Method for dyeing keratin fibers, comprising the use of a dye containing chitosane and a dyeing compound, and the use of a shampoo

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 a shampoo (S) on the keratin fibers, containing water and at least one surfactant and having a pH of 4.0 to 8.0, and the dye (F) and the shampoo (S) have different formulations.

Description

[0001] A method for coloring keratin fibers, comprising the application of a colorant containing chitosan and color-imparting compound and the application of a shampoo

[0002] The present application relates to a process for coloring keratin fibers, in particular human hair, which comprises the application of a colorant (F) and the application of a shampoo (S). The colorant (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 shampoo (S) contains water and surfactant and has a pH of 4.0 to 8.0.

[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 shampoo (S) in separately packaged containers.

[0004] A third subject matter of this application is the use of the above-described shampoo (S) for improving the color retention of the 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.

[0007] The use of color pigments is known for temporary color changes on 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 merely deposit externally on the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue after several washes with surfactant-containing cleansers. Various products of this type are available on the market under the name hair mascara.

[0008] 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.

[0009] Despite these many advantages, the pigment-based coloring system still has several 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.

[0010] 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.

[0011] 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.

[0012] The colorations obtained with pigment / dye and chitosan still have disadvantages in terms of washfastness. Achieving uniform coloration across the entire hair length cannot yet be considered optimal, as the durability of the films can vary on different hair sections, especially at the roots and ends.

[0013] 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 carried out with the aid of biopolymers, and the keratin fibers or hair colored in this way should not feel coated or greasy, exhibit a well-groomed shine, and the curl behavior of the keratin fibers should not be negatively affected.

[0014] 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.

[0015] Surprisingly, it has now been found that keratin fibers that have been colored in a first step by applying a colorant containing chitosan and pigment or dye have improved washfastness, especially when a shampoo that is not too acidic or neutral to slightly alkaline is used in a subsequent step.

[0016] A first subject of the present invention is a process for dyeing keratin fibers, in particular human hair, comprising the

[0017] (1) Application of a coloring agent (F) on the keratin fibers, which contains

[0018] (F-1) at least one chitosan and / or a chitosan derivative, and

[0019] (F-2) at least one coloring compound from the group of pigments and direct dyes, and the

[0020] (2) Application to the keratin fibres of a shampoo (S) containing water and at least one surfactant and having a pH of 4.0 to 8.0, the colouring agent (F) and the shampoo (S) being different formulations.

[0021] In step (1) of the process 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 moderately acidic to slightly alkaline shampoo. If the colorant is applied as a rinse-off product and is washed out again after coloring, the shampoo (S) according to the invention can be used to wash out the colorant. In this case, there is only a period of minutes to a few hours between steps (1) and (2). The user can also preferably perform all subsequent hair washes with this shampoo. If the colorant (F) is applied as a leave-on product, the shampoo (S) is not used directly after coloring, but the user applies the shampoo (S) during the first hair wash after coloring.In this case, there can be a period of several hours to a few days between the application of the colorant (F) and the application of the shampoo (S). Even after the first wash, the user can also use the shampoo (S) for subsequent washes.

[0022] The hair dyed or dyed and washed using this process was characterized by coloring with particularly good washfastness.

[0023] Keratin fibers

[0024] Keratin fibers include wool, fur, and feathers, and especially human hair. Human hair is particularly preferred as a keratin fiber.

[0025] Coloring agents

[0026] 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.

[0027] Application of the colorant (F) on keratin fibers

[0028] 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

[0029] Contains chitosan and / or a chitosan derivative (F-1) and at least one colorant compound (F-2) from the group of pigments and direct dyes. The colorant (F) is a ready-to-use colorant.

[0030] When using the colorant (F), it can be applied to the keratin fibers, for example with a gloved hand or with the help of a brush or applicator, and lightly massaged in if necessary.

[0031] Chitosans (F-1) in the dye (F)

[0032] As a first essential component, the coloring agent (F) used in the process according to the invention contains at least one chitosan or a derivative of chitosan (F-1).

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from Sigma-Aldrich, for example. Chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Dalton) is available in pharmaceutical grade from BioLog Heppe (Kraeber), for example. The degree of deacetylation of this chitosan is 88-95%.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] It has proven particularly advantageous if the colorant according to the invention contains the chitosan(s) and / or chitosan derivative(s) (F-1) in specific quantity ranges. 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.%.

[0044] In a further particularly preferred embodiment, a process according to the invention is 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. % coloring compounds (F-2) in the colorant CF).

[0045] As a second essential component, 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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).

[0050] 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.

[0051] 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 are 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). In a further preferred embodiment, a process according to the invention is 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 mica- or mica-based pigments coated with at least one metal oxide and / or one metal oxychloride.

[0052] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (f2) 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).

[0053] 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.

[0054] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise:

[0055] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0056] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

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

[0058] Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0059] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)

[0060] Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0061] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0062] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0063] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0064] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0065] Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 77288 (CHROMIUM OXIDE GREENS)

[0066] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), FERRIC FERROCYANIDE (Cl 77510)

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

[0068] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0069] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0070] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

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

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

[0073] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0074] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

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

[0076] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

[0077] Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0078] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0079] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide)

[0080] Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

[0081] Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0082] Other particularly preferred color pigments with the trade name Xirona® include:

[0083] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0084] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0085] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0086] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0087] In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

[0088] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0089] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0090] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0091] In a further embodiment, the applied colorant may also contain one or more organic pigments. The organic pigments according to the invention are correspondingly insoluble organic dyes or lakes, which may be selected, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindido, dioxazine, and / or triarylmethane compounds.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] Alizarin varnish, for example, can be used as a color varnish. 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 specific application, especially the desired effect on the keratin material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 pm, particularly approximately 5 to 100 pm.

[0100] 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 tested was predispersed in isopropanol for 3 minutes.

[0101] The substrate platelets can be made of any material that can be formed into platelets.

[0102] 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).

[0103] 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.

[0104] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance.

[0105] 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.

[0106] Lenticular (= lens-shaped) substrate platelets have a generally regular, round edge and are also called "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light predominates in pigments based on lenticular substrate platelets.

[0107] 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 thin substrate platelet thickness in the range of 5 to 50 nm and a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum-metallized pigment 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.

[0108] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0109] 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.

[0110] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0111] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

[0112] 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.

[0113] 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).

[0114] 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.

[0115] Direct dyes can be non-ionic, cationic, or anionic. It is very particularly preferred if the colorant (F) contains at least one anionic direct dye, which can alternatively also be referred to as an acid dye. Anionic direct dyes are also referred to as acid dyes. Acid dyes are understood to be direct dyes that have at least one carboxylic acid grouping (-COOH) and / or one sulfonic acid grouping (-SO3H) and / or one sulfate grouping (-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-, -SO5, or -OSO5). With decreasing pH, the proportion of the profaned forms increases. If direct dyes are used in the form of their salts, the carboxylic acid groups orSulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0116] 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.

[0117] 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.

[0118] 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.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 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 .

[0119] In the context of 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 .,

[0120] Since alkaline earth metal salts (such as calcium and magnesium salts) or aluminum salts of acid dyes are less soluble than the corresponding alkali metal salts, an organic dye that, in the form of its alkali metal salt, is considered an acid dye can also exist in the form of a pigment if the counterion for the acid group(s) 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.

[0121] Like pigments, acid dyes are primarily not 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 classified as organic pigments, but which nevertheless have relatively poor solubility. For this reason, acid dyes are particularly preferred as organic coloring compounds (F-2) that have a solubility in water of less than 20 g / L at 25 °C, preferably less than 18 g / L, even more preferably less than 15 g / L, and most preferably less than 12 g / L.

[0122] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) contains, as organic coloring 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.

[0123] 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.

[0124] 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).

[0125] 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).

[0126] 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).

[0127] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)- 1 H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

[0128] 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).

[0129] 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%.

[0130] 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). 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; its water solubility is stated to be greater than 10 g / L (25 °C).

[0131] 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).

[0132] 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.

[0133] 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.

[0134] 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

[0135] As an optional component, the agent (F) or the colorant (F) may contain at least one organic and / or inorganic acid (F-3).

[0136] 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 value 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 even the film forms on the hair. By forming a particularly uniform film, colorations with particularly good washfastness could also be achieved. In addition, the presence of the acid(s) (F-3) in the colorant also means that the chitosan can form a particularly thin film on the hair.Comparative studies have shown that a uniformly thin film has better resistance to external mechanical influences.

[0137] Particularly suitable organic acids include acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

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

[0139] 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.

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

[0141] 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).

[0142] 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 2.0 to 7.5, preferably from 3.0 to 7.0, more preferably from 3.5 to 6.5, and most preferably from 4.0 to 6.0. To allow the pH of the agent (F) to be measured, the agent additionally contains water (F-4).

[0143] 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.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 2.0 to 7.5, preferably of 3.0 to 7.0, more preferably of 3.5 to 6.5 and most preferably of 4.0 to 6.0.

[0144] Amount of components (F-1), (F-2), (F-3) and (F-4) in the dye

[0145] 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.

[0146] It was found that the films produced with the colorant (F) were particularly thin, uniform, and stable when the colorant consisted largely of the components (F-1), (F-2), (F-3), and (F-4). It is suspected that additional components could disrupt the film's uniformity by integrating into the film, weakening it at this point, or forming a surface vulnerable to external forces. For this reason, it is particularly preferred when the components (F-1), (F-2), (F-

[0147] 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.%.

[0148] 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-

[0149] 4) are different, are contained in the colorant (F) only in a maximum proportion of 10 wt.%, but preferably in even smaller proportions.

[0150] 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.%.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] Most preferably, the colorant (F) is free from 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.%.

[0157] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) is free from solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycols.

[0158] Ethanol has the Cas number 64-17-5.

[0159] Isopropanol is alternatively referred to as 2-propanol and has the CAS number 67-63-0. 1,2-Propylene glycol is alternatively referred to as 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].

[0160] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0161] Glycerin is also known as 1,2,3-propanetriol and has the CAS number 56-81-5.

[0162] 1-Butanol can also be referred to as n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0163] Phenoxyethanol has the Cas number 122-99-6.

[0164] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0165] 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.

[0166] Shampoo (S)

[0167] In step (2) of the process according to the invention, a shampoo (S) is applied to the keratin fibers, in particular the human hair, which shampoo contains water and at least one surfactant and has a pH of 4.0 to 8.0.

[0168] As already described, the shampoo (S) 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 help of the shampoo. In this embodiment, the shampoo can then be applied directly to the keratin fibers still coated with the colorant.

[0169] Additionally or instead, it is also possible for the user not to rinse out the colorant (F) even after coloring, but for the colorant to remain on the keratin fibers in the form of a leave-on product. In this case, the shampoo (S) can be used, for example, when the next hair wash is due. Depending on the user's habits, the time between applying both products (F) and (S) can be several hours, but also one to several days. The shampoo (S) is intended to cleanse the hair and contains surfactants and water for this purpose. In particular, the pH value of the shampoo is set to a value that prevents excessive swelling of the chitosan film. It has been found that the chitosan film coating the fibers begins to swell if the shampoo has a pH value that is too low. The film then becomes softer or less stable and detaches from the keratin fibers more quickly.

[0170] However, if the shampoo (S) has a pH value of 4.2 to 7.0, preferably 4.4 to 6.8, more preferably 4.6 to 6.6, even more preferably 4.8 to 6.4 and most preferably 5.0 to 6.2, the swelling or softening of the chitosan film is prevented, the film retains greater resistance to external influences and adheres better to the keratin fiber.

[0171] In a further particularly preferred embodiment, a process according to the invention is characterized in that the shampoo (S) has a pH of 4.2 to 7.0, preferably of 4.4 to 6.8, more preferably of 4.6 to 6.6, even more preferably of 4.8 to 6.4 and most preferably of 5.0 to 6.2.

[0172] To ensure a sufficiently high cleaning performance, the shampoo (S) contains one or more surfactants, preferably one or more anionic surfactants.

[0173] 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 the sodium, potassium and ammonium as well as the 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), ether carboxylic acids of the formula RO-(CH2-CH2O)x-CH2-COOH, in which R is a linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16, acyl sarcosides with 8 to 24 C atoms in the acyl group, acyl taurides with 8 to 24 C atoms in the acyl group, acyl isethionates with 8 to 24 C atoms in the acyl group, are long-known, skin-friendly surface-active substances which are produced by esterification of fatty acids with the sodium salt of 2-Hydroxyethanesulfonic acid (isethionic acid) are accessible. If fatty acids with 8 to 24 carbon atoms, such as lauric, myristic, palimitic, or stearic acid, or even technical fatty acid fractions, such asBy using the C12-cis fatty acid fraction obtainable from coconut fatty acid, the C12-cis acyl isethionates that are particularly 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. Needles, granules, noodles, or bars can be produced in this way. One application of acyl isethionates is toilet soap bars and syndets.

[0174] 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,

[0175] Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms,

[0176] 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

[0177] 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 - (CHOSC>3M)-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,

[0178] 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,

[0179] 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,

[0180] 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,

[0181] 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 an alkali metal, in particular sodium, potassium, lithium, an 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 e independently of each other, represent hydrogen or a C1 to C4 hydrocarbon residue. Such products are available, for example, from Chem-Y under the product name Akypo®.

[0182] Acylglutamates of the formula XOOC-CH2CH2CH(C(NH)OR)-COOX, in which RCO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and X represents hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium,

[0183] Condensation products of a water-soluble salt of a water-soluble protein hydrolysate-fatty acid condensation product. These are produced by the condensation of C8-C30 fatty acids, preferably fatty acids with 12-18 carbon 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®.

[0184] Certain surfactants have proven particularly suitable for use in shampoo (S). Particularly good washfastness of the dye (F) was observed when the shampoo (S) contained at least one surfactant from the group consisting of Cs-Cs-alkyl isethionates, Cs-Cs-alkyl sulfosuccinates, and / or their salts.

[0185] In a further particularly preferred embodiment, a process according to the invention is characterized in that the shampoo (S) contains at least one surfactant from the group consisting of Cs-Cso-alkyl isethionates, Cs-Cso-alkyl sulfosuccinates and / or salts thereof.

[0186] Cs-Cso-alkyl isethionates are the esters of long-chain Cs-Cso carboxylic acids with isethionic acid (2-hydroxyethanesulfonic acid) or their salts, such as ammonium, potassium, or sodium isethionate. Cs-Cso-alkyl isethionates are anionic surfactants of the formula (T-1) where n is a number from 1 to 12, preferably a number from 1 to 7, and

[0187] M1 represents hydrogen or a metal such as alkali metal, in particular sodium, potassium, lithium,

[0188] Alkaline earth metal, especially magnesium, calcium, zinc, or an ammonium ion (NH4 + ) stands.

[0189] A particularly suitable surfactant is sodium cocoyl isethionate, which has the CAS number 61789-32-0 and is commercially available from Akzo Nobel under the trade names Eifan AT 84 and Eifan AT 84 G.

[0190] Sodium cocoyl isethionate can also be purchased commercially from Finetex under the trade name Tauranol I 78 or from Rhone Poulenc under the trade name Geropon AC 78 NP.

[0191] Cs-Cs-alkyl sulfosuccinates are the esters of long-chain Cs-Cs-alcohols with sulfosuccinic acid. Both the monoesters and diesters of sulfosuccinic acid belong to the group of Cs-Cs-alkyl sulfosuccinates. Salts such as ammonium, potassium, or sodium Cs-Cs-alkyl sulfosuccinates are also suitable surfactants of this type. Cs-Cs-alkyl sulfosuccinates are surfactants of the formula (T-2) where

[0192] M2 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 (NH4 + ) stands, and

[0193] M3, M4 independently of one another represent a Cs-Cso-alkyl group, preferably a Cs-C2o-alkyl group, a hydrogen atom, a metal such as an alkali metal, in particular sodium, potassium, lithium, an alkaline earth metal, in particular magnesium, calcium, zinc, or an ammonium ion (NH4 +), where at least one of the residues M3 and / or M4 represents a Cs-Cs0-alkyl group, preferably a Cs-C20-alkyl group. Disodium lauryl sulfosuccinate with the CAS number 26838-05-1 can be purchased, for example, in the form of the raw material Rewopol SB F 12 P from Evonik Degussa.

[0194] Another very suitable raw material containing a mixture of Cs-Cs-alkyl isethionates and Cs-Cs-alkyl sulfosuccinates is, for example, the product Tensioanol LSASP 2, which is available from KLK Tensachem. Tensioanol LSASP 2 contains wheat starch along with sodium cocoyl isethionate, disodium lauryl sulfosuccinate, cetearyl alcohol, water, and glycerin. Shampoos (S) containing this raw material delivered particularly good results.

[0195] Dye (F) and Shampoo (S)

[0196] In the process according to the invention, in steps (1) and (2), a dye (F) and a shampoo (S) are applied to the keratin fibers, the dye (F) and the shampoo (S) being different formulations.

[0197] Dyes (F) and shampoos (S) are used for different purposes and, due to their different intended uses, contain different ingredients. Dyes (F) are 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.

[0198] The shampoo (S) is used for the subsequent cleaning of the keratin fibers and therefore contains the surfactants necessary for cleaning.

[0199] For this reason, a coloring agent (F) according to the invention is preferably characterized in that it either contains no surfactants or contains them in smaller total amounts than the shampoo (S).

[0200] The shampoo (S) according to the invention is preferably characterized in that it contains no pigments and no direct dyes. Further optional ingredients in the shampoo (S)

[0201] In addition to the components already described which are essential to the invention, the colorant and / or shampoo can also contain further optional ingredients, such as, for example, anionic, non-ionic, zwitterionic and / or cationic polymers; structuring agents such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethyl isosorbide and cyclodextrins; fiber structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose; dyes for coloring the agent; anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and / or plant origin, as well as in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives; vegetable oils; light protectants and UV blockers;Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers; Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2, and air.

[0202] The expert will select these additional substances based on the desired properties of the agent. Regarding further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the expert. The additional active ingredients and excipients are preferably used in the preparations according to the invention in amounts of 0.0001 to 25 wt.%, in particular 0.0005 to 15 wt.%, based on the total weight of the respective agent.

[0203] Steps (1) and (2) of the procedure

[0204] The method according to the invention comprises the application of a colorant (F) to the keratin fibers in step (1) and the application of a shampoo (S) to the keratin fibers in step (2).

[0205] As previously described, it is particularly preferred if the keratin fibers are first colored by applying the coloring agent (F) and then applying the shampoo (S). The time at which the shampoo (S) is applied depends on the user's needs and can be adapted to their habits as previously described.

[0206] For example, it is possible to apply shampoo (S) to the freshly colored, still wet or moist keratin fibers, so that there is a period of only a few minutes to a few hours between rinsing out the colorant (F) and applying the shampoo (S).

[0207] However, it is especially preferred to use the shampoo (S) at the time when the user usually wants to wash their keratin fibers or hair for the first time after coloring. This time is usually between 1 and 3 days after coloring. In a further embodiment, a method comprising

[0208] (1) Application of the colorant (F) on the keratin fibers in a first step, then the

[0209] (2) Application of the shampoo (S) 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 and particularly preferably maximum 48 hours.

[0210] The application of the shampoos can also be repeated once or several times.

[0211] In a further embodiment, a method comprising the

[0212] (1) Application of the colorant (F) on the keratin fibers in a first step, then the

[0213] (2) Application of the shampoo (S) 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 and particularly preferably maximum 48 hours, wherein step (2) is repeated one or more times.

[0214] Multi-component packaging unit

[0215] 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).

[0216] 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 colorant (F) and a second container with a shampoo (S) separately packaged from one another, wherein the colorant (F) and the shampoo (S) have already been disclosed in detail in the description of the first subject of the invention.

[0217] The multi-component packaging unit (kit-of-parts) may also include one or more additional containers with additional formulations.

[0218] Improved color retention

[0219] 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, 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 visual assessment of color retention, such as washfastness, is also possible.

[0220] A third subject matter of the present application is the use of a shampoo (S) for improving the color retention on keratin fibers, in particular human hair, which have been colored by applying a colorant (F), wherein the colorant (F) and the shampoo (S) have already been disclosed in detail in the description of the first subject matter of the invention.

[0221] In other words, a third subject matter of the present application is the use of a shampoo (S) for improving the color retention of a colorant (F) on keratin fibers, wherein the colorant (F) and the shampoo (S) have already been disclosed in detail in the description of the first subject matter of the invention.

[0222] 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.

[0223] Examples

[0224] 1 . Formulations

[0225] The following formulations were prepared (all data in wt.% unless otherwise stated):

[0226] 2. Application to strands

[0227] The dyes were applied to strands of hair (Kerling). 2.0 g of dye (F) was massaged into each gram of hair strand and left to work for 1 minute. The strands still coated with the dye were then dried with a standard hairdryer. The dyed strands were visually assessed by a trained person under a daylight lamp. The strands were stored for 24 hours.

[0228] 3. Measurement of wash fastness

[0229] Following coloring, heat treatment, and storage, each colored strand underwent five manual hair washes. For each wash, the strand was moistened, then shampoo (S1) or (S2) was massaged into the respective 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.

[0230] After each hair wash, the respective strand was again visually assessed under the daylight lamp.

[0231] The hair strands were assessed for their color intensity using a scale from 1 (very low color intensity) to 5 (very high color intensity).

[0232] 0 HW = Color result directly after coloring

[0233] 5 = high intensity 1 = low intensity

[0234] 5 = high intensity 1 = low intensity

Claims

Patent claims 1. Method for dyeing keratinous fibers, especially human hair, comprising the (1) Application of a dye (F) to the keratinous fibers which contains (F-1) at least one chitosan and / or a chitosan derivative, and (F-2) at least one colouring compound from the group of pigments and direct dyes, and the (2) Application of a shampoo (S) to the keratin fibers, which contains water and at least one surfactant and has a pH of 4.0 to 8.0, wherein the dye (F) and the shampoo (S) are different formulations.

2. Method according to claim 1, characterized in that the dye (F) contains at least one chitosan and / or one chitosan derivative (F-1) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

3. Method according to one of claims 1 to 2, characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more chitosans and / or chitosane 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.%.

4. Method according to any one of claims 1 to 3, characterized in that the coloring agent (F) contains at least inorganic pigment (F-2) which is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or micaceous oxide which are coated with at least one metal oxide and / or one metal oxychloride.

5. A method according to any one of claims 1 to 4, characterized in that the coloring agent (F) contains at least one organic pigment (F-2) preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, and orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, Cl 12370, Cl 12420, Cl 12490, Cl 14700, Cl 15525, Cl 15580, Cl 15620, Cl 15630, Cl 15800, Cl 15850, Cl 15865, Cl 15880, Cl 17200, Cl 26100, Cl 45380, Cl 45410, Cl 58000, Cl 73360, Cl 73915 and / or Cl 75470.

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

7. 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. Method according to any 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.

9. Method according to any one of claims 1 to 8, characterized in that the dye (F) contains water (F-4) and has a pH value of 2.0 to 7.5, preferably 3.0 to 7.0, more preferably 3.5 to 6.5 and most preferably 4.0 to 6.

0.

10. Method according to one of claims 8 to 9, characterized in that the components (F-1), (F-2), (F-3) and (F-4) are together contained in the dye (F) in a quantity of at least 90.0 wt.%, preferably at least 93 wt.%, further preferably at least 96 wt.% and most preferably at least 99 wt.%. 1 1 . Method according to one of claims 1 to 10, characterized in that the dye (F) is essentially 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.

12. Method according to one of claims 1 to 11, characterized in that the shampoo (S) has a pH value of 4.2 to 7.0, preferably of 4.4 to 6.8, more preferably of 4.6 to 6.6, even more preferably of 4.8 to 6.4 and most preferably of 5.0 to 6.

2.

13. Method according to any one of claims 1 to 12, characterized in that the shampoo (S) contains at least one surfactant from the group consisting of Cs-Cso-alkyl isethionates, Cs-Cso-alkyl sulfosuccinates and / or their salts.

14. Method according to any one of claims 1 to 13, comprising the (1) Application of the dye (F) to the keratinous fibers in a first step, then the (2) Application of the shampoo (S) to the keratin fibers in a second step, wherein there is a period of at most 72 hours, preferably at most 60 hours and particularly preferably at most 48 hours between steps (1) and (2).

15. Multi-component packaging unit (kit-of-parts) for dyeing keratinous fibers, in particular human hair, comprising separately assembled a first container with a dye (F), and a second container with a shampoo (S), wherein the dye (F) and the shampoo (S) are defined in claims 1 to 13.

16. Use of a shampoo (S) to improve the color retention of a dye (F) on keratinous fibers, in particular human hair, wherein the dye (F) and the shampoo (S) are defined in claims 1 to 13.

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