, x = 0 or a number from 1 to 30 and n is an integer from 2 to 4 and M = H or alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc and / or an ammonium ion, which may optionally be substituted, in particular mono-, di-, tri- or tetraammonium ions with C1 to C4 alkyl, alkenyl or aryl radicals, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylenepropylene glycol ethers of the formula R 1 - (CHOSO3M)-CHR 3 -(OCHR 4 -CH2)n-OR 2 with R 1 , a linear alkyl radical with 1 to 24 C atoms, R 2 represents a linear or branched, saturated alkyl radical having 1 to 24 C atoms, R 3 represents hydrogen or a linear alkyl radical having 1 to 24 C atoms, R 4represents hydrogen or a methyl radical and M represents hydrogen, ammonium, alkylammonium, alkanolammonium, wherein the alkyl and alkanol radicals each have 1 to 4 C atoms, or a metal atom selected from lithium, sodium, potassium, calcium or magnesium and n represents a number in the range from 0 to 12 and furthermore the total number of radicals in R 1 and R 3 contained C atoms is 2 to 44, sulfonates of unsaturated fatty acids with 8 to 24 C atoms and 1 to 6 double bonds,

[0205] Esters of tartaric acid and citric acid with alcohols, which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 C atoms, alkyl and / or alkenyl ether phosphates of the formula,

[0206] R 1 (OCH2CH2)nO-(PO-OX)-OR 2 , in the R 1 preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R 2 for hydrogen, a residue (CH2CH2O)n R 2 orX, n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR 3 R 4 R 5 R e , with R 3 to R e independently of one another standing for hydrogen or a Ci to C4 hydrocarbon radical, sulfated fatty acid alkylene glycol esters of the formula RCO(AlkO) n SC>3M in which RCO- is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk is CH2CH2, CHCH3CH2 and / or CH2CHCH3, n is a number from 0.5 to 5 and M is a metal, such as alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc, or ammonium ion, such as + NR 3 R 4 R 5 R e , with R 3 to R e independently of each other standing for hydrogen or a C1 to C4 hydrocarbon radical,

[0207] Monoglyceride sulfates and monoglyceride ether sulfates of the formula R 8 OC-(OCH2CH2)x-OCH2-[CHO(CH2CH2O) y H]-CH2O(CH2CH2O)z-SO3X, in which R 8 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total represent 0 or numbers from 1 to 30, preferably 2 to 10, and X represents an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates are preferably used in which R 8 CO represents a linear acyl radical with 8 to 18 carbon atoms,

[0208] Amide ether carboxylic acids, R 1 -CO-NR 2 -CH2CH2-O-(CH2CH2O) nCH2COOM, with R 1 as a straight-chain or branched alkyl or alkenyl radical with a number of carbon atoms in the chain from 2 to 30, n stands for an integer from 1 to 20 and R 2 represents hydrogen, a methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or iso-butyl radical and M represents hydrogen or a metal such as alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc, or an ammonium ion, such as + NR 3 R 4 R 5 R e , with R 3 to R eindependently of one another stand for hydrogen or a C1 to C4 hydrocarbon radical. Such products are available, for example, from Chem-Y under the product name Akypo®. Acylglutamates of the formula XOOC-CH2CH2CH(C(NH)OR)-COOX, in which RCO stands for a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and X stands for hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, condensation products of a water-soluble salt of a water-soluble protein hydrolysate-fatty acid condensation product. These are produced by condensation of C8 - C30 fatty acids, preferably fatty acids with 12 - 18 C atoms, with amino acids, mono-, di- and water-soluble oligopeptides and mixtures of such products, as arise from the hydrolysis of proteins.These protein hydrolysate-fatty acid condensation products are neutralized with a base and are then preferably present as alkali, ammonium, mono-, di-, or trialkanolammonium salts. Such products have long been commercially available under the trademarks Lamepon®, Maypon®, Gluadin®, Hostapon® KCG, or Amisoft®.

[0209] In a further particularly preferred embodiment, a method according to the invention comprises

[0210] (1) Application of the colorant (F) on the keratin fibers in a first step, then the

[0211] (2) Application of the after-treatment agent (N) to the keratin fibers in a second step, wherein between steps (1) and (2) there is a period of maximum 72 hours, preferably maximum 60 hours, particularly preferably maximum 48 hours.

[0212] The application of the aftercare agent can also be repeated one or more times.

[0213] In a further embodiment, a method comprising the following steps is particularly preferred:

[0214] (1) Applying the colorant (F) to the keratin fibers,

[0215] (2) Action of the colorant (F) on the keratin fibers, and

[0216] (3) if necessary, rinsing out the dye (F),

[0217] (4) Applying the after-treatment agent (N) to the keratin fibres,

[0218] (5) the post-treatment agent (N) applied in step (4) acts on the keratin fibres, and

[0219] (6) if necessary, rinsing out the after-treatment agent (V).

[0220] In a further embodiment, a method comprising the following steps is particularly preferred:

[0221] (1) Applying the colorant (F) to the keratin fibers,

[0222] (2) Action of the colorant (F) on the keratin fibers, and

[0223] (3) Drying the keratin fibres still coated with the dye (F), (4) Applying the after-treatment agent (N) to the keratin fibres,

[0224] (5) the post-treatment agent (N) applied in step (4) acts on the keratin fibres, and

[0225] (6) if necessary, rinsing out the after-treatment agent (N).

[0226] In a further embodiment, a method comprising the following steps is also particularly preferred:

[0227] (1) Applying the colorant (F) to the keratin fibers,

[0228] (2) Action of the colorant (F) on the keratin fibers,

[0229] (3) Applying the after-treatment agent (N) to the keratin fibres still covered with the colouring agent (F),

[0230] (5) Drying the keratin fibres treated with the colouring agent (F) and the after-treatment agent (N).

[0231] Multi-component packaging unit

[0232] To increase user convenience, all required resources are preferably provided to the user in the form of a multi-component packaging unit (kit of parts).

[0233] A second subject of the present invention is therefore a multi-component packaging unit (kit-of-parts) for coloring keratin fibers, in particular human hair, comprising a first container with a coloring agent (F) and a second container with a post-treatment agent (N) separately packaged from one another, wherein the coloring agent (F) and the post-treatment agent (N) have already been disclosed in detail in the description of the first subject of the invention.

[0234] The multi-component packaging unit (kit-of-parts) may also include one or more additional containers with additional formulations.

[0235] Improved color retention

[0236] For the purposes of the present invention, an improvement in color retention is understood in particular to mean an improvement in washfastness, i.e., with the application of the method according to the invention, fewer pigments / dyes are removed from the hair during subsequent washes. Color retention can be quantified, for example, visually or by colorimetric measurements (measurement of the L, a, b values) and calculation of the color difference. The smaller the color difference between washed and unwashed hair, the better the washfastness or color retention.A third subject matter of the present application is the use of an aftertreatment agent (N) for improving the color retention of or on keratin fibers, in particular human hair, which have been colored by applying a colorant (F), wherein the colorant (F) and the aftertreatment agent (N) have already been disclosed in detail in the description of the first subject matter of the invention.

[0237] In other words, a third subject matter of the present application is the use of an after-treatment agent (N) for improving the color retention of a colorant (F) on keratin fibers, wherein the colorant (F) and the after-treatment agent (N) have already been disclosed in detail in the description of the first subject matter of the invention.

[0238] Regarding the further preferred embodiments of the multi-component packaging unit (kit of parts) according to the invention and use, what has been said regarding the methods according to the invention applies mutatis mutantis.

[0239] Examples

[0240] 1 . Formulations

[0241] The following formulations were prepared (all data in wt.% unless otherwise stated):

[0242] 2. Application to strands

[0243] The dyes were applied to strands of hair (Kerling). 0.25 g of dye (F) was massaged into each gram of hair strand and left on for 1 minute. The strands still coated with the dye were then dried with a standard hairdryer. Each dyed strand was then immersed in the after-treatment product for 30 minutes. After removal, the after-treatment product was removed from the strands, and the strands were dried with a hairdryer and stored for 24 hours. The dyed strands were visually assessed by a trained person under a daylight lamp.

[0244] Reference strands were treated with the respective colorant (F) according to the procedure described above, but no after-treatment agent (N) was applied. These strands were also visually assessed by a trained person under a daylight lamp after drying.

[0245] 3. Measurement of Washfastness Following coloring and aftercare, each strand was subjected to five manual washes. For each wash, the strand was moistened, then a commercially available shampoo (Schauma 7 Kräuter) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). The strand was then rinsed with lukewarm tap water for 30 seconds and dried.

[0246] After each hair wash, the respective strand was again visually assessed under the daylight lamp.

[0247] The hair strands were assessed for their color intensity using a scale from 1 (very low color intensity) to 5 (very high color intensity).

[0248] 0 HW = Color result directly after coloring

[0249] 5 = high intensity 1 = low intensity

[0250] 5 = high intensity 1 = low intensity

[0251] The strands dyed with the process (F1) / (N) and (F2) / (N) according to the invention showed improved wash fastness compared to the corresponding dyeing without post-treatment (N).

Claims

Patent claims 1. A process for dyeing keratin fibers, in particular human hair, comprising (1) Application of a coloring agent (F) on the keratin fibers, which contains (F-1) at least one chitosan and / or a chitosan derivative, and (F-2) at least one coloring compound from the group of pigments and direct dyes, (2) Application of a post-treatment agent (N) to the keratin fibers, which contains (N-1) at least one protein hydrolysate and / or at least one amino acid.

2. The method according to claim 1, characterized in that the coloring agent (F) contains at least one chitosan and / or a chitosan derivative (F-1) having 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. Process according to one of claims 1 to 2, characterized in that the coloring agent - based on the total weight of the coloring agent (F) - contains one or more chitosans and / or chitosan derivatives (F-1) in a total amount of 0.1 to 10.0 wt.%, preferably of 0.2 to 8.0 wt.%, more preferably of 0.5 to 6.0 wt.% and most preferably of 0.7 to 2.0 wt.%.

4. The method according to any one of claims 1 to 3, characterized in that the colorant (F) contains at least one inorganic pigment (F-2), which is preferably selected from the group 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 mica, which are coated with at least one metal oxide and / or one metal oxychloride.

5. The method according to any one of claims 1 to 4, characterized in that the colorant (F) contains at least one organic pigment (F-2), which is 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 CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, Cl 15865, Cl 15880, Cl 17200, Cl 26100, Cl 45380, Cl 45410, Cl 58000, Cl 73360, Cl 73915 and / or Cl 75470.

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

7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennezeichnet, dass das Färbemittel (F) mindestens einen Säurefarbstoff (F-2) enthält, der ausgewählt ist aus der Gruppe aus Acid Yellow 1 , Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121 , Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11 , Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51 , Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1 , Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1 , Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11 , D&C Red 21 , D&C Red 27, D&C Red 33, D&C Violet 2 und / oder D&C Brown 1 .

8. Process according to one of claims 1 to 7, characterized in that the coloring agent (F) contains at least one organic acid (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 and water (F-4).

9. The method according to claim 8, characterized in that the components (F-1), (F-2), (F-3) and (F-4) are contained together in the colorant (F) in a proportion of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.% and most preferably at least 99 wt.%.

10. The method according to any one of claims 1 to 9, characterized in that the colorant (F) is substantially free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and / or polyethylene glycols.

11. Method according to one of claims 1 to 10, characterized in that the aftertreatment agent (N-1) at least one protein hydrolysate from the group of keratin, elastin, collagen, silk and milk protein hydrolysates, soy, almond, pea, moringa, Contains potato and wheat protein hydrolysates, mussel protein hydrolysates, pearl hydrolysates and / or their salts.

12. Method according to one of claims 1 to 11, characterized in that the aftertreatment agent (N-1) contains at least one amino acid from the group consisting of L-aspartic acid, L-leucine, L-tyrosine, L-proline, L-histidine, L-serine, L-arginine, L-glutamic acid, L-lysine, L-asparagine, L-glutamine, L-cysteine, L-methionine, L-tryptophan, L-serine, L-alanine, glycine, L-isoleucine, L-phenylalanine, L-threonine and L-valine.

13. The method according to any one of claims 1 to 12, characterized in that the aftertreatment agent (N) - based on the total weight of the aftertreatment agent (N) - contains one or more protein hydrolysates and / or amino acids (N-1) in a total amount of 0.1 to 20 wt.%, preferably 0.2 to 10 wt.%, more preferably 0.3 to 7.5 wt.% and most preferably 0.4 to 3.0 wt.%.

14. A method according to any one of claims 1 to 13, comprising - Application of the colorant (F) on the keratin fibers in a first step, then the - Application of the after-treatment agent (N) to the keratin fibers in a second step, wherein between steps (1) and (2) there is a period of maximum 72 hours, preferably maximum 60 hours, particularly preferably maximum 48 hours.

15. Multi-component packaging unit (kit-of-parts) for coloring keratin fibers, in particular human hair, comprising a first container with a coloring agent (F) and a second container with a post-treatment agent (N) separately packaged from one another, wherein the coloring agent (F) and the post-treatment agent (N) have been defined in claims 1 to 13.

16. Use of a post-treatment agent (N) for improving the color retention of keratin fibers colored with a colorant (F), wherein the colorant (F) and the post-treatment agent (N) have been defined in claims 1 to 13.

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