Agent for dyeing keratin material with aminosilicone, pigment and polysaccharide

Description

[0001] The present application relates to a dyeing agent for keratinous material, in particular human hair, comprising at least one linear, amino-functionalized silicone polymer (a1), at least one pigment (a2) having a solubility in water at 25 °C of less than 0.05 g / L, and at least one polysaccharide (a3) ​​selected from the group consisting of hydroxy-C1-C30 alkylcelluloses, hydroxy-C1-C30 alkylmethylcelluloses, hydroxy-C1-C30 alkylethylcelluloses, C1-C30 alkylcelluloses, C6-C30 alkylhydroxyethylcelluloses, cellulose, starch, xanthan gum, carboxyalkylcellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan gum, pectin, agaropectin and / or their salts. Furthermore, the product is characterized by the fact that it is free of silicone resins.

[0002] A second subject matter of this application is a method for dyeing keratinous material, in particular human hair, wherein an agent of the first subject matter of the invention is applied to the keratinous material, allowed to act and then washed off again with water.

[0003] Altering the shape and color of keratinous material, 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, oxidative dyes are typically used. These dyes contain oxidative dye precursors, so-called developer components and coupler components, which react with oxidizing agents such as hydrogen peroxide to form the actual dyes. Oxidative dyes are characterized by very long-lasting color results.

[0004] 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.

[0005] US 2011 / 0104094 A1 addresses conditioning agents containing cationic surfactants, fats, direct-drawing dyes and non-ionic thickening polymers.

[0006] US 2016 / 051023 A1 describes a method for dyeing and semi-permanently straightening hair.

[0007] In DE 10 2013 226102 A1, aqueous dyes for keratin fibers with a pH value of 1.0 to 5.5 are described, which contain an amino silicone of formula (I) and at least one direct acid dye.

[0008] The Mintel database discloses the market product "Retok Hair Spray" (XP055749937, database number 5238685), which is available in spray form and contains a linear aminosilicone, a direct-acting acid dye, and xanthan gum as a polysaccharide.

[0009] 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."

[0010] If a user desires particularly long-lasting color, the use of oxidative dyes has so far been their only option. However, despite numerous optimization attempts, an unpleasant ammonia or amine odor cannot be completely avoided with oxidative hair coloring. The hair damage still associated with the use of oxidative dyes also has a detrimental effect on the user's hair. Therefore, the search for alternative, high-performance coloring methods remains a challenge. One possible alternative coloring system that has recently gained increasing attention is based on the use of colored pigments.

[0011] Dyeing with pigments offers several significant advantages. Because the pigments adhere only to the keratin material, particularly the hair fibers, from the outside, the damage associated with the dyeing process is minimal. Furthermore, unwanted dyes can be removed quickly and easily without leaving any residue, allowing users to return to their original hair color immediately and effortlessly. This makes the dyeing process particularly attractive for consumers who do not want to dye their hair regularly.

[0012] Recent studies have addressed the problem of the limited durability of this dyeing system. In this context, it was found that the wash fastness of color results obtained with pigments could be significantly improved by combining the pigments with certain amino-functionalized silicone polymers. Despite these findings, further optimization is still needed, particularly for striking and fashionable shades.

[0013] Pigment-based coloring systems are described, for example, in EP 3058935 B1. To improve the deposition of pigments on the hair and to produce natural-looking colorations, EP 3058935 B1 proposes the use of a formulation which, in an aqueous-alcoholic base, contains, in addition to a pigment, an aminosilicone, a silicone resin, and a thickener system made of various polymers.

[0014] Further research into the teaching of EP 3058935 B1 has revealed that the silicone resins contained in the product can also have a detrimental effect on dyed hair. Firstly, it has been shown that the silicone resins significantly impair the feel of the dyed hair. Secondly, it has also been found that the corresponding dyes containing silicone resins are significantly inferior in terms of color intensity.

[0015] The object of the present invention was to provide a coloring system with which pigments can be fixed to the hair in the most permanent way possible. The application of this coloring system should achieve particularly intense coloring results with good colorfastness. At the same time, the hair should have the most pleasant feel possible and should not feel greasy, weighed down, dull, or coated.

[0016] Surprisingly, it has now been found that the aforementioned task can be excellently accomplished when keratinous materials, especially hair, are dyed with a product containing at least one linear amino-functionalized silicone polymer (a1), at least one pigment (a2), and at least one polysaccharide (a3). Furthermore, experimental series have shown that particularly good dyeing effects were obtained when the corresponding products were free of silicone resins.

[0017] A first object of the present invention is a means for dyeing keratinous material, in particular human hair, comprising (a1) at least one linear, amino-functionalized silicone polymer, and (a2) at least one pigment having a solubility in water at 25 °C of less than 0.05 g / L, and (a3) ​​at least one polysaccharide selected from the group consisting of hydroxy-C1-C30 alkylcelluloses, hydroxy-C1-C30 alkylmethylcelluloses, hydroxy-C1-C30 alkylethylcelluloses, C1-C30 alkylcelluloses, C6-C30 alkylhydroxyethylcelluloses, cellulose, starch, xanthan gum, carboxyalkylcellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan gum, pectin, agaropectin and / or their salts, characterized by the fact that the agent is free of silicone resins

[0018] In the course of the work carried out for this invention, it was surprisingly found that the use of a polysaccharide (a3) ​​in a composition containing an aminosilicone (a1), a pigment (a2), and a lipid component (a4) leads to an increase in color intensity when this composition is applied in a dyeing process to keratinous material, particularly human hair. The composition had to be free of silicone resins. keratinous material

[0019] Keratinous material includes hair, skin, and nails (such as fingernails and / or toenails). Wool, fur, and feathers also fall under the definition of keratinous material.

[0020] The term "keratinous material" preferably refers to human hair, human skin, and human nails, especially fingernails and toenails. Human hair is particularly preferred as a keratinous material. dyeing agents

[0021] 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 coloring compounds, especially pigments. In this coloring process, the pigments are deposited as coloring compounds in a particularly homogeneous, uniform, and smooth film on the surface of the keratin material. Linear amino-functionalized silicone polymers (a1)

[0022] The first ingredient essential to the invention (a1) of the composition contains at least one linear amino-functionalized silicone polymer. The amino-functionalized silicone polymer can alternatively also be referred to as aminosilicone or amodimethicone.

[0023] Silicone polymers are generally macromolecules with a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, and particularly preferably at least 5000 g / mol, comprising repeating organic units.

[0024] The maximum molecular weight of the silicone polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size, and is also determined by the polymerization method. For the purposes of the present invention, it is preferred that the maximum molecular weight of the silicone polymer is not more than 10⁷ < g / mol, preferably not more than 10⁶ < g / mol, and particularly preferably not more than 10⁵ < g / mol.

[0025] Silicone polymers comprise many Si-O repeating units, where the Si atoms can bear organic groups such as alkyl groups or substituted alkyl groups. Therefore, a silicone polymer is also alternatively referred to as polydimethylsiloxane.

[0026] In accordance with the high molecular weight of the silicone polymers, these are based on more than 10 Si-O repeat units, preferably more than 50 Si-O repeat units and particularly preferably more than 100 Si-O repeat units, most preferably more than 500 Si-O repeat units.

[0027] An amino-functionalized silicone polymer is defined as a functionalized silicone that contains at least one structural unit with an amino group. Preferably, the amino-functionalized silicone polymer contains several structural units, each with at least one amino group. An amino group is defined as a primary amino group, a secondary amino group, or a tertiary amino group. All of these amino groups can be protonated in an acidic environment and then exist in their cationic form.

[0028] A linear silicone polymer is understood to be a linear polymer without branches, consisting only of one polymer chain, the main chain.

[0029] In other words, a linear amino-functionalized silicone polymer is a polysiloxane of the type (Si-linear) That is, the residues R' located on the silicon atoms can (each independently of the others) represent organic residues such as methyl groups, C1-C20 alkyl groups, amino-C1-C20 alkyl groups or substituted C1-C20 alkyl groups, but the siloxane main chain itself formed by the sequence of silicon atoms and oxygen atoms is not branched and is therefore linear.

[0030] In principle, good results could be achieved with linear amino-functionalized silicone polymers (a1) if they contained at least one primary, at least one secondary and / or at least one tertiary amino group. However, the best wash fastness was observed when a linear amino-functionalized silicone polymer (a1) containing at least one secondary amino group was used (a).

[0031] In a particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one linear amino-functionalized silicone polymer (a1) with at least one secondary amino group.

[0032] The secondary amino group(s) can be located at various positions within the amino-functionalized silicone polymer. Particularly good results were observed when an amino-functionalized silicone polymer (a1) was used that possesses at least one, preferably several, structural units of the formula (Si-Amino).

[0033] In the structural units of the formula (Si-Amino), the abbreviations ALK1 and ALK2 stand independently for a linear or branched, divalent C 1 -C 20 -alkylene group.

[0034] In a further particularly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one linear amino-functionalized silicone polymer (a1) comprising at least one structural unit of the formula (Si-Amino), where ALK1 and ALK2 independently represent a linear or branched, divalent C1-C20 alkylene group.

[0035] The positions marked with an asterisk (*) indicate the bond to other structural units of the silicone polymer. For example, the silicon atom adjacent to the asterisk may be bonded to another oxygen atom, and the oxygen atom adjacent to the asterisk may be bonded to another silicon atom or to a C1-C6 alkyl group.

[0036] A divalent C1-C20 alkylene group can alternatively also be referred to as a divalent or divalent C1-C20 alkylene group, meaning that each group ALK1 or AK2 can form two bonds.

[0037] In the case of ALK1, a bond is formed from the silicon atom to the ALK1 group, and the second bond is formed between ALK1 and the secondary amino group.

[0038] In the case of ALK2, a bond is formed from the secondary amino group to the ALK2 group, and the second bond is formed between ALK2 and the primary amino group.

[0039] Examples of linear divalent C1-C20 alkylene groups are, for example, the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-), and the butylene group (-CH2-CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C20 alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0040] In a further particularly preferred embodiment, the structural units of formula (Si-Amino) represent repeating units in the linear amino-functionalized silicone polymer (a1), such that the silicone polymer comprises several structural units of formula (Si-Amino).

[0041] The following is a list of particularly suitable amino-functionalized silicone polymers (a1) with at least one secondary amino group.

[0042] Dyes with the very best wash fastness could be obtained when, in the inventive process, at least one agent (a) was applied to the keratinous material, which contains at least one linear amino-functionalized silicone polymer (a1) comprising structural units of formula (Si-I) and formula (Si-II).

[0043] In a further explicitly preferred embodiment, a method according to the invention is characterized in that the agent (a) contains at least one linear amino-functionalized silicone polymer (a1) comprising structural units of formula (Si-I) and formula (Si-II).

[0044] An example of a corresponding amino-functionalized silicone polymer with the structural units (Si-I) and (Si-II) is the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is commercially distributed by the Dow Chemical Company and bears the name "Siloxanes and Silicones, 3-[(2-Aminoethyl)amino]-2-methylpropyl Me, Di-Me-Siloxane" and the CAS number 106842-44-8.

[0045] In a further preferred embodiment, a method according to the invention is characterized by the application of an agent (a) to the keratinous material, wherein the agent (a) contains at least one amino-functional silicone polymer (a1) of the formula (Si-III), where m and n represent numbers chosen such that the sum (n + m) is in the range of 1 to 1000, n is a number in the range of 0 to 999 and m is a number in the range of 1 to 1000, R1, R2 and R3, which may be the same or different, represent a hydroxy group or a C1-4 alkoxy group, where at least one of the groups R1 to R3 represents a hydroxy group;

[0046] Further methods preferred according to the invention are characterized by the application of an agent (a) to the keratinous material, wherein the agent (a) contains at least amino-functional silicone polymer (a1) of the formula of formula (Si-IV), in the p and q represent numbers chosen such that the sum (p + q) is in the range of 1 to 1000, p is a number in the range of 0 to 999 and q is a number in the range of 1 to 1000, R1 and R2, which are different, represent a hydroxy group or a C1-4 alkoxy group, where at least one of the groups R1 to R2 represents a hydroxy group.

[0047] The silicones of formulas (Si-III) and (Si-IV) differ in the grouping at the silicon atom bearing the nitrogenous group: In formula (Si-III), R2 represents a hydroxyl group or a C1-4 alkoxy group, while in formula (Si-IV) the group is a methyl group. The individual silicon groups, designated with the indices m and n or p and q, do not necessarily exist as blocks; rather, the individual units can also be statistically distributed. That is, in formulas (Si-III) and (Si-IV), not every R1-Si(CH3)2 group is necessarily bonded to a -[O-Si(CH3)2] group.

[0048] Methods according to the invention have also proven to be particularly effective with regard to the desired effects, in which an agent (a) is applied to the keratin fibers, which contains at least one linear amino-functional silicone polymer (a1) of the formula of the formula (Si-V). in the A represents a group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3; D represents a group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3; b, n, and c represent integers between 0 and 1000. with the stipulations n > 0 and b + c > 0 at least one of the conditions A = -OH or D = -H is satisfied.

[0049] In the above-mentioned formula (Si-V), the individual siloxane units with the indices b, c and n are statistically distributed, i.e., they do not necessarily have to be block copolymers.

[0050] The agent (a) may furthermore contain one or more different amino-functionalized silicone polymers described by the formula (Si-VI) M(R a Q b SiO (4-ab) / 2)x (R c SiO (4-c) / 2)y M (Si-VI), where in the above formula R is a hydrocarbon or a hydrocarbon residue with 1 to about 6 carbon atoms, Q is a polar residue of the general formula -R 1< HZ, wherein R 1< is a divalent, connecting group bonded to hydrogen and the residue Z, composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and Z is an organic, amino-functional residue containing at least one amino-functional group;"a" takes on values ​​in the range of about 0 to about 2, "b" takes on values ​​in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range of about 1 to about 3, and x is a number in the range of 1 to about 2,000, preferably from about 3 to about 50 and most preferably from about 3 to about 25, and y is a number in the range of about 20 to about 10,000, preferably from about 125 to about 10,000 and most preferably from about 150 to about 1,000, and M is a suitable silicon end group as known in the prior art, preferably trimethylsiloxy. Non-restrictive examples of residues represented by R include alkyl residues such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and similar; alkenyl residues such as vinyl, halogenovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl residues such as cyclobutyl, cyclopentyl, cyclohexyl and similar;Phenyl groups, benzyl groups, halogenated hydrocarbon groups such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and similar, as well as sulfur-containing groups such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and similar; preferably R is an alkyl group containing 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R 1< include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH(CH 3 )CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 OCH 2 -, -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )C(O)OCH 2 -, -(CH 2 ) 3 CC(O)OCH 2 CH 2 -, -C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and -(CH 2 ) 3 C(O)SCH 2 CH 2 -.;

[0051] Z is an organic, amino-functional residue containing at least one functional amino group. One possible formula for Z is NH(CH₂)zNH₂, where z is 1 or more. Another possible formula for Z is -NH(CH₂)z(CH₂)zzNH, where both z and zz are independently 1 or more, this structure including diamino ring structures such as piperazinyl. Z is most preferably an -NHCH₂CH₂NH₂ residue. Another possible formula for Z is -N(CH₂)z(CH₂)zzNX₂ or -NX₂, where each X of X₂ is independently selected from the group consisting of hydrogen and alkyl groups with 1 to 12 carbon atoms, and zz is 0.

[0052] Q is most preferably a polar, amine-functional residue of the formula -CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2 . In the formulas, "a" takes values ​​in the range of about 0 to about 2, "b" takes values ​​in the range of about 2 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range of about 1 to about 3. The molar ratio of the RaQbSiO(4-ab) / 2 units to the RcSiO(4-c) / 2 units is in the range of about 1:2 to 1:65, preferably from about 1:5 to about 1:65, and most preferably from about 1:15 to about 1:20. If one or more silicones of the above formula are used, then the various variable substituents in the above formula can differ depending on the different silicone components present in the silicone mixture.

[0053] In a particularly preferred embodiment, a method according to the invention is characterized by the application of an agent (a) to the keratinous material, wherein the agent (a) contains an amino-functional silicone polymer of the formula (Si-VII) R' a G 3-a -Si(OSiG 2 ) n -(OSiG b R' 2- b ) m -O-SiG 3-a -R' a (Si-VII), wherein: G is-H, a phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-CH2CH2CH3, -CH2CH2CH3, -O-CH(CH3)2, -CH(CH3)2, -O-CH2CH2CH2CH3, -CH2CH2CH2CH3, -O-CH2CH(CH3)2, -CH2CH(CH3)2, -O-CH(CH3)CH2CH3, -CH(CH3)CH2CH3, -OC(CH3)3, -C(CH3)3; a represents a number between 0 and 3, in particular 0; b represents a number between 0 and 1, in particular 1, m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably takes values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably takes values ​​from 1 to 2000, in particular from 1 to 10, R' is a monovalent residue selected from ∘ -QN(R")-CH 2 -CH 2 -N(R") 2 ∘ -QN(R") 2 ∘ -QN +< (R") 3 A -< ∘ -QN +< H(R") 2 A -< ∘ -QN +< H 2 (R")A -< ∘ -QN(R")-CH 2 -CH 2 -N'R"H 2 A -< , where each Q represents a chemical bond, -CH 2 -, -CH 2 -CH 2 -, -CH 2 CH 2 CH 2 -, -C(CH 3 ) 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 C(CH 3 ) 2 -, -CH(CH 3 )CH 2 CH 2 -, R" represents identical or different residues from the group -H, -Phenyl, -Benzyl, -CH 2 -CH(CH 3 )Ph, the C 1-20 alkyl residues, preferably -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 H 3 , -CH 2 CH(CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 , -C(CH 3 ) 3 , and A an anion which is preferably selected from chloride, bromide, iodide or methosulfate.

[0054] In a further preferred embodiment, a method according to the invention is characterized by the application of an agent (a) to the keratinous material, wherein the agent (a) contains at least one amino-functional silicone polymer (a1) of the formula (Si-Vlla), wherein m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, wherein n preferably takes values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably takes values ​​from 1 to 2000, in particular from 1 to 10.

[0055] According to the INCI declaration, these silicones are called Trimethylsilylamodimethicone.

[0056] In a further preferred embodiment, a method according to the invention is characterized by the application of an agent (a) to the keratinous material, wherein the agent (a) contains at least one amino-functional silicone polymer of the formula (Si-Vllb). containing, wherein R represents -OH, -O-CH 3 or a -CH 3 group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2000, preferably between 50 and 150, wherein the sum (n1 + n2) preferably takes values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably takes values ​​from 1 to 2000, in particular from 1 to 10.

[0057] These amino-functionalized silicone polymers are called Amodimethicone according to the INCI declaration.

[0058] Regardless of which amino-functional silicones are used, compositions (a) according to the invention are preferred which contain an amino-functional silicone polymer whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g, and particularly above 0.4 meq / g. The amine number represents the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and can also be expressed in mg KOH / g.

[0059] It has proven particularly advantageous if the agent according to the invention contains the linear amino-functionalized silicone polymer(s) (a1) in certain quantity ranges.

[0060] Particularly good results were obtained when the agent contains one or more linear amino-functionalized silicone polymers in a total amount of 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, more preferably 0.3 to 3.0 wt.% and most preferably 0.4 to 2.5 wt.%, based on the total weight of the agent.

[0061] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains - based on the total weight of the means - one or more linear amino-functionalized silicone polymers (a1) in a total amount of 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, more preferably 0.3 to 3.0 wt.% and most preferably 0.4 to 2.5 wt.%. Pigments (a2)

[0062] The second essential component of the composition according to the invention contains at least pigment.

[0063] For the purposes of this invention, pigments are understood to be coloring compounds that have a solubility in water of less than 0.05 g / L at 25 °C. The water solubility can be determined, for example, by the following method: 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 pigment remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0064] Suitable color pigments can be of inorganic and / or organic origin.

[0065] In a preferred embodiment, a means according to the invention is characterized in that it contains at least one color-giving compound (a2) from the group of inorganic and / or organic pigments.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] 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).

[0070] In a further preferred embodiment, a composition according to the invention is characterized in that it contains at least one coloring compound (a2) from the group of inorganic pigments, which is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or micaceous oxide, which are coated with at least one metal oxide and / or one metal oxychloride.

[0071] In a further preferred embodiment, a composition according to the invention is characterized in that it (a) contains at least one coloring compound (a2) from the group of pigments 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).

[0072] 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.

[0073] Particularly favored color pigments with the trade name Colorona ® include, for example: 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) ,

[0074] 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 Dioxide), Tin Oxide.

[0075] Furthermore, particularly preferred color pigments with the trade name Unipure ®< are, 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

[0076] 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.

[0077] For example, alizarin lacquer can be used as a colored lacquer.

[0078] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the agent (a) of the process according to the invention is particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. Therefore, according to the invention, it is advantageous if the at least one pigment has a mean particle size D50 of 1.0 to 50 µm, preferably of 5.0 to 45 µm, more preferably of 10 to 40 µm, and particularly of 14 to 30 µm. The mean particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0079] The (a2) pigments constitute the second essential component of the composition according to the invention and are preferably used in the composition in certain quantity ranges.

[0080] Particularly good results were obtained when the agent contained one or more pigments (a2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.5 wt.% and most preferably 0.25 to 1.5 wt.%.

[0081] In a further particularly preferred embodiment, a composition according to the invention is characterized in that the composition contains - based on the total weight of the composition - one or more pigments (a2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.1 to 5.0 wt.%, more preferably 0.2 to 2.5 wt.% and most preferably 0.25 to 1.5 wt.%.

[0082] As a further optional component, the compositions according to the invention can also contain one or more direct dyes. Direct dyes are dyes that adhere directly to the hair and do not require an oxidative process to develop the color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0083] 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.

[0084] Direct-drawing dyes can be divided into anionic, cationic, and nonionic direct-drawing dyes.

[0085] In a further embodiment, a method according to the invention is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of anionic, nonionic and cationic direct dyes.

[0086] Suitable cationic direct dyes are, for example, 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.

[0087] Examples of nonionic direct-drawing dyes include nonionic nitro and quinone dyes and neutral azo dyes. Suitable 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.

[0088] Anionic direct-drawing dyes are also known as acid dyes. Acid dyes are defined as direct-drawing dyes that possess at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO₃H). Depending on the pH, the protonated forms (-COOH, -SO₃H) of the carboxylic acid or sulfonic acid groups exist in equilibrium with their deprotonated forms (-COO⁻, -SO₃⁻). The proportion of protonated forms increases with decreasing pH. When direct-drawing dyes are used in the form of their salts, the carboxylic acid 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 potassium salts.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] In a further embodiment, a method for dyeing keratinous material is characterized in that the agent (a) contains at least one anionic direct dye selected from the group consisting of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, wherein the dyes from the aforementioned group each have at least one carboxylic acid group (-COOH), one sodium carboxylate group (-COONa), one potassium carboxylate group (-COOK), one sulfonic acid group (-SO3H), one sodium sulfonate group (-SO3Na) and / or one potassium sulfonate group (-SO3K).

[0093] Suitable acid dyes can be, for example, one or more compounds selected from the following group: 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 (CI 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;CI 20170;KATSU201;nosodiumsalt;Brown No.201;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201;D & C Brown No.1), Acid Red 14 (CI14720), 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, lodeosin), 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.

[0094] 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 inspected 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.

[0095] 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).

[0096] Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of 20 g / L (25 °C).

[0097] 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).

[0098] 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.

[0099] 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).

[0100] 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 diantrium salt of 5-amino-4-hydroxy-3-(phenylazo)naphthalene-2,7-disulfonate; its water solubility is 2.5 g / L (25 °C).

[0101] 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).

[0102] 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).

[0103] In einer weiteren Ausführungsform ist ein erfindungsgemäßes Mittel daher dadurch gekennzeichnet, dass es mindestens einen direktziehenden Farbstoff (a2) enthält, der ausgewählt ist aus der Gruppe aus Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33,D&C Violet 2 and / or D&C Brown 1.,

[0104] The direct dye(s) can be used in varying amounts in the composition, depending on the desired color intensity. Good results have been obtained when the composition contains one or more direct dyes (a2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.1 to 8.0 wt.%, more preferably 0.2 to 6.0 wt.%, and most preferably 0.5 to 4.5 wt.%, based on the total weight of the composition.

[0105] Furthermore, the agent can also contain at least one photochromic or thermochromic dye as a coloring compound (a2).

[0106] Photochromic dyes are dyes that react to irradiation with UV light (sunlight or black light) with a reversible change in hue. The UV light alters the chemical structure of the dyes and thus their absorption behavior (photochromism).

[0107] Thermochromic dyes are dyes that react to temperature changes with a reversible change in hue. The temperature change alters the chemical structure of the dyes and thus their absorption behavior (thermochromism).

[0108] The composition may contain – based on the total weight of the composition – one or more photochromic dyes (a2) in a total amount of 0.01 to 10.0 wt.%, preferably 0.1 to 8.0 wt.%, more preferably 0.2 to 6.0 wt.% and most preferably 0.5 to 4.5 wt.% Polysaccharides (a3)

[0109] As a third essential component (a3) ​​of the invention, the compositions according to the invention contain at least one polysaccharide selected from the group consisting of hydroxy-C1-C30-alkyl celluloses, hydroxy-C1-C30-alkyl methyl celluloses, hydroxy-C1-C30-alkyl ethyl celluloses, C1-C30-alkyl celluloses, C6-C30-alkyl hydroxyethyl celluloses, cellulose, starch, xanthan gum, carboxyalkyl cellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan gum, pectin, agaropectin and / or their salts

[0110] The term polysaccharide is the collective term for macromolecular carbohydrates whose molecules consist of a large number of monosaccharide molecules linked together by glycosidic bonds (with a molar mass of at least 5000 g / mol).

[0111] Particularly good suitability was shown by nonionic polysaccharides selected from the group consisting of hydroxy-C 1 -C 30 -alkylcelluloses, hydroxy-C 1 -C 30 -alkylmethylcelluloses, hydroxy-C 1 -C 30 -alkylethylcelluloses, C 1 -C 30 -alkylcelluloses and cellulose.

[0112] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains at least one non-ionic polysaccharide (a3) ​​selected from the group consisting of hydroxy-C1-C30 alkylcellulose, hydroxy-C1-C30 alkylmethylcellulose, hydroxy-C1-C30 alkylethylcellulose, C1-C30 alkylcellulose, C6-C30 alkylhydroxyethylcelluloses, cellulose and starch.

[0113] Hydroxy-C 1 -C 30 -alkylcelluloses are cellulose ethers that are produced industrially by etherification of alkylcellulose with the corresponding alkyl oxide.

[0114] Particularly preferred hydroxy-C 1 -C 30 -alkylcelluloses are hydroxyethylcellulose and hydroxypropylcellulose.

[0115] Hydroxyethylcellulose is a cellulose ether that is produced industrially by etherification of alkali cellulose with ethylene oxide. Since the primary hydroxy group of a 2-hydroxyethyl substituent, which is formed in the first etherification step of a cellulose OH group with ethylene oxide, reacts faster with further ethylene oxide than the hydroxy groups of the cellulose itself, longer oligo- or polyethylene oxide side chains are present in the resulting HECs alongside unreacted cellulose OH groups.

[0116] A particularly suitable hydroxyethylcellulose can, for example, be obtained commercially in the form of the raw material Natrosol 250 HHX from the company Ashland.

[0117] Another particularly suitable hydroxyethylcellulose is commercially marketed by Dow under the trade name Cellosize WP 300 H.

[0118] Hydroxypropyl celluloses are cellulose ethers produced industrially by reacting alkali celluloses with methyloxirane (propylene oxide). Commercially available hydroxypropyl celluloses typically have an average molar substitution (MS) of approximately 4–4.5.

[0119] A particularly suitable hydroxypropyl cellulose can, for example, be purchased in the form of the raw material Klucel H CS from the company Hercules.

[0120] In a particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one polysaccharide (a3) ​​selected from the group consisting of hydroxyethylcellulose and hydroxypropylcellulose.

[0121] Hydroxy-C 1 -C 30 -alkylmethylcelluloses are alkoxylated methylcelluloses.

[0122] One particularly favored hydroxy-C1-C30 alkylmethylcellulose is, for example, hydroxyethylmethylcellulose. Hydroxyethylmethylcellulose is a collective term for chemical compounds produced by the etherification of cellulose. In these compounds, some of the hydroxyl groups of the cellulose are linked as ethers to methyl and hydroxyethyl groups.

[0123] Another particularly favored hydroxy-C1-C30 alkylmethylcellulose is, for example, hydroxypropylmethylcellulose. Hydroxypropylmethylcellulose is a methylcellulose substituted with propylene oxide. It is available on the market in various degrees of polymerization and different degrees of substitution.

[0124] A particularly suitable hydroxypropyl methyl cellulose can be purchased commercially, for example, in the form of the product Benecel K 4 M from the company Ashland.

[0125] Hydroxy-C 1 -C 30 -alkylethylcelluloses are alkoxylated ethylcelluloses.

[0126] Examples of suitable C1-C30 alkyl celluloses include methylcellulose and ethylcellulose.

[0127] Various methylcelluloses from the company Herkules are available for purchase under the trade names Culminal DM 40 and Culminal MC 12000.

[0128] Ethylcellulose is obtained semi-synthetically from naturally occurring cellulose and is a cellulose ether that comes in different types which differ in their degree of polymerization (molecular mass distribution) and in their degree of etherification.

[0129] A particularly suitable ethylcellulose can be obtained commercially, for example, under the trade name Aqualon EC N 10 Ethylcellulose from the company Ashland.

[0130] C6-30 alkylhydroxyethylcelluloses are cellulose compounds in which hydrophobic C6-30 alkyl groups are bonded to the cellulose backbone via ethylene oxide units. Due to the introduction of C6-30 alkyl groups onto ethylene oxide units of the backbone, these celluloses exhibit hydrophobic properties and are also referred to as hydrophobically modified hydroxyethylcelluloses.

[0131] 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) within 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 not considered an anionic polysaccharide.

[0132] The cellulose used according to the invention has a degree of polymerization (DP), i.e., a chain length of glucopyranose units, of 10 to approximately 8000. However, it has been found that celluloses with a low degree of polymerization, in particular, have a positive effect on the dyeing properties of the agents.

[0133] In particular, so-called microcrystalline cellulose exhibits advantageous effects in this context. 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.

[0134] 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.

[0135] Preferred celluloses are therefore microcrystalline celluloses with a degree of polymerization of 30 to 400.

[0136] One embodiment of the present invention is therefore characterized in that the agent contains microcrystalline cellulose as cellulose.

[0137] Starch is a polysaccharide with the formula (C₆H₁₀O₅)n, composed of α-D-glucose units. This macromolecule belongs to the carbohydrates. Starch is one of the most important storage substances in plant cells.

[0138] A starch that can be used according to the invention can be obtained, for example, from potatoes, corn, rice, peas, acorns, chestnuts, barley, wheat, bananas, sago, millet, sorghum, oats, rye, beans, sweet potatoes, maranta or cassava.

[0139] In a further preferred embodiment, a means according to the invention is characterized in that it contains at least one polysaccharide (a3) ​​selected from the group consisting of potato starch, maize starch, rice starch, pea starch, acorn starch, chestnut starch, barley starch, wheat starch, rye starch, banana starch, sago starch, millet starch, sorghum starch, oat starch, bean starch, sweet potato starch, maranta starch and cassava starch.

[0140] In a particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one anionic polysaccharide (a3) ​​selected from the group consisting of xanthan gum, carboxyalkylcellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan gum, pectin, agaropectin and / or their salts.

[0141] Xanthan gum is a polysaccharide composed, among other things, of the structural components D-glucose, D-mannose, D-glucuronic acid, acetate, and pyruvate, and is also known by the INCI name Xanthan Gum. Xanthan gum contains carboxyl groups and is anionic or anionizable. The physiologically compatible salts of xanthan gum are also produced according to the invention.

[0142] Alginates (INCI name Algin) are the salts of alginic acid. Alginates are acidic polysaccharides containing carboxy groups, consisting of D-mannuronic acid and D-guluronic acid in varying ratios, linked by 1,4-glycosidic bonds. According to the invention, the alkali and alkaline earth salts of alginic acids are particularly suitable. The use of alginic acid, sodium alginate, potassium alginate, ammonium alginate, and / or calcium alginate in the preparations according to the invention has proven especially advantageous.

[0143] Carboxyalkyl celluloses are cellulose ethers in which the hydrogen atoms of the hydroxyl groups of the cellulose are partially or completely substituted by carboxyalkyl groups. A preferred carboxyalkyl cellulose is carboxymethylcellulose, which can preferably be used as an anionic polymer in the form of its sodium salt (sodium carboxymethylcellulose).

[0144] Carrageenan is also known as carrageenan. It is sulfated galactan, which can be obtained, for example, by extraction from red algae. The carrageenan precipitated from the hot water extract of the algae is a colorless to sandy-colored powder with a molecular weight of 100,000–800,000 and a sulfate content of approximately 25%, and is very soluble in warm water. Three main components of carrageenan with different properties are distinguished: κ-carrageenan, The compounds are -carrageenan and λ-carrageenan. The gel-forming κ-fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately linked by glycosidic bonds at the 1,3- and 1,4-positions. The non-gelling λ-fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. λ-Carrageenan, composed of D-galactose-4-sulfate linked at the 1,3-position and 3,6-anhydro-α-D-galactose-2-sulfate linked at the 1,4-position, is soluble in hot water and also gel-forms.

[0145] Within the group of anionic polysaccharides, xanthan gum has proven to be particularly well-suited for achieving intense color results. Therefore, compositions according to the invention containing xanthan gum (a3) ​​are explicitly preferred.

[0146] In a particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one xanthan (a3).

[0147] The polysaccharide(s), in particular the previously described preferred and especially preferred representatives, are preferably used in certain quantity ranges in the composition according to the invention to achieve the best possible color intensity.

[0148] In this context, it has proven particularly advantageous if the composition according to the invention contains one or more polysaccharides (a3) ​​in a total amount of 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.%.

[0149] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains - based on the total weight of the composition - one or more polysaccharides (a3) ​​in a total amount of 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.%.

[0150] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains - based on the total weight of the composition - one or more non-ionic polysaccharides (a3) ​​in a total amount of 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.%.

[0151] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains - based on the total weight of the composition - one or more anionic polysaccharides (a3) ​​in a total amount of 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.%.

[0152] It is explicitly and particularly preferred if the composition according to the invention contains 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.% hydroxyethylcellulose, based on the total weight of the composition.

[0153] It is further explicitly and particularly preferred if the composition according to the invention contains 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.% hydroxypropylcellulose, based on the total weight of the composition.

[0154] It is further explicitly and particularly preferred if the composition according to the invention contains 0.1 to 6.0 wt.%, preferably 0.5 to 5.0 wt.%, more preferably 1.0 to 4.0 wt.% and most preferably 1.5 to 3.5 wt.% xanthan gum, based on the total weight of the composition. Avoidance of silicone resins in the average

[0155] The work leading to this invention has shown that the previously described agents, which additionally contain at least one silicone resin, have significant disadvantages with regard to the production of colorations with high color intensity. For this reason, the agent according to the invention is characterized in that it is free of silicone resins.

[0156] For the purposes of this definition, a silicone resin is understood to be an MX resin, where "M" represents a Me3SiO unit and "Q" represents a SiO4 unit. Silicone resins thus comprise at least one, preferably several, "M" units and at least one, preferably several, Q units. Due to the SiO4 unit, silicone resins are therefore branched, unlike linear silicone polymers (a1).

[0157] Regarding the further definition of silicone resins, reference is made in full to document EP 3058935 B1.

[0158] In other words, the subject matter of the present invention is a means for dyeing keratinous material, in particular human hair, comprising (a1) at least one linear, amino-functionalized silicone polymer, and (a2) at least one pigment having a solubility in water at 25 °C of less than 0.05 g / L, and (a3) ​​at least one polysaccharide selected from the group consisting of hydroxy-C1-C30 alkylcelluloses, hydroxy-C1-C30 alkylmethylcelluloses, hydroxy-C1-C30 alkylethylcelluloses, C1-C30 alkylcelluloses, C6-C30 alkylhydroxyethylcelluloses, cellulose, starch, xanthan gum, carboxyalkylcellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan gum, pectin, agaropectin and / or their salts, characterized in that the agent is free of MQ silicone resins

[0159] Examples of silicone resins are commercially available from Wacker-Chemie AG, D-81737 Munich.

[0160] For example, the MQ silicone resin POWDER 803 TF is the product of a co-hydrolysis of tetraalkoxysilane (Q unit) and trimethyl ethoxysilane (M unit) and can be understood as a three-dimensional network of polysilicic acid blocked at the ends with trimethylsilyl groups.

[0161] Other MQ silicone resins can also be obtained from Dow Corning. For example, Dow Corning® MQ-1640 Flake Resin is a combination of MQ and T propyl silicone resin and has the INCI name: Trimethylsiloxysilicate (and) Polypropyl silsesquioxane.

[0162] A mixture of aminosilicone and MQ resin can, for example, also be purchased commercially in the form of the trade product Belsil ADM 8301 E from Wacker; this substance bears the INCI name Amodimethicone / Morpholinomethyl Silsesquioxane Copolymer.

[0163] A characteristic feature of the composition according to the invention is that it does not contain the previously described MQ resins, i.e., the total amount of all MQ silicone resins contained in the composition according to the invention is - based on the total amount of the composition - 0 wt.%. Fat components (a4)

[0164] As a further optional component, the composition according to the invention can additionally contain at least one fat component (a4). It has been found that the use of at least one fat component (a4) results in the composition being in the form of an emulsion which has the optimal viscosity and has also proven advantageous with regard to improving color intensity.

[0165] For the purposes of this invention, "fat components" are defined as organic compounds with a solubility in water at room temperature (22 °C) and atmospheric pressure (760 mmHg) of less than 1 wt.%, preferably less than 0.1 wt.%. The definition of fat components explicitly includes only uncharged (i.e., nonionic) compounds. Fat components possess at least one saturated or unsaturated alkyl group with at least 12 carbon atoms. The molecular weight of the fat components is a maximum of 5000 g / mol, preferably a maximum of 2500 g / mol, and particularly preferably a maximum of 1000 g / mol. The fat components are neither polyoxyalkylated nor polyglycerylated compounds.

[0166] The fatty components (a4) contained in the medium are particularly preferred, selected from the group of C 12 -C 30 fatty alcohols, C 12 -C 30 fatty acid triglycerides, C 12 -C 30 fatty acid monoglycerides, C 12 -C 30 fatty acid diglycerides and / or hydrocarbons.

[0167] In a further preferred embodiment, a composition according to the invention is characterized in that it contains one or more fatty components (a4) from the group consisting of C 12 -C 30 fatty alcohols, C 12 -C 30 fatty acid triglycerides, C 12 -C 30 fatty acid monoglycerides, C 12 -C 30 fatty acid diglycerides and / or hydrocarbons.

[0168] Particularly preferred fat components in this context are those from the group consisting of C12-C30 fatty alcohols, C12-C30 fatty acid triglycerides, C12-C30 fatty acid monoglycerides, C12-C30 fatty acid diglycerides, and / or hydrocarbons. For the purposes of the present invention, only nonionic substances are explicitly considered fat components. Charged compounds such as fatty acids and their salts are not considered fat components.

[0169] C12-C30 fatty alcohols can be saturated, mono- or polyunsaturated, linear or branched fatty alcohols with 12 to 30 carbon atoms.

[0170] Examples of preferred linear saturated C12-C30 fatty alcohols are dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachiyl alcohol (eicosan-1-ol), heneicosyl alcohol (heneicosan-1-ol) and / or behenyl alcohol (docosan-1-ol).

[0171] Preferred linear unsaturated fatty alcohols are (9 Z )-Octadec-9-en-1-ol (oleyl alcohol), (9E)-Octadec-9-en-1-ol (elaidyl alcohol), (9 Z 12 Z )-Octadeca-9,12-dien-1-ol (linoleyl alcohol), (9 Z 12 Z 15 Z )-Octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleyl alcohol ((9 Z )-Eicos-9-en-1-ol), arachidone alcohol ((5 Z 8 Z ,11 Z 14 Z )-Eicosa-5,8,11,14-tetraen-1-ol), Erucyl alcohol ((132)-Docos-13-en-1-ol) and / or Brassidyl alcohol ((13E)-Docosen-1-ol).

[0172] The preferred representatives for branched fatty alcohols are 2-octyl-dodecanol, 2-hexyl-dodecanol and / or 2-butyl-dodecanol.

[0173] In a further preferred embodiment, a composition according to the invention is characterized in that it comprises one or more C 12 -C 30 fatty alcohols (a4) from the group consisting of Dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecyl alcohol, stearyl alcohol), arachyl alcohol (eicosan-1-ol), heneicosyl alcohol (heneicosan-1-ol), Behenyl alcohol (docosan-1-ol), (9 Z )-Octadec-9-en-1-ol (oleyl alcohol), (9 E )-Octadec-9-en-1-ol (elaidyl alcohol), (9 Z 12 Z )-Octadeca-9,12-dien-1-ol (linoleyl alcohol), (9 Z 12 Z 15 Z )-Octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleyl alcohol ((9 Z)-Eicos-9-en-1-ol), arachidone alcohol ((5 Z 8 Z ,11 Z 14 Z )-Eicosa-5,8,11,14-tetraen-1-ol), erucyl alcohol ((13 Z )-Docos-13-en-1-ol), brassidyl alcohol ((13E)-docosen-1-ol), 2-octyl-dodecanol, 2-hexyl-dodecanol and / or 2-butyl-dodecanol.

[0174] It has proven to be particularly advantageous to use one or more C 12 -C 30 fatty alcohols (a4) in very specific quantity ranges.

[0175] It is particularly preferred if the composition contains one or more C 12 -C 30 fatty alcohols (a4) in a total amount of 2.0 to 50.0 wt.%, preferably 3.0 to 30.0 wt.%, more preferably 4.0 to 20.0 wt.%, even more preferably 5.0 to 15.0 wt.% and most preferably 5.0 to 10.0 wt.%.

[0176] Furthermore, as a very suitable fatty component (a4), the composition can also contain at least one C12-C30 fatty acid triglyceride, one C12-C30 fatty acid monoglyceride, and / or one C12-C30 fatty acid diglyceride. For the purposes of the present invention, a C12-C30 fatty acid triglyceride is understood to be the triester of the trihydric alcohol glycerol with three equivalents of fatty acid. Both structurally identical and different fatty acids within a triglyceride molecule can participate in the esterification.

[0177] According to the invention, fatty acids are understood to be saturated or unsaturated, unbranched or branched, unsubstituted or substituted C12-C30 carboxylic acids. Unsaturated fatty acids can be monounsaturated or polyunsaturated. In an unsaturated fatty acid, its C12-C30 double bond(s) can have a cis or trans configuration.

[0178] Fatty acid triglycerides are characterized by their particular suitability, in which at least one of the ester groups starting from glycerol is formed with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z, 12Z)-octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)-Octadeca-9,12,15-trienoic acid, elaeostearic acid [(9 Z ,11E,13E)-Octadeca-9,11,3-trienic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-tetraenoic acid] and / or nervonic acid [(15Z)- Tetracos-15-enoic acid].

[0179] The fatty acid triglycerides can also be of natural origin. The fatty acid triglycerides or mixtures thereof occurring in soybean oil, peanut oil, olive oil, sunflower oil, macadamia nut oil, moringa oil, apricot kernel oil, marula oil and / or optionally hydrogenated castor oil are particularly suitable for use in the product according to the invention.

[0180] A C12-C30 fatty acid monoglyceride is defined as the monoester of the trihydric alcohol glycerol with one equivalent of fatty acid. Either the central hydroxyl group of glycerol or the terminal hydroxyl group of glycerol can be esterified with the fatty acid.

[0181] C12-C30 fatty acid monoglycerides are characterized by their particular suitability, in which a hydroxyl group of the glycerol is esterified with a fatty acid, the fatty acids being selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z, 12Z)-Octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)-Octadeca-9,12,15-trienoic acid, elaeostearinic acid [(9Z,11E,13E)-Octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-tetraenoic acid] or nervonic acid [(15Z)-tetracos-15-enoic acid].

[0182] A C12-C30 fatty acid diglyceride is defined as the diester of the trihydric alcohol glycerol with two equivalents of fatty acid. Either the central and one terminal hydroxyl group of the glycerol can be esterified with two equivalents of fatty acid, or both terminal hydroxyl groups of the glycerol can be esterified with one fatty acid each. The glycerol can be esterified with either two structurally identical or two different fatty acids.

[0183] Fatty acid diglycerides are characterized by their particular suitability, in which at least one of the ester groups starting from glycerol is formed with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z, 12Z)-octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)-Octadeca-9,12,15-trienic acid, Elaeostearinic acid [(9Z,11E,13E)-Octadeca-9,11,3-trienic acid], Arachidonic acid [(5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-tetraenic acid] and / or Nervonic acid [(15Z)-Tetracos-15-enoic acid].

[0184] Particularly good results were obtained when composition (B) contained at least one C12-C30 fatty acid monoglyceride selected from the monoesters of glycerol with one equivalent fatty acid from the group consisting of dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z, 12Z)-Octadeca-9,12-dienoic acid, linolenic acid [(9Z,12Z,15Z)-Octadeca-9,12,15-trienoic acid, elaeostearinic acid [(9Z,11E,13E)-Octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-tetraenoic acid] and / or nervonic acid [(15Z)-tetracos-15-enoic acid].

[0185] In a further embodiment, a composition according to the invention is characterized in that it contains at least one C 12 -C 30 fatty acid monoglyceride (a4) which is selected from the monoesters of glycerol with an equivalent fatty acid from the group consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, tetracosanoic acid, octadecanoic acid, eicosanoic acid and / or docosanoic acid.

[0186] It has proven preferable to use one or more C 12 -C 30 fatty acid mono-, C 12 -C 30 fatty acid di- and / or C 12 -C 30 fatty acid triglycerides (a4) in very specific quantity ranges on average.

[0187] With regard to solving the problem according to the invention, it has proven advantageous if the agent - based on the total weight of the agent - contained one or more C 12 -C 30 fatty acid mono-, C 12 -C 30 fatty acid di- and / or C 12 -C 30 fatty acid triglycerides (a4) in a total amount of 0.1 to 20.0 wt.%, preferably 0.3 to 15.0 wt.%, more preferably 0.5 to 10.0 wt.% and most preferably 0.8 to 5.0 wt.%.

[0188] In a particularly preferred embodiment, a method according to the invention is characterized in that the agent contains, based on the total weight of the agent, one or more C 12 -C 30 fatty acid mono-, C 12 -C 30 fatty acid di- and / or C 12 -C 30 fatty acid triglycerides in a total amount of 0.1 to 20.0 wt.%, preferably 0.3 to 15.0 wt.%, more preferably 0.5 to 10.0 wt.% and most preferably 0.8 to 5.0 wt.%.

[0189] The C12-C30 fatty acid mono-, C12-C30 fatty acid di- and / or C12-C30 fatty acid triglycerides can be used as the sole fat components (a4) in the composition. However, according to the invention, it is also possible to incorporate at least one C12-C30 fatty acid mono-, C12-C30 fatty acid di- and / or C12-C30 fatty acid triglyceride in combination with at least one C12-C30 fatty alcohol into the composition.

[0190] Furthermore, as a particularly preferred fatty component (a4), the product may also contain at least one hydrocarbon.

[0191] Hydrocarbons are compounds consisting exclusively of carbon and hydrogen atoms, with 8 to 80 carbon atoms. Particularly preferred in this context are aliphatic hydrocarbons such as mineral oils, liquid paraffin oils (e.g., paraffinum liquidum or paraffinum perliquidum), isoparaffin oils, semi-solid paraffin oils, paraffin waxes, hard paraffin (paraffinum solidum), petrolatum, and polydecenes.

[0192] Liquid paraffin oils (paraffinum liquidum and paraffinum perliquidum) have proven particularly suitable in this context. Paraffinum liquidum, also known as white oil, is especially preferred as the hydrocarbon. Paraffinum liquidum is a mixture of purified, saturated, aliphatic hydrocarbons, consisting largely of hydrocarbon chains with a carbon chain distribution of 25 to 35 carbon atoms.

[0193] Particularly good results were obtained when the product contained at least one hydrocarbon (a4) selected from the group of mineral oils, liquid paraffin oils, isoparaffin oils, semi-solid paraffin oils, paraffin waxes, hard paraffin (Paraffinum Solidum), petrolatum and polydecenes.

[0194] In a particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one fatty component (a4) from the group of hydrocarbons.

[0195] With regard to solving the problem according to the invention, it has proven to be particularly advantageous if the agent - based on the total weight of the agent - contained one or more hydrocarbons (a4) in a total amount of 0.5 to 20.0 wt.%, preferably 0.7 to 10.0 wt.%, more preferably 0.9 to 5.0 wt.% and most preferably 1.0 to 4.0 wt.%.

[0196] In a particularly preferred embodiment, a composition according to the invention is characterized in that it contains – based on the total weight of the composition – one or more hydrocarbons (a4) in a total quantity of 0.5 to 20.0 wt.%, preferably 0.7 to 10.0 wt.%, more preferably 0.9 to 5.0 wt.% and most preferably 1.0 to 4.0 wt.%.

[0197] The hydrocarbon(s) can be used as the sole fat component (a4) in the composition. However, it is also according to the invention to incorporate at least one hydrocarbon in combination with at least one other component into the composition.

[0198] The composition most preferably contains at least one fatty component (a4) from the group of C 12 -C 30 fatty alcohols and at least one further fatty component from the group of hydrocarbons. Average water content

[0199] The previously described agent is a ready-to-use agent that can be applied to the keratinous material. This ready-to-use agent preferably has a high water content. It has been found that agents containing 50.0 to 98.0 wt.%, preferably 60.0 to 90.0 wt.%, more preferably 70.0 to 90.0 wt.%, and most preferably 75.0 to 90.0 wt.% water, based on the total weight of the agent, are particularly suitable.

[0200] In a further explicitly preferred embodiment, a composition according to the invention is characterized in that it contains - based on the total weight of the composition - 50.0 to 98.0 wt.%, preferably 60.0 to 90.0 wt.%, more preferably 70.0 to 90.0 wt.% and most preferably 75.0 to 90.0 wt.% water. Surfactants on average

[0201] Due to its water and fat content (a4), the composition according to the invention is particularly preferably in the form of an emulsion. To further optimize the formation of the emulsion, it has proven particularly advantageous to include at least one surfactant in the composition.

[0202] Therefore, the product preferably contains at least one additional surfactant.

[0203] In a further particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one surfactant.

[0204] The term surfactants (T) refers to surface-active substances that form adsorption layers on surfaces and interfaces or can aggregate in bulk phases to form micelle colloids or lyotropic mesophases. A distinction is made between anionic surfactants, consisting of a hydrophobic residue and a negatively charged hydrophilic head group; amphoteric surfactants, which carry both a negative and a compensating positive charge; cationic surfactants, which have a hydrophobic residue and a positively charged hydrophilic group; and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

[0205] In a particularly preferred embodiment, a means according to the invention is characterized in that it contains at least one anionic and / or nichitonic surfactant.

[0206] Suitable anionic surfactants that can be used in the compositions according to the invention include: Linear and branched fatty acids with 8 to 30 carbon atoms (soaps), ether carboxylic acids of the formula RO-(CH₂-CH₂O)ₓ-CH₂-COOH, in which R is a linear or branched, saturated or unsaturated alkyl group with 8 to 30 carbon atoms and x = 0 or 1 to 16, acyl sarcosides with 8 to 24 carbon atoms in the acyl group, acyl taurides with 8 to 24 carbon atoms in the acyl group, acylisethionates with 8 to 24 carbon atoms in the acyl group, sulfosuccinic acid mono- and / or dialkyl esters with 8 to 24 carbon atoms in the alkyl group, and sulfosuccinic acid monoalkyl polyoxyethyl esters with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups. Alpha-olefin sulfonates with 8 to 24 carbon atoms, alkyl sulfate and / or alkyl polyglycol ether sulfate salts of the formula R-(OCH2-CH2)x-OSO3-<X+<, in which R is a preferably linear or branched, saturated or unsaturated alkyl group with 8 to 30 carbon atoms, x = 0 or 1 to 12 and X is an alkali or ammonium ion,Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds, esters of tartaric acid and citric acid with alcohols, representing addition products of approximately 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms, alkyl and / or alkenyl ether phosphates of the formula, , in the R 1 preferably for an aliphatic hydrocarbon residue with 8 to 30 carbon atoms, R 2 for hydrogen, a remainder (CH 2 CH 2 O) n R 1 or X, n for numbers from 0 to 10 and X for hydrogen, an alkali or alkaline earth metal, or NR 3 R 4 R 5 R 6 , with R 3 to R 6 independently of each other, representing a C 1 up to C 4 -Hydrocarbon residue, stands.

[0207] Non-ionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups as their hydrophilic group. Examples of such compounds are... Addition products of 2 to 50 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide to linear and branched fatty alcohols with 6 to 30 carbon atoms, the fatty alcohol polyglycol ethers or the fatty alcohol polypropylene glycol ethers or mixed fatty alcohol polyethers; addition products of 2 to 50 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide to linear and branched fatty acids with 6 to 30 carbon atoms, the fatty acid polyglycol ethers or the fatty acid polypropylene glycol ethers or mixed fatty acid polyethers; addition products of 2 to 50 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide to linear and branched alkylphenols with 8 to 15 carbon atoms in the alkyl group, the alkylphenol polyglycol ethers or the alkyl polypropylene glycol ethers, or mixed alkylphenol polyethers. End-group sealed addition products of 2 to 50 mol ethylene oxide and / or 0 to 5 mol propylene oxide to linear and branched fatty alcohols with 8 to 30 carbon atoms, with a methyl or C2-C6 alkyl group,fatty acids with 8 to 30 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group, such as the types available under the trade names Dehydol® LS, Dehydol® LT (Cognis), C12-C30 fatty acid mono- and diesters of adsorption products of 1 to 30 mol of ethylene oxide to glycerol, adsorption products of 5 to 60 mol of ethylene oxide to castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the trade product Hydagen® HSP (Cognis) or Sovermol® types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of the formula (Tnio-1) R1 CO-(OCH2 CHR2) w OR3 (Tnio-1) in the R1 CO represents a linear or branched, saturated and / or unsaturated acyl group with 6 to 22 carbon atoms, R 2< represents hydrogen or methyl, R 3< represents linear or branched alkyl groups with 1 to 4 carbon atoms, and w represents numbers from 1 to 20. Examples include amine oxides and hydroxyl mixed ethers.as described, for example, in DE-OS 19738866, sorbitan fatty acid esters and adsorption products of ethylene oxide to sorbitan fatty acid esters such as polysorbates, sugar fatty acid esters and adsorption products of ethylene oxide to sugar fatty acid esters, adsorption products of ethylene oxide to fatty acid alkanolamides and fatty amines, sugar surfactants of the type of alkyl and alkenyl oligoglycosides according to formula (E4-II), R 4< O-[G] p (Tnio-2) where R 4< represents an alkyl or alkenyl residue with 4 to 22 carbon atoms, G represents a sugar residue with 5 or 6 carbon atoms, and p represents numbers from 1 to 10. They can be obtained according to the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose,The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglycosides. The index p in the general formula (Tnio-2) indicates the degree of oligomerization (DP), i.e., the distribution of mono- and oligoglycosides, and represents a number between 1 and 10. While p in a single molecule must always be an integer and can primarily take the values ​​p = 1 to 6, the value p for a specific alkyl oligoglycoside is an analytically determined calculated quantity, which usually represents a fraction. Preferably, alkyl and / or alkenyl oligoglycosides with a mean degree of oligomerization p of 1.1 to 3.0 are used. From an application-related point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and, in particular, between 1.2 and 1.4 are preferred. The alkyl or alkenyl residue R 4< can differ from primary alcohols with 4 to 11,preferably derived from 8 to 10 carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol, and undecyl alcohol, as well as their technical mixtures, such as those obtained, for example, during the hydrogenation of technical fatty acid methyl esters or during the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides of chain length C8-C10 (DP = 1 to 3), which are obtained as foreshots during the distillative separation of technical C8-C18 coconut fatty alcohol and may be contaminated with less than 6 wt% C12 alcohol, as well as alkyl oligoglucosides based on technical C9 / 11 oxo alcohols (DP = 1 to 3), are preferred. The alkyl or alkenyl group R 15< can also be derived from primary alcohols with 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.Elaidyl alcohol, petroselinyl alcohol, arachiyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and their technical mixtures, which can be obtained as described above. Preferably, alkyl oligoglucosides based on hydrogenated C12 / 14 coconut alcohol with a DP of 1 to 3 are used. Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide type, a nonionic surfactant of the formula (Tnio-3), R5<CO-NR6<-[Z] (Tnio-3) in which R5<CO represents an aliphatic acyl group with 6 to 22 carbon atoms, R6< represents hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl group with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. Fatty acid N-alkylpolyhydroxyalkylamides are well-known substances that are usually produced by reductive amination of a reducing sugar with ammonia,Fatty acid N-alkylpolyhydroxyalkylamides can be obtained by reacting an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester, or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the formula (Tnio-4): R 7< CO-(NR 8< )-CH 2 -[CH(OH)] 4 -CH 2 OH (Tnio-4). Preferably, the fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (Tnio-4), in which R 8< represents hydrogen or an alkyl group and R 7< CO represents the acyl group of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid.Behenic acid or erucic acid, or their technical mixtures, are preferred. Particularly preferred are fatty acid N-alkylglucamides of the formula (Tnio-4), which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid, or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

[0208] Other typical examples of non-ionic surfactants are fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, mixed ethers or mixed formals, protein hydrolysates (especially plant-based products based on wheat) and polysorbates.

[0209] Preferred non-ionic surfactants include alkylene oxide adsorption products to saturated linear fatty alcohols and fatty acids, each containing 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, as well as sugar surfactants. Preparations with excellent properties are also obtained when they contain fatty acid esters of ethoxylated glycerol as non-ionic surfactants.

[0210] These compounds are characterized by the following parameters. The alkyl group R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear groups and 2-methyl-branched aliphatic groups are preferred. Examples of such alkyl groups are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl, and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, and 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

[0211] The compounds with alkyl groups used as surfactants can each be a single, homogeneous substance. However, it is generally preferred to start with native plant or animal raw materials for their production, resulting in mixtures of substances with varying alkyl chain lengths, depending on the specific raw material.

[0212] The surfactant(s) can be contained in an average amount of 0.1 to 18.0 wt.%, preferably 0.5 to 16.0 wt.%, more preferably 1.0 to 14.0 wt.% and most preferably 1.5 to 12.0 wt.%, based on the total weight of the product. other optional ingredients in the medium

[0213] In addition to the components essential to the invention (a1) to (a3) ​​already described, the agent may also contain further optional ingredients.

[0214] The products may also contain other active ingredients, excipients, and additives, such as solvents, structuring agents like glucose, maleic acid, and lactic acid; hair-conditioning compounds like 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; colorants for coloring the product; 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; vegetable oils; sunscreens and UV blockers; Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidone carboxylic acids and their salts, as well as bisabolol;Polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifying agents such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; and blowing agents such as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and air.

[0215] The selection of these additional substances will 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. pH value of the medium

[0216] The pH values ​​of the composition according to the invention can be adjusted to a slightly acidic to alkaline pH value. Most preferably, the dye (F) has a pH value in the range of 5.0 to 10.0, more preferably 6.0 to 9.5, more preferably 6.0 to 8.7, and most preferably 6.0 to 7.5.

[0217] Alkalizing and acidifying agents known to those skilled in the art can be used to adjust the desired pH values. The pH values ​​referred to in the present invention are pH values ​​measured at a temperature of 22°C.

[0218] The alkalizing agents can include, for example, ammonia, alkanolamines and / or basic amino acids.

[0219] The alkanolamines usable in the composition according to the invention are preferably selected from primary amines with a C2-C6 alkyl backbone bearing at least one hydroxyl group. Preferred alkanolamines are selected from the group consisting of 2-aminoethanol-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, and 2-amino-2-methylpropan-1,3-diol.

[0220] According to the invention, particularly preferred alkanolamines are selected from 2-aminoethanol-1-ol and / or 2-amino-2-methylpropan-1-ol. A particularly preferred embodiment is therefore characterized in that the composition according to the invention contains an alkanolamine selected from 2-aminoethanol-1-ol and / or 2-amino-2-methylpropan-1-ol as an alkalizing agent.

[0221] For the purposes of this invention, an amino acid is defined as an organic compound whose structure contains at least one protonable amino group and at least one -COOH or -SO3H group. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0222] According to the invention, basic amino acids are understood to be those amino acids which have an isoelectric point pl of greater than 7.0.

[0223] Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. Within the scope of the present invention, both possible enantiomers can be used as specific compounds or mixtures thereof, particularly as racemates. However, it is especially advantageous to use the naturally occurring isomeric form, usually in the L-configuration.

[0224] The basic amino acids are preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, particularly preferably from arginine and lysine. In a further particularly preferred embodiment, a composition according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group consisting of arginine, lysine, ornithine, and / or histidine.

[0225] Furthermore, the composition may contain additional alkalizing agents, in particular inorganic alkalizing agents. Inorganic alkalizing agents that can be used according to the invention are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0226] The desired pH value is also adjusted according to the invention using a buffer system. A buffer or buffer system is typically understood to be a mixture of a weak or moderately strong acid (e.g., acetic acid) with a practically completely dissociated neutral salt of the same acid (e.g., sodium acetate). If some base or acid is added, the pH value hardly changes (buffering). The effect of the buffer substances contained in a buffer solution is based on the trapping reaction of hydrogen or hydroxide ions, forming weak acids or bases due to their dissociation equilibrium.

[0227] A buffer system can be formed from a mixture of an inorganic or organic acid and a corresponding salt of that acid.

[0228] Acids can be buffered by all salts of weak acids and strong bases, and bases by salts of strong acids and weak bases. For example, strong hydrochloric acid (completely dissociated into ions) can be buffered by adding sodium acetate. This is in accordance with the equilibrium. Hydrochloric acid is converted to weak acetic acid by sodium acetate, forming table salt. Acetic acid dissociates only to a very small extent in the presence of an excess of sodium acetate. Buffers that act against both acids and bases are mixtures of weak acids and their salts.

[0229] Well-known examples of buffer systems from the literature are acetic acid / sodium acetate, boric acid / sodium borate, phosphoric acid / sodium phosphate and hydrogen carbonate / soda.

[0230] The pH value of the composition according to the invention can be adjusted, for example, by adding an inorganic or organic buffer system. For the purposes of the present invention, an inorganic buffer system is understood to be a mixture of an inorganic acid and its conjugate corresponding inorganic base.

[0231] For the purposes of the present invention, an organic buffer system is understood to be a mixture of an organic acid and its conjugate base. Due to the organic acid residue, the conjugate base of the organic acid is also organic. The cation present for neutralizing the charge of the acid anion can be either inorganic or organic.

[0232] Examples of inorganic acids are sulfuric acid, hydrochloric acid, and phosphoric acid (H₃PO₄). Phosphoric acid is a moderately strong acid that is particularly favored.

[0233] Potassium dihydrogen phosphate is a particularly suitable inorganic acid. It has the molecular formula KH₂PO₄ and the CAS number 7778-77-0. Potassium dihydrogen phosphate has a molar mass of 136.09 g / mol. It is readily soluble in water (222 g / L at 20 °C) and reacts acidic in water. A 5% solution of potassium dihydrogen phosphate in water has a pH of 4.4.

[0234] Another particularly suitable inorganic acid is sodium dihydrogen phosphate. Sodium dihydrogen phosphate has the molecular formula NaH₂PO₄ and the CAS numbers 7558-80-7 (anhydrous), 10049-21-5 (monohydrogenate), and 13472-35-0 (dihydrate). Anhydrous sodium dihydrogen phosphate has a molar mass of 119.98 g / mol. Sodium dihydrogen phosphate reacts as an acid in aqueous solution.

[0235] Dipotassium hydrogen phosphate is particularly preferred as the corresponding salt of the aforementioned two acids. Dipotassium hydrogen phosphate has the molecular formula K₂HPO₄ and bears the CAS numbers 7758-11-4 (anhydrous) and 16788-57-1 (trihydrate). Anhydrous dipotassium hydrogen phosphate has a molar mass of 174.18 g / mol. Dipotassium hydrogen phosphate reacts alkaline in aqueous solution.

[0236] Disodium hydrogen phosphate is also particularly favored as a corresponding salt of the aforementioned two acids. Disodium hydrogen phosphate has the molecular formula Na₂HPO₄ and bears the CAS numbers 7558-79-4 (anhydrous), 10028-24-7 (dihydrate), 7782-85-6 (heptahydrate), and 10039-32-4 (dodecahydrate). Anhydrous disodium hydrogen phosphate has a molar mass of 141.96 g / mol. Disodium hydrogen phosphate reacts alkaline in aqueous solution.

[0237] Examples of organic acids are citric acid, succinic acid, tartaric acid, lactic acid, acetic acid, malic acid, malonic acid and maleic acid.

[0238] Examples of the corresponding salts of these organic acids are the sodium and potassium salts of citric acid, the sodium and potassium salts of succinic acid, the sodium and potassium salts of tartaric acid, the sodium and potassium salts of lactic acid, the sodium and potassium salts of acetic acid, the sodium and potassium salts of malic acid, the sodium and potassium salts of malonic acid, and the sodium and potassium salts of maleic acid. Method for staining keratin material

[0239] The agents described above are ideally suited for use in processes for dyeing keratinous material, especially human hair.

[0240] A second object of the present invention is therefore a method for dyeing keratinous material, in particular human hair, comprising the following steps: (1) Applying a dye to the keratinous material, wherein the dye is an agent as disclosed in detail in the description of the first subject matter of the invention, (2) allowing the dye to act on the keratinous material and (3) rinsing the dye with water.

[0241] In step (1) of the method according to the invention, the agent of the first invention is applied to the keratinous material, which is most preferably human hair.

[0242] In step (2) of the method according to the invention, the agent is then allowed to act after its application to the keratinous material. In this context, various exposure times of, for example, 30 seconds to 60 minutes are conceivable.

[0243] A major advantage of the dyeing system according to the invention is that an intense color result can be achieved even in very short periods of time after short exposure times. For this reason, it is advantageous if the application mixture remains on the keratin material for only relatively short periods of time after application, from 30 seconds to 15 minutes, preferably from 30 seconds to 10 minutes, and particularly preferably from 1 to 5 minutes.

[0244] In a further preferred embodiment, a method according to the invention is characterized by (2) the action of the dye on the keratinous material for a period of 30 seconds to 15 minutes, preferably from 30 seconds to 10 minutes, and particularly preferably from 1 to 5 minutes.

[0245] Following the application of the mixture to the keratin material, it is finally rinsed off with water in step (3) of the procedure.

[0246] In one embodiment, the application mixture can be rinsed off with water alone, i.e., without the use of a post-treatment agent or shampoo. The application of a post-treatment agent or conditioner in step (6) is also conceivable in principle.

[0247] However, to solve the problem according to the invention and to increase ease of use, it has proven to be particularly preferred to rinse the agent in step (3) exclusively with water without the aid of any further after-treatment agent, shampoo or conditioner.

[0248] In a further preferred embodiment, a method according to the invention is characterized by (3) rinsing the dye exclusively with water.

[0249] Regarding the other preferred embodiments of the methods according to the invention, the following applies: mutatis mutantis that which was said about the agent according to the invention. Examples 1. Formulations

[0250] The following formulations were produced (all values, unless otherwise stated, are in wt.%): Dye (V1) (V2) (E1) (E2) Cetyl alcohol 3,0 3,0 3,0 3,0 C 12 -C 18 fatty alcohols (Lorol techn.) 3,0 3,0 3,0 3,0 Phenoxyethanol 0,9 0,9 0,9 0,9 Sodium salicylate 0,4 0,4 0,4 0,4 Unipure Red LC 3071 (CI 15850) 1,0 1,0 1,0 1,0 Dow Corning 2-8566 (Siloxanes and Silicones, 3-[(2-Aminoethyl)amino]-2-methylpropyl Me, Di-Me-Siloxane 1,0 --- 1,0 1,0 Belsil ADM 8301 E (Amodimethicone / Morpholinomethyl Silsesquioxane Copolymer, Wacker) --- 1,0 --- --- 1,2-Propanediol 10,0 10,0 10,0 10,0 Potassium dihydrogen phosphate 0,35 0,35 0,35 0,35 Disodium hydrogen phosphate 0,72 0,72 0,72 0,72 Emuglade CM (BASF, cetearyl isononanoate, ceteareth-20, cetearyl alcohol, glyceryl steareate, glycerin, ceteareth-12, cetyl palmitate) 3,0 3,0 3,0 3,0 Natrosol 250 HR (Hydroxyethylcellulose) --- --- 2,0 --- Keltrol CG-SFT (CP, Kelco, Xanthan Gum) --- 2,0 --- 2,0 Water ad 100 ad 100 ad 100 ad 100 2. Application

[0251] The previously prepared solution was applied to strands of hair (Kerling, Euronaturhaar white, ratio: 1 g of dye (E1) per g of hair strand). The solution was left on for five minutes. Afterwards, the hair strand was thoroughly rinsed (for one minute) with water, dried, and then colorimetrically measured using a Datacolor Spectraflash 450 colorimeter.

[0252] The dE value used to assess the different color intensities is derived from the L*a*b* color measurements taken on the respective strand section as follows: dE = L i − L 0 2 + a i − a 0 2 + b i − b 0 1 / 2 L 0 , a 0 and b 0 = measured values ​​of the uncolored strand L i , ai and bi = measured values ​​of the colored strand

[0253] The larger the dE value, the greater the color difference between undyed and dyed strands, and the higher the color intensity. Medium L a b dE Kerling, uncolored 73,18 2,35 22,09 -- Comparison (V1) 44,17 45,43 7,40 53,97 Comparison (V2) 65,32 11,00 8,50 17,92 Invention (E1) 38,11 45,76 9,03 57,31 Invention (E2) 39,98 46,67 9,39 56,81

Claims

1. An agent for dyeing keratinous material, in particular human hair, containing (a1) at least one linear, amino-functionalized silicone polymer, and (a2) at least one pigment having a solubility in water at 25 °C of less than 0.05 g / L, and (a3) at least one polysaccharide selected from the group of hydroxy C1-C30 alkylcelluloses, hydroxy C1-C30 alkylmethylcelluloses, hydroxy C1-C30 alkylethylcelluloses, C1-C30 alkylcelluloses, C6-C30 alkylhydroxyethylcelluloses, cellulose, starch, xanthan gum, carboxyalkylcellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan, pectin, agaropectin and / or the salts thereof, characterized in that the agent is free of silicone resins.

2. The agent according to claim 1, characterized in that it contains at least one linear, amino-functionalized silicone polymer (a1) having at least one secondary amino group.

3. The agent according to one of claims 1 to 2, characterized in that it contains at least one linear, amino-functionalized silicone polymer (a1) which comprises at least one structural unit of the formula (Si-amino), where ALK1 and ALK2 represent, independently of one another, a linear or branched, divalent C1-C20 alkylene group.

4. The agent according to one of claims 1 to 3, characterized in that it contains at least one linear, amino-functionalized silicone polymer (a1) which comprises structural units of formula (Si-I) and formula (Si-II) 5. The agent according to one of claims 1 to 4, characterized in that it contains, based on the total weight of the agent, one or more linear, amino-functionalized silicone polymers (a1) in a total amount from 0.1 to 8.0 wt.%, preferably from 0.2 to 5.0 wt.%, more preferably from 0.3 to 3.0 wt.%, and very particularly preferably from 0.4 to 2.5 wt.%.

6. The agent according to one of claims 1 to 5, characterized in that it contains at least one inorganic pigment (a2), which is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from mica-based colored pigments which are coated with at least one metal oxide and / or a metal oxychloride.

7. The agent according to one of claims 1 to 6, characterized in that it contains, based on the total weight of the agent, one or more pigments (a2) in a total amount from 0.01 to 10.0 wt.%, preferably from 0.1 to 5.0 wt.%, more preferably from 0.2 to 2.5 wt.%, and very particularly preferably from 0.25 to 1.5 wt.%.

8. The agent according to one of claims 1 to 7, characterized in that it contains, based on the total weight of the agent, one or more polysaccharides (a3) in a total amount from 0.1 to 6.0 wt.%, preferably from 0.5 to 5.0 wt.%, more preferably from 1.0 to 4.0 wt.%, and very particularly preferably from 1.5 to 3.5 wt.%.

9. The agent according to one of claims 1 to 8, characterized in that it contains one or more fatty components (a4) from the group of C12-C30 fatty alcohols, C12-C30 fatty acid triglycerides, C12-C30 fatty acid monoglycerides, C12-C30 fatty acid diglycerides and / or hydrocarbons.

10. A method for dyeing keratinous material, in particular human hair, comprising the following steps: (1) applying a dyeing agent according to one of claims 1 to 9 to the keratinous material, (2) allowing the dyeing agent to act on the keratinous material, and (3) rinsing out the dyeing agent using water.

11. The method according to claim 10, characterized by (2) allowing the dyeing agent to act on the keratinous material for a period of 30 seconds to 15 minutes, preferably 30 seconds to 10 minutes, and particularly preferably 1 to 5 minutes.