Method for dyeing keratin fibres, comprising the use of a dye having a film-forming polymer and a dyeing compound, and the use of an aftertreatment agent having a film-forming polymer

Abstract

The present invention relates to a method for dyeing keratin fibres, in particular human hair, comprising (1) applying a silicone-free dye (F) to the keratin fibres, said dye containing (F-1) at least a film-forming polymer and (F-2) at least a dyeing compound from the group of pigments, direct dyes and oxidation dye precursors, and (2) applying a non-dyeing, silicone-free aftertreatment agent (N) to the keratin fibres, said aftertreatment agent containing (N-1) at least a film-forming polymer.

Description

[0001] Method for dyeing keratin fibers, comprising the application of a dyeing agent with film-forming polymer and coloring compound and the application of a post-treatment agent with film-forming polymer

[0002] The present application relates to a process for dyeing keratinous fibers, in particular human hair, comprising the application of a dyeing agent (F) and the application of a post-treatment agent (N). The dyeing agent (F) is silicone-free, contains at least one film-forming polymer (F-1), and at least one coloring compound (F-2) from the group consisting of pigments, direct dyes, and oxidation dye precursors. The post-treatment agent (N) is also silicone-free and contains at least one film-forming polymer (N-1).

[0003] A second subject matter of the present application is a non-staining, silicone-free post-treatment agent for use on dyed keratinous fibers, which contains chitosan and / or chitosan derivatives, at least one acid, ethanol and water in specified quantity ranges.

[0004] The alteration of the shape and color of keratin fibers, particularly human hair, represents an important area of ​​modern cosmetics. Silicones have been widely used in hair dyes because they form a glossy film on the hair, making it appear fuller, smoother, and healthier. Pigment-based surface colorations often utilize silicones or reactive silane compounds to bind the pigments to the hair surface as permanently as possible. However, there has been a growing trend toward using the most environmentally friendly products possible, and sustainability-conscious consumers are increasingly seeking silicone-free cosmetics. Therefore, there is a strong need for the development of silicone-free dyes with good coloring performance.

[0005] Depending on the desired result, a professional hairstylist knows various coloring systems for changing hair color. For permanent, intense colorations with good colorfastness and gray coverage, oxidation dyes are typically used. These dyes contain oxidation dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidation dyes are characterized by very long-lasting color results. With direct dyes, pre-formed dyes diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, colors achieved with direct dyes are less durable and fade more quickly.Dyes using direct dyes typically remain on the hair for a period of between 5 and 20 washes.

[0006] For temporary color changes to hair and / or skin, the use of color pigments is well-known. Pigments, or color pigments, are generally understood to be insoluble, coloring substances. These are present in the coloring formulation in the form of small particles and are simply deposited on the hair fibers and / or the skin surface. Therefore, they can usually be removed completely after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name "hair mascara."

[0007] Dyeing with pigments offers several significant advantages. Since the pigments adhere only to the keratin material, particularly the hair fibers, unwanted colors can be removed quickly, easily, and completely, allowing users to return to their original hair color immediately and effortlessly. This makes the dyeing process especially attractive for consumers who don't want to regularly dye their hair.

[0008] Despite these many advantages, the pigment-based dyeing system still has some disadvantages, which stem from the limited penetration depth of the pigments into the keratinous material. Since the pigments do not diffuse into the keratin fiber but merely deposit on the outside of the fiber in the form of a coating or film, the wash fastness of dyes produced with this system still needs improvement. Various studies have attempted to bind the pigment(s) more permanently to the hair surface using film-forming materials, mostly polymers.

[0009] For example, German patent DE 19847883 A1 deals with achieving pigment-based colorations using dyes containing at least one chitosan and one pigment. Combining the pigments with chitosan should improve the abrasion resistance of the colorations. The major advantage of chitosan as a film-forming material is that it is based on biopolymers and therefore offers improved environmental compatibility and biodegradability. As many users show increasing interest in products made with sustainable or renewable raw materials, the use of biopolymers is becoming increasingly important.

[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, rather than pigments, were used as the coloring compounds.

[0011] Even though colorations achieved with pigment or dye and chitosan offer good initial intensity, they still have drawbacks regarding their wash fastness. Achieving even coloring across the entire hair length also cannot yet be considered optimal, as the durability of the films can vary on different sections of the hair, especially at the roots and ends.

[0012] The objective of the present application was therefore to provide a dye that binds coloring compounds (especially pigments) to the surface of keratin fibers via a film, enabling intense colorations with improved wash fastness. The dyeing process was to be carried out using biopolymers, and the keratin fibers or hair dyed in this way were not to feel coated or greasy, but rather to exhibit a healthy shine, and the elasticity of the keratin fibers was not to be negatively affected.

[0013] Since organosilicon compounds such as silicones and silanes possess excellent application properties but are poorly biodegradable, the products and processes in which they are used should be free of organosilicon compounds such as silicones and silanes. When applied to keratin fibers or human hair, intense coloring results with good fastness properties, particularly good wash fastness and color retention, should be achieved. To date, it has proven difficult to maintain the excellent application results obtained with silicones and organosilicon compounds without their use.

[0014] Surprisingly, it has now been found that keratin fibers, initially dyed using a chitosan-based dye and pigment or dye, exhibit particularly improved wash fastness when a polymer-containing, especially chitosan-containing, non-dyeing post-treatment or sealing agent is applied in a subsequent step. In this way, intense, highly durable colorations could be achieved on the hair even without the use of organosilicon compounds.

[0015] A first object of the present invention is a method for dyeing keratinous fibers, in particular human hair, comprising the

[0016] (1) Application of a silicone-free dye (F) to the keratinous fibers, which contains

[0017] (F-1) at least one film-forming polymer and (F-2) at least one colouring compound from the group consisting of pigments, direct dyes and oxidation dye precursors, and the

[0018] (2) Application of a non-staining, silicone-free after-treatment agent (N) to the keratinous fibers, which contains

[0019] (N-1) at least one film-forming polymer.

[0020] In step (1) of the process according to the invention, the dye is applied to the keratin fibers. The dye contains at least one film-forming polymer (F-1) and at least one coloring compound (F-2). The film-forming polymer (F-1) is preferably a biodegradable polymer. The dye (F) is silicone-free, meaning that it is free of organosilicon compounds. The coloring compound (F-2) can be one or more pigments, direct dyes, and / or oxidation dye precursors. The subsequent application (2) following step (1) comprises the application of the silicone-free, non-coloring post-treatment agent (N). This means that the post-treatment agent (N), like the dye (F), is free of organosilicon compounds.The post-treatment agent (N) contains at least one film-forming polymer (N-1), particularly preferably at least one biodegradable film-forming polymer.

[0021] The hair dyed or dyed and washed using these methods was characterized by colorations with particularly high intensity and good wash fastness.

[0022] Keratinous fibers

[0023] Keratinous fibers include wool, fur, feathers, and especially human hair. Human hair is particularly favored as a keratinous fiber.

[0024] dyeing agents

[0025] The term "coloring agent" is used within the scope of this invention to describe the coloring of keratin material, particularly hair, by the use of pigments and / or direct dyes and / or oxidation dye precursors. Pigments are particularly preferred for this coloring process because they are integrated as color-imparting compounds into the polymer film, which is deposited on the surface of the keratin fibers or surrounds them in the form of a particularly homogeneous, thin, uniform, and smooth film.

[0026] Application of the dye (F) to keratinous fibers

[0027] In step (1) of the dyeing process according to the invention, a dyeing agent (F) is applied to the keratinous fibers or the human hair, which contains at least one film-forming polymer (F-1) and at least one coloring compound (F-2) from the group consisting of pigments, direct dyes and oxidation dye precursors.

[0028] The dye (F) is a ready-to-use dye.

[0029] When applying the dye (F), it can be applied to the keratin fibers, for example with a gloved hand or using a brush or applicator, and gently massaged in if necessary. Silicone-free products

[0030] Both the dyeing agent (F) and the after-treatment agent (N) are characterized by being silicone-free.

[0031] For the purposes of this application, the term "silicone-free" means that both products are free of organosilicon compounds. Organosilicon compounds are organic compounds whose structure includes at least one silicon atom. Examples of organosilicon compounds commonly used in cosmetics include silicones, silicone derivatives, polydimethylsiloxanes, polydimethylsiloxane derivatives, silanes, and silane derivatives.

[0032] In other words, the first subject matter of the invention relates to a method for dyeing keratinous fibers, in particular human hair, comprising the

[0033] (1) Application of a dye (F) to the keratinous fibers which contains

[0034] (F-1) at least one film-forming polymer and

[0035] (F-2) at least one colouring compound from the group consisting of pigments, direct dyes and oxidation dye precursors, and the

[0036] (2) Application of a non-staining after-treatment agent (N) to the keratinous fibers, which contains

[0037] (N-1) at least one film-forming polymer wherein the dye (F) and the post-treatment agent (N) are free of organosilicon compounds.

[0038] The term "free from" means that the dye (F) contains no organosilicon compounds, i.e., that the total content of organosilicon compounds in the dye (F) is 0% by weight. Similarly, the post-treatment agent (N) also contains no organosilicon compounds, i.e., the total content of organosilicon compounds in the post-treatment agent (N) is 0% by weight. Film-forming polymers (F-1) in the dye (F) and in the post-treatment agent: As a first essential component, the dye (F) used in the process according to the invention contains at least one film-forming polymer (F-1). The post-treatment agent (N) used in the process according to the invention also contains at least one film-forming polymer (F-1).

[0039] Polymers are defined as macromolecules with a molecular weight of at least 1000 g / mol, preferably at least 2500 g / mol, and particularly preferably at least 5000 g / mol, which consist of identical (or a group of identical), repeating organic units.

[0040] The maximum molecular weight of the polymer can depend on the degree of polymerization (number of polymerized monomers) and the batch size, and is also determined by the polymerization method. For polymers from natural sources, the maximum molecular weight depends on the source from which the polymer is obtained. For the purposes of the present invention, it is preferred if the maximum molecular weight of the film-forming polymer (F-1) and / or (N-1) does not exceed 10 7 g / mol, preferably not more than 10 6 g / mol and particularly preferably not more than 10 5 g / mol.

[0041] For the purposes of the invention, a film-forming polymer is understood to be a polymer capable of forming a film on a substrate, for example, on a keratin fiber or hair. The formation of a film can be demonstrated, for example, by examining the keratin fibers treated with the polymer under a microscope.

[0042] Based on the experiments conducted, the theory was developed that the coloring compounds, especially pigments, are deposited on the surface of the keratin fibers in the film formed by the film-forming polymer(s) (F-1). The film's resistance proved to be greatest when it was as intact and undamaged as possible, thus offering no point of attack against external forces. The coloration obtained from the dye (F) resulted in high intensity immediately after dyeing, but this washed out relatively quickly after several shampooing treatments. The application of the non-coloring aftertreatment agent (N) increased the film thickness, but, more importantly, it also appeared to subsequently cover incompletely or unevenly coated areas of the fibers, leading to greater uniformity and thus increased film resistance.

[0043] Microscopic images suggest that the pigment embedded in the film, which is essential for coloration, can represent a weakening defect where the film degrades first. This defect could be covered by depositing an additional polymer layer without pigments. The layering of the film by applying the post-treatment agent (N) worked best when the same polymer or polymer type was present in both the dye (F) and the non-dyeing post-treatment agent (N). For example, if the dye (F) contained at least one chitosan (F-1), particularly resistant films were produced when the post-treatment agent (N) also contained at least one chitosan (N-1).

[0044] In a particularly preferred embodiment, a method according to the invention is therefore characterized in that the post-treatment agent (N) contains at least one film-forming polymer (N-1) which is also contained in the dyeing agent (F).

[0045] Nonionic, anionic, and cationic polymers can be used as film-forming polymers in the dye (F) and / or the post-treatment agent (N). Since the dye (F) and the post-treatment agent (N) should be as sustainable as possible, a biodegradable and / or nature-based film-forming polymer is particularly preferred as the film-forming polymer (F-1) and (N-1), respectively.

[0046] A biodegradable polymer is defined as a polymer that, after 6 months in an aqueous medium, has been converted to carbon dioxide by 70 wt%.

[0047] A nature-based polymer is a polymer derived from a natural source and used either as such or first derivatized and then used. Particularly suitable nature-based polymers can be selected from the group of polysaccharides and natural gums. Polyaminosaccharides, especially chitosan and / or chitosan derivatives, are explicitly preferred.

[0048] In a further particularly preferred embodiment, a method according to the invention is characterized in that the coloring agent (F) and / or the post-treatment agent (N) contains at least one nature-based film-forming polymer, which is preferably selected from the group consisting of polysaccharides and natural gums, particularly preferably from the group consisting of polyaminosaccharides, and most preferably from the group consisting of chitosan and the derivatives of chitosan.

[0049] Examples of suitable film-forming, hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, and carob gum.

[0050] For the purposes of this invention, cellulose refers to both cellulose itself and a derivative thereof, i.e., a chemically or physically modified cellulose. Cellulose is composed of β-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions alternate with those of lower order (amorphous regions) in cellulose. Natural and manufacturing-related impurities, such as the presence of carboxyl groups, are typically in the range of approximately 1%. According to the invention, cellulose itself is therefore considered a nonionic polysaccharide.

[0051] A cellulose that can be used according to the invention can have a degree of polymerization (DP), i.e. a chain length of glucopyranose units, of 10 to approximately 8000.

[0052] Microcrystalline cellulose, for example, can be used as a suitable cellulose. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of celluloses, in which only the amorphous regions of the semi-crystalline cellulose are attacked and completely dissolved. This initially results in microfine cellulose, which is then disaggregated into microcrystalline cellulose in aqueous suspension under mechanical stress.

[0053] The degree of polymerization remaining after hydrolysis (also called leveling-off polymerization degree = LODP) of microcrystalline cellulose is in the range of approximately 30-400. Therefore, microcrystalline celluloses with a degree of polymerization of 30 to 400 are particularly suitable.

[0054] For the purposes of this invention, cellulose also includes derivatives of cellulose, i.e., cellulose that can be modified with substituents and / or bear further chemical functional groups by reaction with a chemical agent. Such chemically modified celluloses can be nonionic, cationic, and / or anionic.

[0055] A suitable cationic cellulose is marketed, for example, under the name Polymer JR® 400 by Amerchol and has the INCI name Polyquaternium-10. Another cationic cellulose bears the INCI name Polyquaternium-24 and is marketed under the trade name Polymer LM-200 by Amerchol or also Quatrisoft® LM 200. Other commercially available products include the compounds Celquat® H 100, Celquat®, and L 200. The aforementioned commercial products are preferred cationic celluloses.

[0056] Nonionic celluloses are particularly preferred. These can be selected, for example, from the group consisting of hydroxypropyl methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methylcellulose, hydroxyethyl ethylcellulose, ethylcellulose, methyl ethylcellulose, and methylcellulose. These are marketed, for example, under the brand names Culminal® and Benecel®, and Natrosol® by companies such as Aqualon, Hercules, and Ashland. Suitable anionic celluloses include, for example, carboxymethylcellulose and / or one of its physiologically compatible salts, such as their sodium and / or potassium salts.

[0057] A method for dyeing keratinous fibers, especially human hair, is particularly preferred, encompassing the

[0058] (1) Application of a silicone-free dye (F) to the keratinous fibers, which contains

[0059] (F-1) at least one polysaccharide and

[0060] (F-2) at least one colouring compound from the group consisting of pigments, direct dyes and oxidation dye precursors, and the

[0061] (2) Application of a non-staining, silicone-free after-treatment agent (N) to the keratinous fibers, which contains

[0062] (N-1) at least one polysaccharide.

[0063] Polyaminosaccharides are particularly well-suited for this purpose. Polyaminosaccharides are wholly or partially composed of amino sugars in which one or more hydroxyl groups are replaced by an amino group.

[0064] The use of chitosan and / or a chitosan derivative in the dye (F) and / or in the post-treatment agent (N) is explicitly preferred. It is most preferred if both the dye (F) and the post-treatment agent (N) contain chitosan.

[0065] A method for dyeing keratinous fibers, especially human hair, is also explicitly and particularly preferred, encompassing the

[0066] (1) Application of a silicone-free dye (F) to the keratinous fibers, which contains

[0067] (F-1) at least one chitosan and / or one chitosan derivative and

[0068] (F-2) at least pigment, and the

[0069] (2) Application of a non-staining, silicone-free after-treatment agent (N) to the keratinous fibers, which contains

[0070] (N-1) at least one chitosan and / or one chitosan derivative.

[0071] The most preferred method is one for dyeing keratinous fibers, especially human hair, comprising the

[0072] (1) Application of a silicone-free dye (F) to the keratinous fibers, which contains

[0073] (F-1) at least one chitosan and

[0074] (F-2) at least pigment, and (2) the application of a non-staining, silicone-free after-treatment agent (N) to the keratinous fibers, which contains (N-1) at least chitosan.

[0075] Chitosan, also known as polyglucosamine or poly-D-glucosamine, is a naturally occurring biopolymer derived from chitin, which is composed of β-1,4-glycosidically linked N-acetylglucosamine residues (specifically, 2-acetamido-2-deoxy-β-D-glucopyranose residues). Like chitin, it is a polyaminosaccharide. Chitosan is produced by deacetylating chitin, resulting in a molecule consisting solely of linearly linked 2-amino-2-deoxy-β-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4.

[0076] Chitosan is preferably produced from chitin, which is found in shellfish or crustaceans. Chitosan is industrially produced from chitin by deacetylation. This can be achieved, for example, using (hot) sodium hydroxide or enzymatically. Both processes are used industrially, but the alkaline method is clearly the most prevalent in terms of volume. The degree of deacetylation can vary: it can be complete or partial, resulting in a distribution of strongly deacetylated areas alongside weakly deacetylated areas, or a homogeneous deacetylation distribution. Simultaneously, this chemical process can decrease the polymer chain length (depolymerization). The molecular weight of chitosan can range widely, for example, from 20,000 to approximately 5 million g / mol.

[0077] Chitosan derivatives are compounds with a chitosan core structure in which at least some of the existing functional groups have been chemically modified. Chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure.

[0078] For example, a chitosan with a molecular weight of 20,000 to 800,000 g / mol is very suitable, preferably 50,000 to 600,000 g / mol, more preferably 80,000 to 450,000 g / mol and most preferably 100,000 to 300,000 g / mol.

[0079] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains at least one chitosan and / or one chitosan derivative (F-2) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

[0080] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and the post-treatment agent (N) contain at least one chitosan and / or one chitosan derivative (F-2) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

[0081] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from the company Sigma Aldrich, for example.

[0082] A chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Daltons) is, for example, commercially available in pharmaceutical purity from BioLog Heppe (Kraeber). The degree of deacetylation of this chitosan is 88–95%.

[0083] Another low molecular weight chitosan with a molecular weight of approximately 70,000 g / mol, which also bears the CAS number 9012-76-4, can be obtained commercially from the company Fluka as deacetylated chitin of a white solid.

[0084] Chitosan in the form of its hydrochloride can be obtained as vegan chitosan from the company Sandream Impact. The hydrochloride of chitosan is a chitosan derivative according to the invention.

[0085] Another very suitable chitosan can also be purchased commercially under the trade name HYDAMER™ HCMF from Chitinor (Seagarden). The degree of deacetylation of this chitosan raw material is at least 75%.

[0086] Chitosan 027 is a suitable, commercially available, high molecular weight chitosan from the company Polymar, which has a molecular weight of 100,000 - 2,000,000 g / mol.

[0087] The thickness of the polymer film that forms on the keratin fibers can be influenced by both the amount of dye or post-treatment agent applied and the polymer content of both agents. On the one hand, the film must not be too thin so that it possesses sufficient resistance to external influences.

[0088] Preferably, at least 0.01 wt.%, more preferably at least 0.05 wt.%, even more preferably at least 0.2 wt.% and most preferably at least 0.3 wt.% chitosan and / or chitosan derivative are used in the dyeing agent (F) and in the post-treatment agent (N).

[0089] On the other hand, the film should not be too thick, as it is otherwise more likely to form unevenly or become inflexible. If the keratin fibers are coated with a film that is too thick, the hair will also feel significantly stiffer and more coated. Since thin formulations coat the keratin fibers more quickly and evenly, the viscosity of the coloring agent (F) and the after-treatment agent (N) is preferably not chosen to be too high. Chitosan, especially when used in a water-based cosmetic carrier, also possesses thickening properties itself; therefore, it has proven particularly advantageous not to exceed a chitosan or chitosan derivative content in the coloring agent (F) and / or the after-treatment agent (N) of 2.5 wt.%, preferably 1.5 wt.%, more preferably 1.3 wt.%, and most preferably 1.1 wt.%.All figures given in weight percent refer to the total weight of the respective product.

[0090] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and / or the post-treatment agent (N) - each based on the total weight of the respective agent - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 2.5 wt.%, preferably 0.05 to 1.5 wt.%, more preferably 0.2 to 1.3 wt.%, and most preferably 0.3 to 1.1 wt.%.

[0091] In a further particularly preferred embodiment, a method according to the invention is characterized in that

[0092] - the dye (F) - based on the total weight of the dye (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 2.5% by weight, and

[0093] - the post-treatment agent (N) - based on the total weight of the dye (N) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 2.5 wt.%.

[0094] In a further particularly preferred embodiment, a method according to the invention is characterized in that

[0095] - the dye (F) - based on the total weight of the dye (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.05 to 1.5% by weight, and

[0096] - the post-treatment agent (N) - based on the total weight of the dye (N) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.05 to 1.5 wt.%.

[0097] In a further particularly preferred embodiment, a method according to the invention is characterized in that

[0098] - the dye (F) - based on the total weight of the dye (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.2 to 1.3 wt.%, and

[0099] - the post-treatment agent (N) - based on the total weight of the dye (N) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.2 to 1.3 wt.%. In a further particularly preferred embodiment, a method according to the invention is characterized in that

[0100] - the dye (F) - based on the total weight of the dye (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.3 to 1.1% by weight, and

[0101] - the post-treatment agent (N) - based on the total weight of the dye (N) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.3 to 1.1 wt.%.

[0102] Further investigations have shown that the films produced by the dye (F) and the post-treatment agent (N) preferentially have comparable thicknesses. When the dyed film obtained after application of the dye (F) was approximately the same thickness as the undyed film that formed over the dyed film after application of the post-treatment agent (N), the resulting film composed of the two layers was particularly resistant, yet still intensely colored. With comparable compositions of the dye (F) and the post-treatment agent (N), it can be assumed that the thickness of the formed film depends primarily on the amounts of the film-forming polymers (especially the chitosan derivatives) in the two agents.For these reasons, it is particularly preferred if the coloring agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​contain the film-forming polymer(s) (F-1) and the film-forming polymer(s) (N-1) in a weight ratio (F-1) / (N-1) of 1:4 to 4:1, preferably of 1:3 to 3:1, more preferably of 1:2 to 2:1, even more preferably of 1:1.5 to 1.5:1 and particularly preferably of 1:1.2 to 1.2:1.

[0103] In a further particularly preferred embodiment, a method according to the invention is characterized in that the coloring agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​contain the film-forming polymer(s) (F-1) and the film-forming polymer(s) (N-1) in a weight ratio (F-1) / (N-1) of 1 :4 to 4:1, preferably of 1 :3 to 3:1, more preferably of 1 :2 to 2:1, even more preferably of 1 :1.5 to 1.5:1 and particularly preferably of 1 :1.2 ​​to 1.2:1.

[0104] Example

[0105] In the inventive method, 100 g of dyeing agent (F) and 100 g of after-treatment agent (N) are applied to the head of a test subject.

[0106] The dye (F) contains 0.9 g of chitosan. Based on the total weight of the dye (F), the dye contains 0.9 wt% chitosan (F-1).

[0107] The post-treatment agent (N) contains 0.9 g of chitosan. Based on the total weight of the post-treatment agent (N), the post-treatment agent contains 0.9 wt% chitosan (N-1).

[0108] The weight ratio (F-1 ) / (N-1 ) is 0.9 wt.% / 0.9 wt.% = 1 : 1. Coloring compounds (F-2) in the dye (F)

[0109] As a second essential component, the dye (F) used in step (1) of the process according to the invention contains at least one coloring compound (F-2) from the group consisting of pigments, direct dyes and oxidation dye precursors.

[0110] In principle, the dye (F) can also contain oxidation dye precursors, however, the process is particularly suitable for the formation of colorations via surface coloration, in which direct dyes, but especially preferably one or more pigments, are used as coloring compounds.

[0111] For the purposes of this invention, pigments are understood to be coloring compounds which have a solubility in water at 25 °C of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. The water solubility can be determined, for example, by the method described below: 0.5 g of the pigment is weighed into a beaker. A magnetic stir bar is added. Then one liter of distilled water is added. This mixture is heated to 25 °C for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L. If the pigment-water mixture cannot be visually assessed due to the high intensity of the pigment, which may be finely dispersed, the mixture is filtered.If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0112] 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 post-treatment agent is applied to keratin material which has been colored by the application of at least one inorganic and / or organic pigment. Pigments with a specific shape and / or metallic pigments have also proven to be particularly well suited for solving the problem described in the invention.

[0113] In a further particularly preferred embodiment, a method according to the invention is characterized in that the coloring agent (F) contains at least one coloring compound (F-2) from the group of pigments, which is preferably selected from the group of inorganic pigments, organic pigments, pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0114] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be produced, for example, from chalk, ochre, umber, green earth, burnt sienna, or graphite. Furthermore, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0115] Particularly suitable are colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates. Especially preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0116] Colored pearlescent pigments are also particularly preferred according to the invention. These are typically mica- and / or micaceous and can be coated with one or more metal oxides. Mica belongs to the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0117] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as a pearlescent pigment. Particularly favored pearlescent pigments are based on natural or synthetic mica and coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by changing the thickness of the metal oxide layer(s).

[0118] In a further preferred embodiment, a method according to the invention is characterized in that the coloring agent (F) contains at least inorganic pigment (F-2), which is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or micaceous oxide, which are coated with at least one metal oxide and / or one metal oxychloride.

[0119] In a further preferred embodiment, a method according to the invention is characterized in that the coloring agent (F) contains at least one pigment (F-2) selected from mica- or micaceous-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510). Examples of particularly suitable color pigments are available commercially under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[0120] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise:

[0121] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0122] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0123] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0124] Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0125] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0126] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0127] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0128] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0129] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0130] Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0131] Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)

[0132] Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)

[0133] Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)

[0134] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510)

[0135] Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0136] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0137] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0138] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

[0139] Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0140] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0141] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0142] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0143] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0144] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0145] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0146] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides) Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0147] Other particularly preferred color pigments with the trade name Xirona® include, for example:

[0148] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0149] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0150] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0151] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0152] Furthermore, particularly preferred color pigments with the trade name Unipure® include, for example:

[0153] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0154] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0155] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0156] In another embodiment, the applied dye may also contain one or more organic pigments.

[0157] The organic pigments according to the invention are correspondingly insoluble organic dyes or color lakes, which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolin, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine, and / or triarylmethane compounds.

[0158] Particularly suitable organic pigments include, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, and red pigments with the Color Index Numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.In a further particularly preferred embodiment, a method according to the invention is 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 C1 11680, C1 11710, C1 15985, C1 19140, CI 20040, CI 21 100, CI 21 108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, and orange pigments with the color index Numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0159] The organic pigment can also be a paint lake. For the purposes of this invention, the term "paint lake" refers to particles comprising a layer of absorbed dyes, wherein the particle-dye unit is insoluble under the aforementioned conditions. These particles can be, for example, inorganic substrates such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum itself.

[0160] For example, alizarin lacquer can be used as a colored lacquer.

[0161] Pigments with a specific shape can also be used to stain keratin fibers. For example, a pigment based on a lamellar and / or lenticular substrate platelet can be used. Furthermore, staining based on a substrate platelet containing a vacuum-metallized pigment is also possible.

[0162] In a further preferred embodiment, a method according to the invention is 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.

[0163] The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred thickness ranges for the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm; 2.5 to 20 nm, 5 to 20 nm, and 10 to 20 nm. Preferably, each substrate platelet has as uniform a thickness as possible. Due to the small thickness of the substrate platelets, the pigment exhibits particularly high opacity.

[0164] The substrate platelets are preferably monolithic. In this context, monolithic means consisting of a single, closed unit without fractures, layering, or inclusions, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous, meaning that no concentration gradient exists within the platelets. In particular, the substrate platelets are not layered and do not contain any particles or other distributed particles.

[0165] The size of the substrate platelet can be tailored to the specific application, particularly the desired effect on the keratinous material. Typically, the substrate platelets have a mean maximum diameter of approximately 2 to 200 pm, especially approximately 5 to 100 pm.

[0166] In a preferred embodiment, the aspect ratio, expressed as the ratio of the mean size to the mean thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The mean size of the uncoated substrate platelets is defined as the d50 value of the uncoated substrate platelets. Unless otherwise specified, the d50 value was determined using a Sympatec Heios instrument with Quixel wet dispersion. For sample preparation, the sample to be tested was pre-dispersed in isopropanol for 3 minutes.

[0167] The substrate plates can be made from any material that can be formed into platelet form.

[0168] They can be of natural origin or synthetically produced. Materials from which the substrate plates can be constructed include, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. Preferably, the substrate plates are composed of metal (alloys).

[0169] Any metal suitable for metallic luster pigments can be used. Such metals include iron and steel, as well as all air- and water-resistant (semi-)metals such as platinum, zinc, chromium, molybdenum, and silicon, and their alloys such as aluminum bronzes and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum and brass platelets, with aluminum platelets being particularly preferred. Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

[0170] Due to their irregular structure, pigments based on lamellar substrate platelets produce a high proportion of scattered light. Furthermore, these pigments do not completely mask the existing color of a keratinous material, and effects similar to natural graying can be achieved.

[0171] Lenticular (lens-shaped) substrate platelets have a generally regular, rounded edge and are also referred to as "silver dollars" due to their appearance. Because of their regular structure, pigments based on lenticular substrate platelets have a high proportion of reflected light.

[0172] Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated films. They are characterized by a particularly thin substrate platelet, ranging from 5 to 50 nm, and by a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum metallized pigment are also referred to as VMP substrate platelets within the scope of this application. Aluminum VMP substrate platelets, for example, can be obtained by releasing aluminum from metallized films.

[0173] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0174] Uncoated lamellar, lenticular and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect the incident light to a high degree and produce a light-dark flop. These have proven particularly advantageous for use in dyes.

[0175] Suitable pigments based on a lamellar substrate platelet include, for example, the VISIONAIRE series pigments from Eckart.

[0176] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH. Pigments based on a substrate platelet containing a vacuum metallized pigment are available, for example, under the names Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0177] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the composition according to the invention is particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. Therefore, according to the invention, it is advantageous if the at least one pigment has a mean particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, and particularly of 14 to 30 pm. The mean particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0178] As a coloring compound (F-2), the dye (F) may also contain at least one direct dye. Direct dyes are dyes that adhere directly to the hair and do not require an oxidative process to develop the color. Typical direct dyes are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0179] Direct dyes can be nonionic, cationic, or anionic. It is particularly preferred if the dye (F) contains at least one anionic direct dye, which can alternatively also be referred to as an acid dye.

[0180] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) contains at least one coloring compound (F-2) from the group of direct dyes, particularly preferably from the group of anionic direct dyes.

[0181] Anionic direct-drawing dyes are also known as acid dyes. Acid dyes are defined as direct-drawing dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H) and / or one sulfate group (-OSO3H). Depending on the pH, the rudimentary forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups exist in equilibrium with their deprotonated forms (-COO-, -SOs, or -OSOs-). The proportion of rudimentary forms increases with decreasing pH. When direct-drawing dyes are used in the form of their salts, the carboxylic acid or sulfonic acid groups exist in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or potassium salts.Alkaline earth salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali salts. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), they do not fall under the definition of a direct-drawing dye.

[0182] A key characteristic of acid dyes is their ability to form anionic charges, with the carboxylic acid or sulfonic acid groups responsible for this typically being linked to various chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes, and / or indophenol dyes.

[0183] Als Beispiele für Säurefarbstoffe können genannt werden: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n° : C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2- Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (C.l. 16230; Orange G sodium salt), Acid Orange 11 (Cl 45370), Acid Orange 15 (Cl 50120), Acid Orange 20 (Cl 14600), Acid Orange 24 (BROWN 1 ;CI20170;KATSU201 ;nosodiumsalt;Brown No.201 ;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201 ;D & C Brown No.1), Acid Red 14 (C.1.14720), Acid Red 18 (E124, Red 18; Cl 16255), Acid Red 27 (E 123, Cl 16185,C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, Cl 17200), Acid Red 35 (Cl C.l.18065), Acid Red 51 (Cl 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (Cl 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (Cl 27290), Acid Red 87 (Eosin, Cl 45380), Acid Red 92 (COLIPA n° C53, Cl 45410), Acid Red 95 (Cl 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (Cl 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.l. 60730, COLIPA n° C063), Acid Violet 49 (Cl 42640), Acid Violet 50 (Cl 50325), Acid Blue 1 (Patent Blue, Cl 42045), Acid Blue 3 (Patent Blau V, Cl 42051), Acid Blue 7 (Cl 42080), Acid Blue 104 (Cl 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, Cl 42090, C.l. Food Blue 2), Acid Blue 62 (Cl 62045), Acid Blue 74 (E 132, Cl 73015), Acid Blue 80 (Cl 61585), Acid Green 3 (Cl 42085,Foodgreenl), Acid Green 5 (Cl 42095), Acid Green 9 (C.1.42100), Acid Green 22 (C.1.42170), Acid Green 25 (Cl 61570, Japan Green 201 , D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, Cl 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 and / or D&C Brown 1. 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 und / oder D&C Brown 1 .,

[0184] Since the alkaline earth salts (such as calcium and magnesium salts) or aluminum salts of acid dyes have lower solubility than the corresponding alkali metal salts, an organic dye that can be considered an acid dye in the form of its alkali metal salt can also exist as a pigment if the counterion for the acid group(s) is not an alkali metal ion, but an alkaline earth metal or an analogous, correspondingly more highly charged counterion. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), the compounds do not fall under the definition of a direct-drawing dye.

[0185] Like pigments, acid dyes are not intended to diffuse primarily into the keratin fiber, but rather to be preferentially deposited embedded in the chitosan film on the surface of the keratin fibers. For this reason, acid dyes are particularly preferred, even those whose solubility is so high that they can no longer be classified as organic pigments, but which nevertheless have relatively poor solubility.

[0186] For this reason, acid dyes are particularly preferred as organic coloring compounds (F-2) which have a solubility in water at 25 °C of more than 0.5 g / L and less than 20 g / L, preferably less than 18 g / L, even more preferably less than 15 g / L and most preferably less than 12 g / L.

[0187] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the dye (F) as an organic coloring compound (F-2) contains at least one acid dye which has a solubility in water at 25 °C of more than 0.5 g / L and less than 20 g / L, preferably more than 0.5 g / L and less than 18 g / L, more preferably more than 0.5 g / L and less than 15 g / L, and most preferably more than 0.5 g / L and less than 12 g / L. The water solubility of the anionic direct dyes can be determined, for example, by the following method. 0.1 g of the anionic direct dye is placed in a beaker. A magnetic stir bar is added. Then 100 ml of water are added. This mixture is heated to 25 °C on a magnetic stirrer while stirring. Stirring continues for 60 minutes. The aqueous mixture is then visually inspected.If undissolved dye remains, the amount of water is increased – for example, in 10 ml increments. Water is added until the entire amount of dye used is dissolved. If the dye-water mixture cannot be visually assessed due to the high intensity of the dye, the mixture is filtered. If some undissolved dye remains on the filter paper, the solubility test is repeated with a larger amount of water. If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g / L.

[0188] 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).

[0189] Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonic acids of 2-(2-quinolyl)- 1 H-indene-1 ,3(2H)-dione and has a water solubility of 20 g / L (25 °C).

[0190] 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).

[0191] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

[0192] 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).

[0193] 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.%.

[0194] 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).

[0195] Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose water solubility is given as greater than 10 g / L (25 °C).

[0196] Brilliant Blue FCF, also known as Food Blue 2 or Acid Blue 9, is known as disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl}{(4Z)-4-[ethyl(3-sulfonatobenzyl)amino]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate and has the CAS number 3844-45-9. The disodium salt of Acid Blue 9 has a water solubility of more than 20% by weight (25 °C). Acid Blue 74 is also known as Indigo Carmine, Food Blue 1, or FD&C Blue 2, and its chemical name is indigo-5,5'-disulfonic acid, disodium salt, or disodium 5,5'-(2-(1,3-dihydro-3-oxo-2H-indazol-2-ylidene)-1,2-dihydro-3H-indol-3-one)disulfonate. Acid Blue 74, in its disodium salt form, has a solubility of 10 g / L in water at 25 °C. Acid Blue 74 (disodium salt) has the Color Index number 73015 and can be purchased, for example, under the trade name Bleu Covalac W6504.

[0197] The coloring compound(s) (F-2) constitute the second essential component of the dye (F) according to the invention and are preferably used in specific average quantities. Particularly good results were obtained when the dye (F) contained one or more coloring compounds (F-2) in a total amount of 0.10 to 2.5 wt.%, preferably 0.15 to 1.7 wt.%, more preferably 0.2 to 1.3 wt.%, even more preferably 0.25 to 0.8 wt.%, and most preferably 0.3 to 1.0 wt.%.

[0198] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more coloring compounds (F-2) in a total amount of 0.10 to 2.5 wt.%, preferably 0.15 to 1.7 wt.%, more preferably 0.2 to 1.3 wt.%, even more preferably 0.25 to 0.8 wt.% and most preferably 0.3 to 1.0 wt.%.

[0199] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more pigments (F-2) in a total amount of 0.10 to 2.5 wt.%, preferably 0.15 to 1.7 wt.%, more preferably 0.2 to 1.3 wt.%, even more preferably 0.25 to 0.8 wt.% and most preferably 0.3 to 1.0 wt.%.

[0200] In a further embodiment, the robustness of the films obtained by the dyeing process could also be improved when the film-forming polymers (N-1) were used in a specific weight ratio to the coloring compounds (F-2). When the dyeing agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​contained the film-forming polymer(s) (N-1) and the coloring compound(s) (F-2) in a weight ratio (N-1) / (F-2) of 5:1 to 1:1, preferably 4:1 to 1:1, more preferably 3:1 to 1:1, and particularly preferably 3:1 to 1.5:1, the films produced by the dyeing process exhibited particularly good wash fastness.In a further preferred embodiment, a method according to the invention is therefore characterized in that the coloring agent (F) and the post-treatment agent (N) - each based on the total weight of the respective agent - contain the film-forming polymer(s) (N-1) and the coloring compound(s) (F-2) in a weight ratio (N-1) / (F-2) of 5:1 to 1:1, preferably of 4:1 to 1:1, more preferably of 3:1 to 1:1 and particularly preferably of 3:1 to 1.5:1.

[0201] In a further preferred embodiment, a method according to the invention is therefore characterized in that the coloring agent (F) and the post-treatment agent (N) - each based on the total weight of the respective agent - contain the chitosans and / or chitosan derivatives (N-1) and the pigments (F-2) in a weight ratio (N-1) / (F-2) of 5:1 to 1:1, preferably of 4:1 to 1:1, more preferably of 3:1 to 1:1 and particularly preferably of 3:1 to 1.5:1.

[0202] Example

[0203] In the inventive method, 100 g of dyeing agent (F) and 100 g of after-treatment agent (N) are applied to the head of a test subject.

[0204] The colorant (F) contains 0.4 g of pigments, corresponding to 0.4 wt% pigments (F-2).

[0205] The post-treatment agent (N) contains 0.9 g chitosan, corresponding to 0.9 wt% chitosan (N-1). The weight ratio (N-1) / (F-2) is 0.9 wt% / 0.4 wt% = 2.25 : 1. Non-staining post-treatment agent

[0206] A distinctive feature of the post-treatment agent (N) is that it is non-coloring. For the purposes of this application, this feature means that the post-treatment agent (N) does not contain any coloring compounds, so that it is free of pigments, direct dyes, and oxidation dye precursors.

[0207] The total content of coloring compounds contained in the dye (N) from the group consisting of pigments, direct dyes, and oxidation dye precursors is therefore 0 wt.%. organic and / or inorganic acids

[0208] As an optional component, the dye (F) and / or the post-treatment agent (N) may contain at least one organic and / or inorganic acid.

[0209] The pH of the dye (F) or the post-treatment agent (N) can be lowered by using one or more acids. When chitosans are used as film-forming polymers, they can be wholly or partially protonated in this way, allowing them to dissolve more readily. Macroscopically, the protonation of the chitosan in water is observed as swelling, from which, when the preferred or highly preferred pH is established, a particularly uniform and thin film is deposited on the keratin fibers. It has been shown that the more uniformly the film forms on the hair, the better its durability. Forming a particularly uniform film has also resulted in dyes with exceptionally good wash fastness. Furthermore, the presence of the acid(s) also enables the chitosan to form a particularly thin film on the hair.Comparative studies have shown that a uniformly thin film has better resistance to external mechanical influences.

[0210] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains at least one organic acid from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0211] Particularly suitable organic acids include, for example, acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0212] Formic acid and propanoic acid are also suitable as organic acids.

[0213] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing 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 that the post-treatment agent (N) contains at least one organic acid (N-2) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0214] Acetic acid dissolves chitosan particularly well and leads to very thin and uniform films; therefore, a dye (F) containing acetic acid is especially preferred. The post-treatment agent (N) also preferably contains acetic acid.

[0215] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) contains acetic acid as an organic acid (F-3), and that the post-treatment agent (N) contains acetic acid as an organic acid (N-2).

[0216] By using the acid(s) in suitable quantities, the pH of the dye (F) or the post-treatment agent (N) can be adjusted to the desired pH range. In this context, it has proven particularly preferred to adjust the pH of the agent (F) to a range 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. To enable measurement of the pH of the agent, the respective agent also contains water.

[0217] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains water and has a pH value of 2.0 to 7.5, preferably 2.5 to 7.0, more preferably 2.5 to 6.5 and most preferably 3.0 to 5.0.

[0218] In a further particularly preferred embodiment, a method according to the invention is therefore characterized in that the dyeing agent (F) and the post-treatment agent (N) contain water and both have a pH value of 2.0 to 7.5, preferably of 2.5 to 7.0, more preferably of 2.5 to 6.5 and most preferably of 3.0 to 5.0.

[0219] Cosmetic carrier of the dye or the after-treatment agent

[0220] The coloring agent (F) and the after-treatment agent (N) contain the essential ingredients (F-1) and (F-2) or (N-1) as well as the optionally present acids (F-3) or (N-2) in a cosmetic carrier, particularly preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. Such carriers can be, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations suitable for application to hair.

[0221] Particularly good results were obtained when the cosmetic carrier was a solvent-based system. Solvents selected from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol, and polyethylene glycol, particularly preferably ethanol, are especially suitable for solving the problem described in the invention.

[0222] In a further particularly preferred embodiment, a dye (F) used in the process is therefore characterized in that it contains at least one solvent (F-4) other than water from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, particularly preferably ethanol.

[0223] In a further particularly preferred embodiment, a post-treatment agent (N) used in the process is also characterized in that it contains at least one solvent (N-3) other than water from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, particularly preferably ethanol.

[0224] The experiments conducted have shown that ethanol is particularly compatible with pigments or chitosans and also with acetic acid; therefore, the use of ethanol in the dye (F) is especially preferred. It is also most preferred to use ethanol as a solvent (N-3) in the post-treatment agent (N).

[0225] Ethanol has the Cas number 64-17-5.

[0226] Isopropanol is also alternatively called 2-propanol and has the CAS number 67-63-0.

[0227] 1,2-Propylene glycol is also alternatively referred to as 1,2-propanediol and bears the CAS numbers 57-55-6 [(RS)-1,2-Dihydroxypropane], 4254-14-2 [(R)-1,2-Dihydroxypropane] and 4254-15-3 [(S)-1,2-Dihydroxypropane],

[0228] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0229] Glycerin is also alternatively known as 1,2,3-propanetriol and has the CAS number 56-81-5. 1-Butanol can also be called n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0230] Phenoxyethanol has the Cas number 122-99-6.

[0231] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0232] Polyethylene glycols according to the present invention are preferably polymers of the general molecular formula C2nH4n+2O that are liquid at room temperature (25 °C). n+i . The repeating unit of the linearly structured polymer is (-CH2-CH2-O-), with a molar mass of approximately 44 g mol -1 Chemically, it is a polyether. Polyethylene glycols are therefore understood to be ethylene glycols of the formula (EG). where x represents an integer from 2 to 10000, preferably an integer from 2 to 1000, and most preferably an integer from 2 to 200.

[0233] The solvent(s) are preferably used in certain quantity ranges in the dye (F) and / or in the post-treatment agent (N).

[0234] Particularly uniform and resistant colorations could be achieved when the dye – based on its total weight – contained one or more solvents other than water (F-4) in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0235] Furthermore, very good results were also achieved when the post-treatment agent (N) - based on its total weight - contained one or more solvents other than water (N-3) in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0236] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and / or the post-treatment agent (N) – each based on the total weight of the respective agent – ​​contains one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0237] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more solvents (F-4) from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0238] In a further particularly preferred embodiment, a method according to the invention is characterized in that the post-treatment agent (N) - based on the total weight of the post-treatment agent (N) - contains one or more solvents (N-3) from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

[0239] In a further particularly preferred embodiment, a process according to the invention is characterized in that the dyeing agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​each contain one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol, and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.%, and most preferably 50 to 80 wt.%. In a further particularly preferred embodiment, a process according to the invention is characterized in that the dyeing agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​each contain 20 to 95 wt.%, preferably 30 to 90 wt.%, and more preferably 40 to 85 wt.%.-% and most preferably containing 50 to 80 wt% ethanol.

[0240] In another particularly suitable embodiment, the solvent(s) (F-4) and (N-3) together with water form the cosmetic carrier. Since the solvent content is particularly preferably relatively high, in the range of 50 to 80 wt.%, it is advantageous to choose a correspondingly low water content. The coloring agent (F) therefore particularly preferably contains 5 to 70 wt.%, more preferably 10 to 60 wt.%, further preferably 15 to 50 wt.%, and most preferably 20 to 40 wt.% water. The post-treatment agent (N) also particularly preferably contains 5 to 70 wt.%, more preferably 10 to 60 wt.%, further preferably 15 to 50 wt.%, and most preferably 20 to 40 wt.% water. The quantities of water mentioned here are based on the total weight of the respective agent.

[0241] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and / or the post-treatment agent (N) - each based on the total weight of the respective agent - contains 5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water.

[0242] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent - contains 5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water (F-5).

[0243] In a further particularly preferred embodiment, a method according to the invention is characterized in that the post-treatment agent (N) - based on the total weight of the post-treatment agent (N) - contains 5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water (N-4).

[0244] In a further particularly preferred embodiment, a method according to the invention is characterized in that the dyeing agent (F) and the post-treatment agent (N) both contain – based on the total weight of the respective agent – ​​5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.%, and most preferably 20 to 40 wt.% water. Composition of dyeing agent (F) and post-treatment agent (N)

[0245] As previously mentioned, particularly uniform and wash-fast films were obtained when the dye (F) and the post-treatment agent (N) were essentially identical in composition, i.e., when both agents contained essentially the same ingredients in similar or identical quantities. In this case, the dye (F) and post-treatment agent (N) differ primarily in the presence of the coloring compound (or pigment) (F-2) in the dye, while the post-treatment agent (N) is non-coloring and therefore contains no coloring compounds.

[0246] The more similar the dye (F) and the post-treatment agent (N) were to each other with regard to the ingredients contained in both agents, the more uniform the resulting films were.

[0247] In a further particularly preferred embodiment, a method according to the invention is characterized in that at least 60 wt.%, preferably at least 70 wt.%, more preferably at least 80 wt.%, even more preferably at least 90 wt.% and most preferably at least 96 wt.% of the components contained in the dyeing agent (F) and in the post-treatment agent (N) are identical.

[0248] Example

[0249] 100 g of a dye (F) contains 1.0 wt% chitosan (F-1), 0.5 wt% pigment (F-2), 0.5 wt% acetic acid (F-3), 65 wt% ethanol (F-4) and 33 wt% water (F-5).

[0250] 100 g of a post-treatment agent contains 1.0 wt% chitosan (N-1), 0.5 wt% acetic acid (N-2), 60 wt% ethanol (N-3) and 38.5 wt% water (N-4).

[0251] Both products contain:

[0252] 1.0 wt% chitosan, 0.5 wt% acetic acid, 60 wt% ethanol (the dye contains an additional 5 wt% more ethanol) and 33 wt% water (the after-treatment agent contains an additional 5.5 wt% more water).

[0253] 94.5% by weight of the components are the same in the dye (F) and the after-treatment agent (N), i.e.

[0254] 94.5% by weight of the components are identical in both products. Further components in the dye and the after-treatment product.

[0255] In addition to the essential and optional ingredients already described, the coloring agent (F) and / or the after-treatment agent (N) may also contain further optional ingredients, such as anionic, non-ionic, zwitterionic and / or cationic surfactants; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; other fat components and / or vegetable oils; structuring agents such as glucose; hair-conditioning compounds such as phospholipids, for example, lecithin and cephalins; perfume oils, dimethyl isosorbide and cyclodextrins; fiber-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, and lactose; anti-dandruff agents such as piroctone olamines, 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, where applicable, anionically or cationically modified derivatives; light protectants and UV blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidone carboxylic 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; swelling and penetration agents such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates; Opaque agents such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents such as ethylene glycol mono- and distearate as well as PEG-3 distearate;as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.;

[0256] The selection of these additional substances will, in principle, be made by a person skilled in the art according to the desired properties of the composition. Regarding further optional components and the quantities of these components used, explicit reference is made to the relevant handbooks known to those skilled in the art. The additional active ingredients and excipients are preferably used in the preparations according to the invention in quantities of 0.0001 to 25 wt.%, and in particular 0.0005 to 15 wt.%, based on the total weight of the respective composition.

[0257] However, it was found that the films produced with the dye (F) were particularly thin, uniform, and stable when the dye consisted largely of components (F-1), (F-2), (F-3), (F-4), and (F-5). It is hypothesized that other components could disrupt the film's uniformity because they could become embedded in the film, weaken it at that point, or provide a point of attack for external forces. For this reason, it is especially advantageous if the components

[0258] (F-1) one or more film-forming polymers, most preferably chitosan and / or chitosan derivatives

[0259] (F-2) one or more colouring compounds, most preferably one or more pigments,

[0260] (F-3) one or more organic acids, preferably one or more acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid,

[0261] (F-4) one or more organic solvents, preferably one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, and

[0262] (F-5) Water together 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.% in the dye (F).

[0263] If components (F-1), (F-2), (F-3), (F-4) and (F-5) are together present in the dye at a quantity of at least 90.0% by weight, then the dye consists – based on its total weight – of components (F-1), (F-2), (F-3), (F-4) and (F-5) to the extent of at least 90% by weight. In other words, in this case, other substances or ingredients different from (F-1) to (F-5) are present in the dye (F) at a quantity of no more than 10% by weight, but preferably at even smaller quantities.

[0264] In a further particularly preferred embodiment, a method according to the invention is characterized in that the components (F-1), (F-2), (F-3), (F-4) and (F-5) are together contained in the dye (F) in a quantity of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.% and most preferably at least 99 wt.%.

[0265] Similarly, the films produced with the post-treatment agent (N) were particularly thin, uniform, and stable when the post-treatment agent (N) consisted largely of components (N-1), (N-2), (N-3), and (N-4). Therefore, it is also particularly preferred if the components

[0266] (N-1) one or more film-forming polymers, most preferably chitosan and / or chitosan derivatives

[0267] (N-2) one or more organic acids, preferably one or more acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid,

[0268] (N-3) one or more organic solvents, preferably one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol, and

[0269] (N-4) Water together 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.% in the dye (F).

[0270] If components (N-1), (N-2), (N-3) and (N-4) are together present in the post-treatment compound (N) in a quantity of at least 90.0 wt.%, then the post-treatment compound (N) consists – based on its total weight – of components (N-1), (N-2), (N-3) and (N-4) to the extent of at least 90 wt.%. In other words, in this case, other substances or ingredients different from (N-1) to (N-4) are present in the post-treatment compound (N) in a quantity of no more than 10 wt.%, but preferably in even smaller quantities.

[0271] In a further particularly preferred embodiment, a method according to the invention is characterized in that the components (N-1), (N-2), (N-3) and (N-4) are together contained in the post-treatment agent (N) in a quantity of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.% and most preferably at least 99 wt.%.

[0272] Steps (1) and (2) of the procedure

[0273] The method according to the invention comprises the application of the dyeing agent (F) to the keratinous fibers in step (1) and the application of the post-treatment agent (N) to the keratinous fibers in step (2).

[0274] Since the post-treatment agent (N) is intended to form a second, undyed film on the film produced by the dye (F), the post-treatment agent (N) must necessarily be applied after the dye (F). The method according to the invention is therefore characterized in that the post-treatment agent (N) is applied to the keratin fibers after the dye (F).

[0275] The timing of the application of the after-treatment agent (N) depends on the user's needs and can be adapted to their habits.

[0276] For example, it is possible to apply the after-treatment product (N) one to three days after applying the dye (F). However, it is particularly advantageous to apply the after-treatment product (N) to the hair dyed with the dye (F) before the first shampoo. Assuming that a user typically washes their hair every one to two days, the after-treatment product (N) is preferably applied within a maximum of 48 hours, more preferably within a maximum of 24 hours, and even more preferably within a maximum of 6 hours after applying the dye.

[0277] The application of dye (F) and after-treatment agent (N) within a single dyeing process is particularly convenient for the user. Therefore, it is especially advantageous if the interval between the application of the dye (F) and the application of the after-treatment agent (N) is no more than 3 hours.

[0278] A procedure encompassing the

[0279] - Application of the dye (F) to the keratinous fibers in a first step, then the

[0280] - Application of the post-treatment agent (N) to the keratinous fibers in a second step, wherein a period of at most 60 hours, preferably at most 48 hours, more preferably at most 24 hours, even more preferably at most 6 hours and most particularly at most 3 hours lies between the application of the dyeing agent (F) and the application of the post-treatment agent (N).

[0281] The application of the post-treatment agent (N) can also be repeated. According to the invention, therefore, the process also encompasses the

[0282] (1) Application of the dye (F) to the keratinous fibers in a first step, then the

[0283] (2) Application of the post-treatment agent (N) to the keratinous fibers in a second step, wherein there is a period of no more than 72 hours between steps (1) and (2) and step (2) is repeated one or more times within this period.

[0284] The dye can be applied as a rinse-off or leave-on product. In the case of a rinse-off application, the dye (F) is applied to the keratin fibers and, after a certain exposure time, rinsed off with water or with water and shampoo. However, particularly good results were obtained when the dye (F) was applied as a leave-on product, i.e., the dye is preferably not rinsed off, but rather the keratin fibers still covered with the dye are dried.

[0285] To accelerate the drying process, the keratin fibers covered with the dye (F) can be heated. Heating accelerates the evaporation of the cosmetic carrier (e.g., water and ethanol) present in the dye (F), allowing the film consisting of pigment, chitosan (derivative), and, if necessary, acid, to form properly.

[0286] The after-treatment product (N) can also be used as a rinse-off or leave-on product. In the case of a rinse-off application, the after-treatment product (N) is applied to the keratin fibers in the same way and, after a certain exposure time, rinsed off with water or with water and shampoo. Very good results were also obtained when the after-treatment product (N), like the dye (F), was applied as a leave-on product; that is, the after-treatment product is preferably not rinsed off, but rather the keratin fibers still covered with the after-treatment product are dried.

[0287] In this further embodiment, a method comprising the following steps in the specified order is therefore particularly preferred.

[0288] (1) Applying the dye (F) to the keratin fibers, (2) Heating the keratin fibers covered with the dye (F) to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 46 °C to 70 °C,

[0289] (3) Application of the post-treatment agent (N) to the keratinous fibers, and

[0290] (4) Heating the keratin fibers covered with the post-treatment agent (N) to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 46 °C to 70 °C.

[0291] The duration of the heat treatment can be adjusted to the selected temperature range. For example, heat treatment can be carried out for a duration of 5 seconds to 60 minutes, preferably from 15 seconds to 45 minutes, more preferably from 15 seconds to 30 minutes, and most preferably from 15 seconds to 15 minutes.

[0292] In the process according to the invention, the keratin fibers can be completely subjected to heat treatment, but the treatment of partial areas of the keratin fibers can also be included. Complete heat treatment of the keratin fibers is preferred, i.e., preferably all keratin fibers to which the dye (F) or the post-treatment agent (N) has been applied are heat treated.

[0293] During the heat treatment, the keratin fibers can also be combed or brushed. This resulted in the strands being separated particularly well and the feel of the film-coated hair being especially pleasant.

[0294] For example, the keratin fibers or hair can be treated with a hairdryer, possibly under combs or brushes, blowing warm or hot air onto the fibers. This air is particularly preferred at a temperature of 40 to 70 °C. Alternatively, the keratin material or hair can be held under an infrared lamp, preferably set to a temperature of 40 to 70 °C.

[0295] In a further particularly preferred embodiment, a method according to the invention is characterized in that the heating of the keratin fibers covered with the dyeing agent (F) and / or the post-treatment agent (N) is carried out by using a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron or an infrared lamp.

[0296] Separate packaging of the after-treatment agent (N)

[0297] To increase user convenience, all necessary components can be provided in a multi-component kit. Alternatively, the user can choose to perform the coloring process with product (F) and the after-treatment with product (N) separately. This might be particularly useful, for example, when the after-treatment is used repeatedly. In this case, the user applies after-treatment (N) for the first time immediately after coloring and can then refresh the color seal with after-treatment (N) again after several shampoos. Separate application can also be used, for example, to preserve the color between coloring sessions. For these purposes, the after-treatment can also be provided as a separately packaged product.

[0298] A second subject matter of the present application is therefore a non-staining, silicone-free post-treatment agent for use on dyed keratinous fibers, containing - based on its total weight -

[0299] (N-1) 0.05 to 1.5 wt.%, preferably 0.2 to 1.3 wt.%, and most preferably 0.3 to 1.1 wt.% chitosan and / or chitosan derivative(s), and

[0300] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0301] (N-3) 20 to 95 wt.%, preferably 30 to 90 wt.%, further preferably 40 to 85 wt.% and most preferably 50 to 80 wt.% ethanol, and

[0302] (N-4) 5 to 70 wt.%, preferably 10 to 60 wt.%, further preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water.

[0303] Particularly preferred is a non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers, containing - based on its total weight -

[0304] (N-1) 0.05 to 1.5 wt.%, preferably 0.2 to 1.3 wt.%, and most preferably 0.3 to 1.1 wt.% chitosan(s), and

[0305] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0306] (N-3) 20 to 95 wt.%, preferably 30 to 90 wt.%, further preferably 40 to 85 wt.% and most preferably 50 to 80 wt.% ethanol, and

[0307] (N-4) 5 to 70 wt.%, preferably 10 to 60 wt.%, further preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water.

[0308] The definitions of the terms "non-staining" and "silicone-free" correspond to the definitions of the first subject matter of the invention. A non-staining, silicone-free post-treatment agent for application to dyed keratinous fibers, containing – based on its total weight –

[0309] (N-1) 0.2 to 1.3 wt%, chitosan and / or chitosan derivative(s), and

[0310] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0311] (N-3) 30 to 90 wt.%, ethanol, and

[0312] (N-4) 10 to 60 wt.% water.

[0313] A non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers is preferred, containing - based on its total weight -

[0314] (N-1) 0.2 to 1.3 wt.%, chitosan(s), and

[0315] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0316] (N-3) 30 to 90 wt.%, ethanol, and

[0317] (N-4) 10 to 60 wt.% water.

[0318] A non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers, containing - based on its total weight - is also preferred.

[0319] (N-1) 0.3 to 1.1 wt%, chitosan and / or chitosan derivative(s), and

[0320] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0321] (N-3) 40 to 85 wt% ethanol, and

[0322] (N-4) 15 to 50 wt.% water.

[0323] A non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers, containing - based on its total weight - is also preferred.

[0324] (N-1) 0.3 to 1.1 wt%, chitosan(s), and

[0325] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0326] (N-3) 40 to 85 wt% ethanol, and

[0327] (N-4) 15 to 50 wt.% water.

[0328] A non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers, containing - based on its total weight - is also preferred.

[0329] (N-1) 0.3 to 1.1 wt% chitosan and / or chitosan derivative(s), and (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0330] (N-3) 50 to 80 wt% ethanol, and

[0331] (N-4) 20 to 40 wt.% water.

[0332] A non-staining, silicone-free post-treatment agent for use on dyed keratinous fibers is also preferred, containing - based on its total weight - (N-1) 0.3 to 1.1 wt.% chitosan(s), and

[0333] (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and

[0334] (N-3) 50 to 80 wt% ethanol, and

[0335] (N-4) 20 to 40 wt.% water.

[0336] Particularly preferred is a non-staining, silicone-free post-treatment agent for use on dyed keratinous fibers, containing – based on its total weight – (N-1) 0.3 to 1.1 wt.% chitosan and / or chitosan derivative(s), and (N-2) acetic acid, and

[0337] (N-3) 50 to 80 wt% ethanol, and

[0338] (N-4) 20 to 40 wt.% water, wherein the components (N-1), (N-2), (N-3) and (N-4) together are contained in the after-treatment agent (N) 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.%.

[0339] Particularly preferred is a non-staining, silicone-free after-treatment agent for use on dyed keratinous fibers, containing – based on its total weight – (N-1) 0.3 to 1.1 wt.% chitosan(s), and (N-2) acetic acid, and

[0340] (N-3) 50 to 80 wt% ethanol, and

[0341] (N-4) 20 to 40 wt.% water, wherein the components (N-1), (N-2), (N-3) and (N-4) are together contained in the post-treatment agent (N) 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.%. Regarding the further preferred embodiments of the post-treatment agent (N) according to the invention, what has been said about the methods according to the invention applies mutatis mutantis.

[0342] Examples

[0343] 1. Formulations

[0344] The following formulations were produced (all values, unless otherwise stated, are in wt.%):

[0345] 2. Application to strands

[0346] The dyes were applied to strands of hair (Kerling brand). For this, 2.0 g of dye (F) per gram of hair strand was massaged in and left on for 1 minute. Afterwards, the strands, still coated with dye, were dried with a standard hairdryer. During drying, the strands were combed through.

[0347] The strands used for comparison were not treated with the after-treatment agent (N), but were assessed under a daylight lamp by a trained person after drying. The strands were then stored for 24 hours. Following drying, the after-treatment agent (N) was applied to the strands according to the invention. For this purpose, 2.0 g of after-treatment agent (N) per gram of hair strand was massaged in and left to act for 1 minute. The strands, still coated with the after-treatment agent, were then dried with a standard hairdryer. During drying, the strands were combed through. After drying, the strands were visually assessed by a trained person under a daylight lamp. The strands were then stored for 24 hours.

[0348] 3. Measuring wash fastness

[0349] To measure colorfastness, the strands dyed and stored according to point 2 were each subjected to 10 manual hair washes (WW). For each wash, the strand was moistened, then a commercially available shampoo (Schauma 7 Herbs) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). Afterwards, the strand was rinsed with lukewarm tap water for 30 seconds and dried.

[0350] After 5 and after 10 hair washes, each strand was visually assessed again under the daylight lamp.

[0351] The hair strands were assessed for their color intensity on a scale from 1 (very high color intensity) to 6 (very low color intensity).

[0352] 0 HW = Color result directly after dyeing

[0353] 1 = very high intensity 6 = very low intensity

[0354] 1 = very high intensity 6 = very low intensity

[0355] The hair strands that were first treated with the dye (F) and then with the after-treatment agent (N) showed improved wash fastness compared to the hair strands that were treated only with the respective dye (F).

Claims

Patent claims 1. Method for dyeing keratinous fibers, especially human hair, comprising the (1) Application of a silicone-free dye (F) to the keratinous fibers, which contains (F-1) at least one film-forming polymer and (F-2) at least one colouring compound from the group consisting of pigments, direct dyes and oxidation dye precursors, and the (2) Application of a non-staining, silicone-free after-treatment agent (N) to the keratinous fibers, which contains (N-1) at least one film-forming polymer.

2. Method according to claim 1, characterized in that the post-treatment agent (N) contains at least one film-forming polymer (N-1) which is also contained in the dyeing agent (F).

3. Method according to one of claims 1 to 2, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains at least one nature-based film-forming polymer, preferably selected from the group consisting of polysaccharides and natural gums, particularly preferably from the group consisting of polyaminosaccharides, and most preferably from the group consisting of chitosan and the derivatives of chitosan.

4. Method according to any one of claims 1 to 3, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains at least one chitosan and / or one chitosan derivative (F-2) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

5. Method according to any one of claims 1 to 4, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) - each based on the total weight of the respective agent - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.01 to 2.5 wt.%, preferably 0.05 to 1.5 wt.%, more preferably 0.2 to 1.3 wt.%, and most preferably 0.3 to 1.1 wt.%.

6. A method according to any one of claims 1 to 5, characterized in that the dyeing agent (F) and the post-treatment agent (N) – each based on the total weight of the respective agent – ​​comprise the film-forming polymer(s) (F-1) and the film-forming polymer(s) (N-1) in a weight ratio (F-1) / (N-1) of 1:4 to 4:1, preferably of 1:3 to 3:1, further preferably from 1:2 to 2:1, even more preferably from 1:1.5 to 1.5:1 and particularly preferably from 1:1.2 to 1.2:

1.

7. Method according to one of claims 1 to 6, characterized in that the coloring agent (F) contains at least one coloring compound (F-2) from the group of pigments, which is preferably selected from the group consisting of inorganic pigments, organic pigments, pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

8. Method according to one of claims 1 to 7, characterized in that the dyeing agent (F) contains at least one coloring compound (F-2) from the group of direct dyes, particularly preferably from the group of anionic direct dyes.

9. Method according to any one of claims 1 to 8, characterized in that the dyeing agent (F) - based on the total weight of the dyeing agent (F) - contains one or more coloring compounds (F-2) in a total amount of 0.1 to 2.5 wt.%, preferably 0.15 to 1.7 wt.%, more preferably 0.2 to 1.3 wt.%, even more preferably 0.25 to 0.8 wt.% and most preferably 0.30 to 1.0 wt.%.

10. Method according to any one of claims 1 to 9, characterized in that the dyeing agent (F) and the post-treatment agent (N) - each based on the total weight of the respective agent - contain the film-forming polymer(s) (N-1) and the coloring compound(s) (F-2) in a weight ratio (N-1) / (F-2) of 5:1 to 1:1, preferably of 4:1 to 1:1, more preferably of 3:1 to 1:1 and particularly preferably of 3:1 to 1.5:

1.

11. Method according to any one of claims 1 to 10, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains at least one organic acid from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

12. Method according to any one of claims 1 to 11, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) contains water and has a pH value of 2.0 to 7.5, preferably 2.5 to 7.0, more preferably 2.5 to 6.5 and most preferably 3.0 to 5.

0.

13. Method according to any one of claims 1 to 12, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) - each based on the total weight of the respective agent - contains one or more solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycol in a total amount of 20 to 95 wt.%, preferably 30 to 90 wt.%, more preferably 40 to 85 wt.% and most preferably 50 to 80 wt.%.

14. Method according to any one of claims 1 to 13, characterized in that the dyeing agent (F) and / or the post-treatment agent (N) - each based on the total weight of the respective agent - contains 5 to 70 wt.%, preferably 10 to 60 wt.%, more preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water.

15. Method according to any one of claims 1 to 14, characterized in that at least 60 wt.%, preferably at least 70 wt.%, further preferably at least 80 wt.%, even more preferably at least 90 wt.% and most preferably at least 96 wt.% of the components contained in the dyeing agent (F) and in the post-treatment agent (N) are identical.

16. Method according to any one of claims 1 to 15, comprising the Application of the dye (F) to the keratinous fibers in a first step, then the Application of the post-treatment agent (N) to the keratinous fibers in a second step, wherein a period of at most 60 hours, preferably at most 48 hours, more preferably at most 24 hours, even more preferably at most 6 hours and most particularly at most 3 hours elapses between the application of the dyeing agent (F) and the application of the post-treatment agent (N).

17. A method according to any one of claims 1 to 16, comprising the following steps in the specified order (1) Application of the dye (F) to the keratinous fibers, (2) Heating the keratin fibers covered with the dye (F) to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 46 °C to 70 °C, (3) Application of the post-treatment agent (N) to the keratinous fibers, and (4) Heating the keratinous fibers covered with the post-treatment agent (N) to a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, further preferably from 45 °C to 170 °C, more preferably from 45 °C to 100 °C and most preferably from 46 °C to 70 °C.

18. Non-staining, silicone-free after-treatment for use on dyed keratinous fibers, containing - based on its total weight - (N-1) 0.05 to 1.5 wt.%, preferably 0.2 to 1.3 wt.%, and most preferably 0.3 to 1.1 wt.% chitosan and / or chitosan derivative(s), and (N-2) one or more organic acids from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid, and (N-3) 20 to 95 wt.%, preferably 30 to 90 wt.%, further preferably 40 to 85 wt.% and most preferably 50 to 80 wt.% ethanol, and (N-4) 5 to 70 wt.%, preferably 10 to 60 wt.%, further preferably 15 to 50 wt.% and most preferably 20 to 40 wt.% water.

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