A preparation for treating keratinous fibers, especially human hair, containing at least one chitosan derivative obtained by reacting organic aldehydes with chitosan.

Abstract

The present invention relates to a means (M) for treating keratinous fibers, in particular human hair, comprising (M-1) at least one chitosan derivative comprising at least one structural unit of the general formula (1) where R1 for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

Description

[0001] The present application relates to a cosmetic agent for treating keratinous fibers, in particular human hair, containing at least one chitosan derivative comprising at least one structural unit of general formula (I). The chitosan derivatives are obtained by reacting chitosan with at least one organic aldehyde.

[0002] Altering the shape and color of keratin fibers, especially human hair, is an important area of ​​modern cosmetics. Depending on the desired color, professionals are familiar with various dyeing systems for changing hair color. For permanent, intense colorations with good colorfastness and gray coverage, oxidation dyes are typically used. These dyes contain oxidation dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidation dyes are characterized by very long-lasting color results.

[0003] When using direct dyes, pre-formed pigments diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, dyes produced with direct dyes are less durable and wash out more quickly. Dyes made with direct dyes typically remain on the hair for between 5 and 20 washes.

[0004] The use of color pigments is well-known for temporary color changes to hair and / or skin. Color pigments are generally understood to be insoluble, coloring substances. These are present in the coloring formulation in the form of small particles and are simply deposited on the hair fibers and / or skin surface. Therefore, they can usually be removed completely after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name "hair mascara."

[0005] Dyeing with pigments offers several significant advantages. Since the pigments adhere only to the outer surface of the keratin fibers, particularly the hair fibers, unwanted dyes can be removed quickly and easily without leaving any residue. This allows users to return to their original hair color immediately and effortlessly. This dyeing process is therefore particularly attractive for consumers who do not want to dye their hair regularly.

[0006] 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.

[0007] For example, German patent DE 19847883 A1 addresses the creation of pigment-based colorations using dyes containing at least one chitosan and one pigment. The combination of pigments with chitosan is intended to improve the abrasion resistance of the colorations. The major advantage of chitosan as a film-forming material lies in its biopolymer base, which offers improved environmental compatibility and biodegradability. As many users show increasing interest in products made with sustainable or renewable raw materials, the use of biopolymers is gaining prominence. Nevertheless, the colorations achieved with pigment and chitosan still have room for improvement.

[0008] The coloring achieved with pigments (or direct dyes, especially poorly soluble direct dyes) and chitosan is a surface coloring, meaning that the applied dyes do not diffuse into the hair but are deposited on the hair surface and embedded there in a film by the simultaneously applied chitosan. Depending on the amount of embedded dyes, this film is modified to a greater or lesser extent. The work leading to this invention revealed that the properties of a film embedding a large number of dyes are also significantly altered. In particular, the feel and rub fastness of the film are adversely affected.

[0009] The objective of this application was therefore to find a dye based on pigments and / or direct dyes that enables intense coloring with improved feel and better rub fastness. The coloring should be achieved using biopolymers, and the keratin fibers or hair colored with the dye should not feel coated, dull, rough, or greasy.

[0010] Surprisingly, it has now been found that this task can be solved if a dye containing a chitosan derivative is used for coloring, the amino group or amino groups of which are located in the C2 position of the D-glucosamine unit have been derivatized by reaction with an organic aldehyde.

[0011] A first object of the present invention is a means (M) for treating keratinous fibers, in particular human hair, comprising (M-1) at least one chitosan derivative comprising at least one structural unit of general formula (1) where R1 for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0012] The chitosan derivative(s) (M-1) formed a very stable film on the hair, which, due to the longer-chain alkyl units bonded to the nitrogen atom, exhibited improved haptic properties compared to non-derivatized chitosan. Modifying the chitosan with 2-ethylhexanal noticeably improved the feel of the treated strands. Such products proved to be very suitable for styling hair as well as for shaping and / or styling. Particularly good results were observed when the product was formulated as a dye and contained at least one coloring compound (M-2) in addition to the chitosan derivative(s) (M-1).

[0013] It was found that a dye containing at least one chitosan derivative (M-1) and a colorant (M-2) is able to color hair with the same intensity as a dye containing non-derivatized chitosan. Surprisingly, such a dye significantly improved the feel of the dyed hair.

[0014] Hair dyed with one of these agents exhibited high color intensity and was characterized by a pleasant, smooth, non-greasy and soft feel. Keratinous fibers

[0015] Keratinous fibers include hair, wool, and fur. Human hair is particularly often considered a keratinous fiber. Agents for the treatment of keratinous fibers

[0016] The term "agent for treating keratin fibers" is used in the application for all treatment methods in which the aim is to form a film on the keratin fibers that is as stable as possible. The agents according to the invention are also referred to as agents (M). These can be, for example, styling agents in which the film, due to its durability, lasts through several hair washes, thus achieving a particularly long-lasting styling effect. Agents for temporarily shaping the keratin fibers, agents for maintaining curls, and smoothing agents also fall into this category.

[0017] The treatment of keratin fibers according to the invention is particularly preferably a coloring process in which the agent contains, in addition to the chitosan derivative(s) (M-1), at least one coloring compound (M-2). The coloring compounds used are particularly preferably those dyes that adhere to the surface of the keratin fibers from the outside and are thus incorporated into the film formed by the chitosan derivative. These coloring compounds are therefore particularly preferably selected from the group consisting of pigments and / or direct dyes, and most preferably from the group consisting of pigments.

[0018] When the substance (M) is used as a dye, it can also be referred to as dye (F). The components (M-1), (M-2), (M-3), (M-4) and (M-5) described in more detail below can then also be referred to as components (F-1), (F-2), (F-3), (F-4) and (F-5). Chitosans (M-1) on average (M)

[0019] As an essential component, the agent (M) according to the invention contains at least one chitosan derivative (M-1) comprising at least one structural unit of the general formula (1). where R1 for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0020] In the chitosan derivatives (M-1), chitosan is used as the starting material and reacted with at least one organic alkanal. The alkanals used in the reaction are C2-C 23 -Alkanals. In this reaction, the amino group located at the C2 position of the D-glucosamine ring unit reacts with the aldehyde group of the alkanal to form an imine. Multiple amino groups of the chitosane preferentially react to form the imines.

[0021] Chitosan, also known as polyglusam or poly-D-glucosamine, is used as a starting material in the synthesis of the chitosan derivative (M-1). It is a naturally occurring biopolymer derived from chitin, which is composed of β-1,4-glycosidically linked N-acetylglucosamine residues (specifically, 2-acetamido-2-deoxy-β-D-glucopyranose residues). Like chitin, it is a polyaminosaccharide. Chitosan is produced by deacetylating chitin, resulting in a molecule consisting of approximately 2000 linearly linked 2-amino-2-deoxy-β-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4.

[0022] Chitosan is preferably produced from chitin, which is found in shellfish or crustaceans. Industrially, chitosan is obtained from chitin through 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.

[0023] The degree of deacetylation can vary considerably: Deacetylation can be complete or partial, resulting in a distribution of strongly deacetylated areas alongside weakly deacetylated areas, or a homogeneous deacetylation distribution. Simultaneously, this chemical intervention can decrease the polymer chain length (depolymerization). The molecular weight of chitosan can be distributed over a wide range, for example, from 20,000 to approximately 5 million g / mol.

[0024] Theoretically, complete deacetylation of chitosan gives it a structure of the formula (Chitosan-I) where n is determined by the molecular weight of the chitosan and preferably represents an integer from 1 to 10,000, more preferably from 10 to 5,000 and most particularly preferably from 50 to 3,000.

[0025] Partially deacetylated chitosans possess an idealized structure of the formula (Chitosan-II) where the remainder R stands for a grouping COCH3.

[0026] The index number n is again determined by the molecular weight of the chitosan and preferably represents an integer from 1 to 10,000, more preferably from 10 to 5,000 and most particularly preferably from 50 to 3,000.

[0027] The structure of the formula (Chitosan-II) is intended to illustrate that chitosan comprises both D-glucosamine and N-acetyl-D-glucosamine units. The structure is idealized; that is, in partially deacetylated chitosan, the deacetylated and acetylated units do not necessarily alternate strictly. Therefore, a D-glucosamine unit does not always have to be directly adjacent to an N-acetyl-D-glucosamine unit. In partially deacetylated chitosan, for example, several D-glucosamine units can follow one another until one or more N-acetylglucosamine units are connected.

[0028] The chitosan derivative (M-1) comprises at least one structural unit of formula (1) where R1 for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0029] Since the chitosan derivative (M-1) according to the invention is a polymer, it preferably comprises several structural units of formula (1), particularly preferably at least 3, more preferably at least 5 and most preferably at least 10 structural units of formula (1).

[0030] The number of structural units of formula (1) in the chitosan derivative (M-1) can be adjusted by the molar ratio in which chitosan and the organic alkanal R1-CHO are reacted together.

[0031] The structural unit of formula (1) represents a substituted glucosamine unit. The dashed line extending from the oxygen atom at position 1 represents the bonding site to the carbon atom of the adjacent N-acyl-glucosamine unit or glucosamine unit to the right. This bond is formed via a β-1,4-glycosidic linkage. If the structural unit of formula (1) is located at the right end of the chitosan derivative polymer chain, the dashed line extending from the oxygen atom at position 1 can also lead to a hydrogen atom.

[0032] The dashed line extending from the carbon atom at position 4 in formula (1) represents the bonding site to the oxygen atom at position 1 of the N-acyl-glucosamine unit or glucosamine unit to its left. If the structural unit of formula (1) is located at the left end of the polymer chain of the chitosan derivative, the dashed line extending from the carbon atom at position 4 can also lead to a hydroxyl group.

[0033] The remainder R1 represents a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0034] Examples of a saturated, linear C1-C 22-Alkyl groups are the methyl group, the ethyl group, the propyl group, the n-butyl group, the n-pentyl group, the n-hexyl group, the n-heptyl group, the n-octyl group, the n-nonyl group, the n-decyl group, the n-undecyl group, the n-dodecyl group, the n-undecyl group, the n-dodecyl group, the n-tridecyl group, the n-tetradecyl group, the n-pentadecyl group, the n-hexadecyl group, the n-heptadecyl group and the n-octadecyl group.

[0035] The C2-C 22 The -alkyl group can also be simply unsaturated.

[0036] Examples of a monounsaturated, linear C2-C 22The alkyl groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexydecenyl, heptadecenyl, and octadecenyl. The double bonds can be located at different positions along the alkyl chain.

[0037] From a chain length of 4 carbon atoms, the C4-C 22 -Alkyl group can also be polyunsaturated.

[0038] Examples of a polyunsaturated, linear C4-C 22The alkyl groups are a butadienyl group, a pentadienyl group, a hexadienyl group, a heptadienyl group, an octadienyl group, a nonadienyl group, a decadienyl group, an undecadienyl group, a dodecydienyl group, a tridecadienyl group, a tetradecadienyl group, a pentadecadienyl group, a hexadecadienyl group, a heptadecydienyl group, and an octadecadienyl group. The double bonds can be located at different positions along the alkyl chain.

[0039] From a chain length of 3 carbon atoms, the residue R1 can also represent a saturated, branched C3-C 22-Alkyl groups. Examples include the isopropyl group, the methylpropyl group, the ethylpropyl group, the methylbutyl group, the ethylbutyl group, the methylpentyl group, the ethylpentyl group, the methylhexyl group, the ethylhexyl group, the methylheptyl group, the ethylheptyl group, the methyloctyl group, and the ethyloctyl group. The alkyl groups (in this case, the methyl and ethyl groups), which represent the branches, can be located at different positions along the alkyl chain.

[0040] If necessary, the C1-C 22 The -alkyl group can also bear one or more substituents. Possible substituents include, for example, the hydroxy group, the C1-C6 alkoxy group, the amino group, the C1-C6 alkylamino group, or the di(C1-C6 alkyl)amino group.

[0041] It has proven preferable if the remainder R1 represents a linear or branched, saturated or mono- or polyunsaturated C1-C 22-alkyl group, which - apart from the alkyl group(s) that represent the branches of the alkyl chain - has no further substitutes.

[0042] A particularly strong improvement in the feel of the treated hair was observed when a product (M) was used which contained at least one chitosan derivative (M-1) comprising a structural unit of formula (1) in which R1 represents a branched saturated C3-C 21 -Alkyl group, preferably for a branched saturated C3-C 15 -Alkyl group, further preferably for a branched saturated C3-C 11 -Alkyl group, even more preferably stands for a branched saturated C5-C9 alkyl group.

[0043] The R1 group is explicitly and particularly preferred to represent a saturated, branched C7 alkyl group. The R1 group is most preferred to represent the 1-ethylpentyl group.

[0044] If the residue R1 represents the 1-ethylpentyl group, chitosan was reacted with the aldehyde 2-ethylhexanal. When the reaction product was used in a dye, the treated hair was intensely colored and simultaneously felt soft and supple, but not coated or greasy. This improvement in feel could also be achieved with the use of higher amounts of coloring compounds (M-2).

[0045] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains at least one chitosan derivative (M-1) wherein R1 represents a branched saturated C3-C 21 -Alkyl group, preferably for a branched saturated C3-C 15 -Alkyl group, further preferably for a branched saturated C3-C 11 -Alkyl group, even more preferably for a branched saturated C5-C9 alkyl group and most preferably for 1-ethylpentyl. Production of chitosan derivatives (M-1)

[0046] The chitosan derivative (M-1) is produced by reacting chitosan with an organic aldehyde R1-CHO.

[0047] The residue R1 here represents the same substituents as it does in the structural unit of formula (1), i.e., R1 represents monolinear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0048] Examples of the aforementioned groups and the preferred and especially preferred structural units for the remainder R1 have already been mentioned.

[0049] The reaction of the aldehyde R1-CHO with chitosan derivatizes the amino group(s) located at the 2-position of each glucosamine unit of the chitosan and converts them into the corresponding imine. Particularly preferential derivatization occurs when multiple amino groups in the chitosan polymer are involved.

[0050] This reaction can be carried out in a solvent such as water, ethanol, or a mixture of water and ethanol. The formation of imine can be accelerated by the presence of acids such as acetic acid. After the reaction, the imine obtained as a product can be precipitated by adding organic solvents such as acetone.

[0051] In a further preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one chitosan derivative (M-1) obtained by reaction of chitosan with an aldehyde R1-CHO, wherein R1 for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group, which may also carry one or more substituents.

[0052] R1 is particularly preferred for a linear or branched, saturated or mono- or polyunsaturated C1-C 22 -Alkyl group that, apart from the alkyl groups forming the branches, bears no further substituents. The corresponding aldehyde R1-CHO is then a linear or branched, saturated or mono- or polyunsaturated C2-C 23 -Alkanal.

[0053] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one chitosan derivative (M-1) which is produced by reacting chitosan with a saturated or unsaturated, linear or branched aliphatic C2-C 23 -Alkanal is obtained.

[0054] One particularly suitable aldehyde is, for example, 2-ethylhexanal. 2-Ethylhexanal can also be called 2-ethylcapronaldehyde and has the CAS number 123-05-7. 2-Ethylhexanal can be purchased from chemical suppliers such as Sigma-Aldrich, Fluka, or Merck.

[0055] In the conversion to the chitosan derivative (M-1), a chitosan with a specific molecular weight is preferably used. 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.

[0056] Accordingly, the chitosan derivative (M-1) also has a molecular weight of this order of magnitude.

[0057] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one chitosan derivative (M-1) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

[0058] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially, for example, from the company Sigma Aldrich. This can be derivatized as described in the example.

[0059] 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%.

[0060] Chitosan O27 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.

[0061] Furthermore, it has proven particularly advantageous if the composition (M) according to the invention contains the chitosan derivative(s) (M-1) in certain quantity ranges. Particularly good results were obtained when the composition (M) – based on the total weight of the composition (M) – contained one or more chitosan derivatives (M-1) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 7.0 wt.%, more preferably 0.2 to 4.5 wt.%, even more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%.

[0062] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition (M) - one or more chitosan derivatives (M-1) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 7.0 wt.%, more preferably 0.2 to 4.5 wt.%, even more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%. color-giving compounds (M-2) on average

[0063] As already described, the composition (M) according to the invention is most preferably a composition for dyeing keratinous fibers. As a dyeing agent (F), the composition most particularly additionally contains at least one coloring compound (M-2).

[0064] The coloring compound(s) are deposited on the surface of the keratin fibers and embedded in the film formed by the chitosan derivative(s) (M-1). These films exhibit excellent resistance to treatments with water and shampooing. Most importantly, the film containing the coloring compounds is characterized by particularly advantageous haptic properties, as the coated hair feels very soft and supple, but not straw-like, greasy, or unpleasant.

[0065] In a further particularly preferred embodiment, a means according to the invention is characterized in that it is a means for dyeing the keratinous fibers, which contains at least one coloring compound (M-2) which is preferably selected from the group of pigments and direct dyes, and most preferably selected from the group of pigments.

[0066] In a particularly preferred embodiment, the composition (M) according to the invention contains at least one pigment as the coloring compound (M-2). For the purposes of this invention, pigments are understood to be coloring compounds which have a solubility in water at 25 °C of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. The water solubility can be determined, for example, by the method described below: 0.5 g of the pigment is weighed into a beaker. A magnetic stir bar is added. Then one liter of distilled water is added. This mixture is heated to 25 °C for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L.If the pigment-water mixture cannot be visually assessed due to the high intensity of the potentially finely dispersed pigment, the mixture is filtered. If a proportion of undissolved pigment remains on the filter paper, the pigment's solubility is below 0.5 g / L.

[0067] Suitable color pigments can be of inorganic and / or organic origin.

[0068] In a preferred embodiment, a means (M) according to the invention is characterized in that it contains at least one color-imparting compound (F-2) from the group of inorganic and / or organic pigments.

[0069] Inorganic pigments generally have a higher refractive index than organic pigments, therefore scattering a greater proportion of light and offering greater opacity. When particularly opaque colorations are desired, the use of one or more inorganic pigments has proven especially advantageous.

[0070] 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.

[0071] 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).

[0072] 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.

[0073] 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).

[0074] In a further preferred embodiment, a method according to the invention is characterized in that the agent (M) contains at least one inorganic pigment (M-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.

[0075] In a further preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one pigment selected from mica- or micaceous-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0076] 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.

[0077] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491(Iron oxides), Tin oxide Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491(Iron oxides) Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

[0078] Other particularly preferred color pigments with the trade name Xirona® include, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0079] In addition, particularly preferred color pigments with the trade name Unipure® include, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0080] In a further embodiment, the agent (M) according to the invention can also contain one or more organic pigments. Organic pigments typically do not have as good an opacity as inorganic pigments, but are often more brilliant and produce particularly vibrant shades. Therefore, if the keratinous fibers are to be colored in particularly vibrant shades, the use of at least one organic pigment is especially preferred.

[0081] 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.

[0082] 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.

[0083] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one organic pigment (M-2) preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, and orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, 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.

[0084] The organic pigment can also be a paint lake. For the purposes of the 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. The particles can be, for example, inorganic substrates such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0085] For example, alizarin lacquer can be used as a colored lacquer.

[0086] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the colorant (F) of the process according to the invention is particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. Therefore, according to the invention, it is advantageous if the at least one pigment has an average particle size D 50 The particle size ranges from 1.0 to 50 µm, preferably from 5.0 to 45 µm, preferably from 10 to 40 µm, and particularly from 14 to 30 µm. The mean particle size D 50 can be determined, for example, using dynamic light scattering (DLS).

[0087] 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.

[0088] In a further preferred embodiment, a means according to the invention is characterized in that it contains at least one pigment selected from the group consisting of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet, and vacuum metallized pigments.

[0089] 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.

[0090] 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.

[0091] 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 µm, especially approximately 5 to 100 µm.

[0092] 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 Helos instrument with Quixel wet dispersion. For sample preparation, the sample to be tested was pre-dispersed in isopropanol for 3 minutes.

[0093] The substrate plates can be made from any material that can be formed into platelet form.

[0094] 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).

[0095] 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 substrate platelets being particularly preferred.

[0096] Platelet-shaped pigments adhere particularly flat to the fibers. When made of metal, they form a reflective surface that makes the keratin fibers shine exceptionally brightly.

[0097] Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0102] Uncoated lamellar, lenticular, and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop. These have proven particularly advantageous for use in dyes.

[0103] Suitable pigments based on a lamellar substrate platelet include, for example, the VISIONAIRE series pigments from Eckart.

[0104] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from the company Schlenk Metallic Pigments GmbH.

[0105] Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0106] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one pigment (M-2) 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.

[0107] The coloring compound(s) (M-2) are preferably used in specific quantity ranges on average. Particularly good results were obtained when the agent (M) – based on the total weight of the agent (M) – contained one or more coloring compounds (M-2) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.%, and most preferably 0.30 to 1.00 wt.%.

[0108] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains – based on the total weight of the composition (M) – one or more color-giving compounds (M-2) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%.

[0109] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition - one or more pigments (M-2) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%.

[0110] The product (M) may also contain one or more direct dyes as coloring compounds. Direct dyes are dyes that adhere directly to the hair and do not require an oxidative process to develop their color. Typical direct dyes include nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0111] The direct-acting dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 0.5 g / L and are therefore not to be considered pigments. Preferably, the direct-acting dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 1.0 g / L.

[0112] However, it may be preferable if the dye (F) does not contain direct dyes.

[0113] Direct-drawing dyes can be divided into anionic, cationic, and nonionic direct-drawing dyes.

[0114] Cationic direct dyes include Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76.

[0115] Examples of nonionic direct-drawing dyes include nonionic nitro and quinone dyes and neutral azo dyes. Examples of nonionic direct-drawing dyes are those known by their international names.Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 bekannten Verbindungen, sowie 1,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1,4-Bis-(2-hydroxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(2-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-Hydroxyethyl)amino]-3-nitro-1-methylbenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2'-Ureidoethyl)amino-4-nitrobenzol, 2-[(4-Amino-2-nitrophenyl)amino]-benzoesäure, 6-Nitro-1,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1,4-naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chlor-6-ethylamino-4-nitrophenol.

[0116] Anionic direct-acting dyes are also known as acid dyes. Acid dyes are defined as direct-acting dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms (-COOH, -SO3H) of the carboxylic acid and sulfonic acid groups, along with their deprotonated forms (-COO), are located at different pH values. - , -SO3 - The carboxylic acid groups (carboxylic acid groups) exist in equilibrium. As the pH decreases, the proportion of protonated forms increases. When direct-acting dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0117] The acid dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 0.5 g / L and are therefore not to be considered pigments. Preferably, the acid dyes according to the present invention have a solubility in water (760 mmHg) at 25 °C of more than 1.0 g / L.

[0118] 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.

[0119] 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.

[0120] Als Beispiele für Säurefarbstoffe können können genannt werden: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403,CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n° : C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (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.I. 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 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.I.14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 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, CI 17200), Acid Red 35 (CI C.I.18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.I. 60730, COLIPA n° C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blau V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, CI 42090, C.I.Food Blue 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9 (C.I.42100), Acid Green 22 (C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, C.I. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n° B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 und / oder D&C Brown 1.

[0121] The water solubility of anionic direct-acting dyes can be determined, for example, using the following method. Place 0.1 g of the anionic direct-acting dye into a beaker. Add a magnetic stir bar. Then add 100 ml of water. Heat this mixture to 25 °C on a magnetic stirrer while stirring. Stir for 60 minutes. Afterward, visually inspect the aqueous mixture. If undissolved dye remains, increase the amount of water—for example, in 10 ml increments. Continue adding water until the dye is completely dissolved. If the dye-water mixture cannot be visually assessed due to the high intensity of the dye, filter the mixture. If some undissolved dye remains on the filter paper, repeat the solubility test with a larger amount of water.If 0.1 g of the anionic direct-drawing dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g / L.

[0122] Acid Yellow 1 is called 8-Hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25°C).

[0123] Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of 20 g / L (25 °C).

[0124] Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid; its water solubility is above 40 g / L (25 °C).

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

[0126] 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).

[0127] 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%. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)naphthalene-2,7-disulfonate; its water solubility is 2.5 g / L (25 °C).

[0128] Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose water solubility is given as greater than 10 g / L (25 °C).

[0129] Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a water solubility of more than 20 wt% (25 °C).

[0130] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition - one or more direct dyes (M-2) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%. organic and / or inorganic acids (M-3)

[0131] As a further optional component, the agent (M) according to the invention may contain at least one organic and / or inorganic acid (M-3).

[0132] The addition of one or more acids can lower the pH of the dye (M), thereby protonating the chitosan derivative (M-1) completely or partially, thus improving its solubility. Macroscopically, the protonation of the chitosan derivative in water is observed as swelling, from which, when the preferred or highly preferred pH is reached, a particularly uniform and thin film is deposited on the keratin fibers, such as hair. It has been shown that the more uniformly the film forms on the hair, the better its durability. The formation of a particularly uniform film has also resulted in dyes with exceptionally good wash fastness. Furthermore, the presence of the acid(s) (M-3) in the dye also enables the chitosan to form a particularly thin film on the hair.Comparative studies have shown that a uniformly thin film has better resistance to external mechanical influences.

[0133] 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, methyllactic acid, glucuronic acid, glycolic acid, pyruvic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, gluconic acid, mandelic acid, phenyllactic acid, gluconic acid, galacturonic acid, aleuric acid, ribonic acid, fumaric acid; salts and mixtures thereof.

[0134] Formic acid and propanoic acid are also suitable acids (M-3).

[0135] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one organic acid (M-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, methyllactic acid, glucuronic acid, glycolic acid, pyruvic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, gluconic acid, mandelic acid, phenyllactic acid, gluconic acid, galacturonic acid, aleuric acid, ribonic acid, fumaric acid; salts and mixtures thereof, in particular acetic acid and / or a salt of acetic acid.

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

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

[0138] By using the acid(s) in suitable quantities, the pH of the dye can be adjusted to the desired pH range. Particularly thin and uniform films were obtained when the dye (M) was adjusted to a pH in the 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.

[0139] In a further particularly preferred embodiment, a composition according to the invention is therefore characterized in that it has a pH value of 2.0 to 7.5, preferably of 3.0 to 7.0, more preferably of 3.5 to 6.5 and most preferably of 4.0 to 6.0.

[0140] Furthermore, particularly good results were obtained when the composition (M) contained water and acids in a specific weight ratio. It has proven especially preferred to adjust the weight ratio of the water (M-4) to the acids (M-3) contained in the composition (M), i.e., the weight ratio (M-4) / (M-3), to a value of 1000 to 10, preferably 500 to 40, more preferably 200 to 60, and most preferably 150 to 85.

[0141] In a further particularly preferred embodiment, a composition according to the invention is therefore characterized in that the weight ratio of the water (M-4) contained in the composition (M) to the acids (M-3), i.e. the weight ratio (M-4) / (M-3), is in a value of 1000 to 10, preferably from 500 to 40, more preferably from 200 to 60 and most preferably from 150 to 85. Average water content (M-4)

[0142] The chitosan derivative(s) (M-1) are particularly preferably incorporated into a cosmetic carrier. The cosmetic carrier is particularly preferably a mixture of organic solvents (M-5) and water (M-4).

[0143] Ethanol is the most preferred organic solvent, so the cosmetic carrier is most preferably a mixture of ethanol and water.

[0144] Since the concentration of the organic solvent(s) is preferably chosen to be relatively high, it is advantageous to reduce the water content accordingly. The composition (M) therefore preferably contains 10 to 50 wt.%, more preferably 15 to 45 wt.%, further preferably 20 to 40 wt.%, and most preferably 25 to 35 wt.% water (M-4). The quantities of water given here are based on the total weight of the composition.

[0145] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition (M) - 10 to 50 wt.%, preferably 15 to 45 wt.%, more preferably 20 to 40 wt.% and most preferably 25 to 35 wt.% water (M-4). Solvent (M-5) on average (M)

[0146] Furthermore, it has also proven advantageous to add one or more solvents other than water to the agent (M). Suitable organic solvents include, for example, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol, 1-hexanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, phenoxyethanol, benzyl alcohol, and / or polyethylene glycols.

[0147] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains at least one organic solvent (M-5) from the group consisting of ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol, 1-hexanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and / or polyethylene glycols.

[0148] Ethanol has the Cas number 64-17-5.

[0149] Isopropanol is also alternatively called 2-propanol and has the CAS number 67-63-0. 1,2-Propylene glycol is also alternatively called 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-15-3 [(S)-1,2-dihydroxypropane].

[0150] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0151] 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.

[0152] Phenoxyethanol has the Cas number 122-99-6.

[0153] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0154] Polyethylene glycols according to the present invention are polymers of the general formula C that are liquid at room temperature (25 °C). 2n H 4n+2 O n+1 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.

[0155] Particularly uniform and resistant colorations could be achieved when the agent contained one or more organic solvents (M-5) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%, based on the total weight of the agent.

[0156] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition (M) - one or more organic solvents (M-5) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%.

[0157] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that it contains - based on the total weight of the composition (M) - one or more organic solvents (M-5) from the group consisting of ethanol, 1-propanol and isopropanol in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%.

[0158] Explicitly and especially preferred is an agent (M) which contains - based on the total weight of the agent (M) - 40 to 95 wt.%, preferably 50 to 90 wt.%, further preferably 55 to 85 wt.% and most preferably 60 to 80 wt.% ethanol (M-5). Average proportion of components (M-1), (M-2), (M-3), (M-4) and (M-5) (M)

[0159] During the work leading to this invention, microscopic images were taken which showed that a thin, uniform film on the keratin fibers possesses particularly good resistance to external influences such as mechanical friction or hair washing. The smoother and more continuous the film, the less surface area it offers to external forces. Once the film is broken in one place, it can be completely removed very quickly by the constant movement of the keratin fibers.

[0160] It was found that the films produced with the agent (M) or with the dye (F) were particularly thin, uniform, and stable when the dye consisted largely of components (M-1), (M-2), (M-3), (M-4), and (M-5). It is suspected that other components could disrupt the uniformity of the film because they could become embedded in the film, weaken it at that point, or create a point of attack for external forces. For this reason, it is especially preferred that components (M-1), (M-2), (M-3), (M-4), and (M-5) are present together in the agent (M) in a proportion of at least 94.0 wt.%, preferably at least 95 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.%, and most preferably at least 99.6 wt.%.

[0161] If components (M-1), (M-2), (M-3), (M-4) and (M-5) together constitute at least 94.0 wt.% of the average (M), then the average (M) consists – based on its total weight – of at least 94 wt.% of components (M-1), (M-2), (M-3), (M-4) and (M-5). In other words, in this case, other substances or ingredients different from (M-1) to (M-5) are present in the average (M) only in a maximum wt.%, but preferably in even smaller, proportions.

[0162] In a further particularly preferred embodiment, a composition (M) according to the invention is characterized in that the components chitosan derivative(s) (M-1), coloring component(s) (M-2), organic acid(s) (M-3), water (M-4) and solvent (M-5) are together contained in the composition in a quantity of at least 94.0 wt.%, preferably at least 95 wt.%, more preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.6 wt.%. Methods for dyeing keratinous fibers

[0163] The agent (M) is used in processes for treating keratinous fibers, especially human hair. It is particularly well-suited as a dye.

[0164] A second subject matter of the present application is therefore a method for treating keratinous fibers, in particular human hair, in which an agent (M) which has already been disclosed in detail in the description of the first subject matter of the invention is applied to the keratinous fibers.

[0165] Particularly preferably, the second object of the present invention is a method for dyeing keratinous fibers, especially human hair, in which the agent (M), which has already been disclosed in detail in the description of the first object of the invention, is applied to the keratinous fibers and optionally rinsed off after an exposure time.

[0166] The dye can be applied to the keratin fibers, for example, with a gloved hand or using a brush or applicator. After application, the dye can be spread over the keratin fibers and, if necessary, gently massaged in.

[0167] In one embodiment, the agent is rinsed off using a rinse-off method and, after a certain exposure time, is rinsed off with water or with water and the aid of shampoo. Suitable exposure times are, for example, 5 to 60 minutes, preferably 5 to 45 minutes, more preferably 5 to 30 minutes, and most preferably 5 to 15 minutes.

[0168] The uniformity of the color and its wash fastness were particularly outstanding when the product was applied as a "leave-on" treatment. In this case, the product was not rinsed off; instead, the keratin fibers still coated with the product were dried. Drying of the keratin fibers can be carried out at room temperature in the open air, or the fibers still coated with the product can be heated to accelerate the drying process.

[0169] A method for treating keratinous fibers, especially human hair, is therefore particularly preferred, comprising - the application of the agent (M) to the keratinous fibers, and - the drying of the keratinous fibers covered with the agent (M), wherein the drying preferably takes place at a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.

[0170] Heating or heat treatment refers to the process of bringing the keratin fibers into contact with a heated device, or applying this heated device to or on the keratin fibers. Furthermore, the keratin material can also be exposed to warm / hot air for heat treatment. Examples of such devices include a hairdryer, a heat cap, a flat iron, a curling iron, or an infrared lamp.

[0171] 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.

[0172] In the process according to the invention, the keratin fibers can be completely subjected to heat treatment, but the treatment of partial areas of the keratin fibers can also be included. Complete heat treatment of the keratin fibers is preferred, i.e., preferably all keratin fibers to which the dye (F) has also been applied are treated with heat.

[0173] 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 preferably between 45 and 70 °C. Alternatively, the keratin material or hair can be held under an infrared lamp, preferably set to a temperature of 45 to 70 °C.

[0174] In a further particularly preferred embodiment, a method according to the invention is characterized in that the heat treatment is carried out by using a hairdryer, a hair dryer, a heat cap, a flat iron, a curling iron or an infrared lamp.

[0175] During heat treatment or heating, the keratin fibers can also be combed or brushed.

[0176] For example, if the hair is combed continuously or occasionally during blow-drying, the individual fibers can be separated particularly well from each other, and the feel of the dyed hair was particularly good and uncoated.

[0177] In a further particularly preferred embodiment, the method according to the invention is therefore characterized in that the keratin fibers or the hair are combed or brushed during drying.

[0178] Regarding the other preferred embodiments of the methods according to the invention, what has been said about the means according to the invention applies mutatis mutantis. Examples 1. Synthesis example

[0179] For the preparation of the chitosan derivative, 1.0 g of chitosan (wt. 100,000–300,000 g / mol, Sigma-Aldrich) was dissolved in 50 mL of 5% acetic acid solution at room temperature for 4 hours using a KPG stirrer at 300 rpm. The mixture was then left to stand overnight at room temperature without stirring. Next, 0.9 g of 2-ethylhexanal was dissolved in 30 mL of ethanol and added dropwise to the chitosan mixture at 60 °C and 300 rpm, with stirring continued for 6 hours to obtain a batch of 84.4 mL. Finally, the mixture was cooled to room temperature and precipitated dropwise in 150 mL of acetone. The resulting precipitate was filtered under vacuum, washed with 30 mL of ethanol, and dried at 48 °C for 24 hours to obtain the reaction product (M-1).

[0180] The reaction proceeded according to the following reaction scheme, where the structure of chitosan is idealized: 2. Spectroscopic investigation of the reaction product (M-1)

[0181] The reaction product obtained in this way (M-1) was oxidized using Raman ( Fig. ) and solid-state NMR spectroscopy ( Fig. ) investigated.

[0182] Analysis using Raman spectroscopy ( Fig. ) showed both an increase in the CH vibration oscillation between 630 - 710 cm -1 as well as the formation of a C=NC bond between 1630-1690 cm -1 These changes result from the formation of a Schiff base through the reaction of the amino group of chitosan with the aldehyde functionality of 2-ethylhexanal and indicate a successful synthesis.

[0183] Analysis using solid-state NMR ( Fig.The results showed a broadening of the signals after the addition of 2-ethylhexanal. This indicates an enlarged, more amorphous structure of the synthesis product (M-1) compared to the untreated chitosan, which results from the higher molar mass of the synthesis product (M-1). 3. Formulations

[0184] The following dyes were produced (all values, unless otherwise stated, are in wt.%): Dyeing agent (M) M1 (wt%)V M2 (wt%) E Chitosan (MW = 100,000 - 300,000 g / mol, Sigma Aldrich) 0,90 - Chitosan (M-1) with R1 = 1-Ethylpentyl (produced in Synthesis Example 1) - 0,90 Unipure Red LC 3079 (Pigment Red 7, Cas No. 5281-04-9 (CI15850) (M-2) 0,40 0,40 Ethanol 70 70 acetic acid 0,60 0,60 Water (distilled) ad 100 ad 100

[0185] V = Comparison E = Invention

[0186] A swelling solution was first prepared from the water, acetic acid, and the respective chitosan. Ethanol was mixed with the pigment. This dispersion was homogenized by rapid stirring.

[0187] Afterwards, the aqueous chitosan swelling and the alcoholic pigment dispersion were mixed together and homogenized by rapid stirring. 4. Application to strands

[0188] The dyes were applied to strands of hair (Kerling brand, shade 8 / 0, length 20 cm). For this, 2.0 g of dye (FM) per gram of hair strand was massaged in and left on for 1 minute. The strands, still coated with dye, were then dried with a standard hairdryer. During drying, the strands were combed through. 5. Measurement of color intensity and hair feel

[0189] The strands dyed in this way were assessed by trained individuals in a blind test. To measure the hair color, the strands dyed with M1 and M2 were laid side by side under a daylight lamp and visually compared. The color was rated using a school grading system (1 = very intense, 6 = no color impression).

[0190] To assess the feel of the hair, each trained person took the strand to be tested in their hand and ran their fingers through it several times. The feel of the hair strands colored with formulations M1 and M2 was then compared. The evaluation was based on a school grading system (1 = smooth, pleasant feel; 6 = particularly dull, rough feel). criterion M1Chitosan M2Chitosan derivative (M-1) Color 3 3 Hair feeling 5 3

[0191] By modifying the chitosan with 2-ethylhexanal, the feel of the dyed strands could be noticeably improved, while maintaining the same color intensity. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] DE 19847883 A1

[0007]

Claims

Composition (M) for treating keratinous fibers, especially human hair, comprising (M-1) at least one chitosan derivative comprising at least one structural unit of general formula (1) where R 1 for a linear or branched, saturated or mono- or polyunsaturated C 1 -C 22 -Alkyl group, which may also carry one or more substituents. Composition (M) according to claim 1, characterized in that it contains at least one chitosan derivative (M-1) wherein R1 represents a branched saturated C3-C21 alkyl group, preferably a branched saturated C3-C15 alkyl group, more preferably a branched saturated C3-C11 alkyl group, even more preferably a branched saturated C5-C9 alkyl group and most preferably 1-ethylpentyl. A composition (M) according to one of claims 1 to 2, characterized in that it contains at least one chitosan derivative (M-1) obtained by reaction of chitosan with a saturated or unsaturated, linear or branched aliphatic C2-C23 alkanal. Composition (M) according to one of claims 1 to 3, characterized in that it contains at least one chitosan derivative (M-1) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol. Composition (M) according to one of claims 1 to 4, characterized in that it contains - based on the total weight of the composition (M) - one or more chitosan derivatives (M-1) in a total amount of 0.01 to 20.0 wt.%, preferably 0.1 to 7.0 wt.%, more preferably 0.2 to 4.5 wt.%, even more preferably 0.3 to 2.5 wt.%, and most preferably 0.4 to 1.2 wt.%. Composition (M) according to one of claims 1 to 5, characterized in that it contains at least one coloring compound (M-2) which is preferably selected from the group consisting of pigments and direct dyes, and most preferably selected from the group consisting of pigments. Composition (M) according to one of claims 1 to 6, characterized in that it contains at least one pigment (M-2) 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. Composition (M) according to one of claims 1 to 7, characterized in that it contains - based on the total weight of the composition - one or more coloring compounds (M-2) in a total amount of 0.10 to 3.00 wt.%, preferably 0.15 to 2.00 wt.%, more preferably 0.2 to 1.50 wt.%, even more preferably 0.25 to 1.25 wt.% and most preferably 0.30 to 1.00 wt.%. A composition (M) according to any one of claims 1 to 8, characterized in that it contains at least one organic acid (M-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, methyllactic acid, glucuronic acid, glycolic acid, pyruvic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, gluconic acid, mandelic acid, phenyllactic acid, gluconic acid, galacturonic acid, aleuric acid, ribonic acid, fumaric acid, salts and mixtures thereof, in particular acetic acid and / or a salt of acetic acid. Composition (M) according to any one of claims 1 to 9, characterized in that it contains - based on the total weight of the composition (M) - 10 to 50 wt.%, preferably 15 to 45 wt.%, more preferably 20 to 40 wt.% and most preferably 25 to 35 wt.% water (M-4). Composition (M) according to any one of claims 1 to 10, characterized in that it contains at least one organic solvent (M-5) from the group consisting of ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol, 1-hexanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and / or polyethylene glycols. Composition (M) according to one of claims 1 to 11, characterized in that it contains - based on the total weight of the composition (M) - one or more organic solvents (M-5) in a total amount of 40 to 95 wt.%, preferably 50 to 90 wt.%, more preferably 55 to 85 wt.% and most preferably 60 to 80 wt.%. Composition (M) according to any one of claims 1 to 12, characterized in that the components chitosan derivative(s) (M-1), coloring component(s) (M-2), organic acid(s) (M-3), water (M-4) and solvent (M-5) are together contained in the composition in a quantity of at least 94.0 wt.%, preferably at least 95 wt.%, further preferably at least 96 wt.%, even more preferably at least 99 wt.% and most preferably at least 99.6 wt.%. Method for treating keratinous fibers, in particular human hair, in which an agent (M) according to one of claims 1 to 13 is applied to the keratinous fibers. The method according to claim 14 comprising: applying the agent (M) to the keratinous fibers, and drying the keratinous fibers covered with the agent (M), wherein the drying preferably takes place at a temperature of 40 °C to 210 °C, more preferably from 40 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 100 °C and most preferably from 45 °C to 70 °C.

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