Method for dyeing keratin fibers, comprising the use of a dye containing amino silicone and pigment as well as the use of an aftertreatment agent containing silsesquioxane

Abstract

The invention relates to a method for dyeing keratin fibers, in particular human hair, comprising (1) the use of a dye (F) on the keratin fibers, said dye containing (f1) at least one amino-functionalized silicone polymer and (f2) at least one pigment, and (2) the use of an aftertreatment agent (N) on the keratin fibers, said aftertreatment agent containing (n1) at least one silsequioxane, said silsequioxane (n1) being different from the amino-functionalized silicone polymer (f1).

Description

[0001] A method for coloring keratin fibers, comprising the application of a colorant containing aminosilicone and pigment and the application of a post-treatment agent containing silsesquioxane

[0002] The present application relates to a method for coloring keratin fibers, in particular human hair, which comprises the application of a colorant (F) and the application of a post-treatment agent (N). The colorant (F) contains at least one amino-functionalized silicone polymer (f1) and at least one pigment (f2). The post-treatment agent (N) contains at least one silsesquioxane (n1) that is different from the amino-functionalized silicone polymer (f1).

[0003] Altering the shape and color of keratin fibers, especially human hair, represents an important area of ​​modern cosmetics. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intense colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by very long-lasting coloring results.

[0004] When using direct dyes, the fully formed pigments diffuse from the dyeing agent into the hair fiber. Compared to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. Colorations with direct dyes typically remain on the hair for between 5 and 20 washes.

[0005] The use of color pigments is known for temporary color changes on hair and / or skin. Pigments or color pigments are generally understood to be insoluble, color-imparting substances. These are present undissolved in the form of small particles in the coloring formulation and merely deposit externally on the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue after several washes with surfactant-containing cleansers. Various products of this type are available on the market under the name hair mascara.

[0006] If the user desires particularly long-lasting color results, the use of oxidative colorants has so far been the 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 colorants 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.

[0007] Coloring with pigments offers several significant advantages. Because the pigments only attach to the keratin fibers, especially the hair fibers, from the outside, the damage associated with the coloring process is extremely minimal. Furthermore, unwanted coloring can be removed quickly and easily without leaving any residue, thus offering the user the opportunity to return to their original hair color immediately and without great effort. This coloring process is therefore particularly attractive for consumers who do not want to recolor their hair regularly.

[0008] Recent work has addressed the problem of the short durability of this coloring system. In this context, it was found that the washfastness of the color results obtained with pigments could be significantly improved by combining the pigments with certain amino-functionalized silicone polymers. Furthermore, by selecting particularly suitable pigments and pigment concentrations, a lighter color result could be achieved on dark hair, so that this coloring system even made it possible to lighten hair, which was previously only possible with oxidative hair treatments (bleaches or bleaching agents).

[0009] To achieve dyeings with the highest possible color stability, various formulations for the application of pigments and aminosilicones have already been described. However, the durability and washfastness achieved with these dyeing systems still require improvement. For this reason, we are continuing to search for ways to further improve the dyeings that can be achieved using pigments in terms of film stability, washfastness, and color retention.

[0010] The object of the present invention was to provide a dyeing system that, if possible, possesses fastness properties comparable to oxidative dyeing. In particular, the washfastness properties should be outstanding, while avoiding the use of the oxidation dye precursors typically used for this purpose. The aim was to find a technology that would enable pigments to be fixed to the hair in an extremely permanent manner. When used in a dyeing process, the agents should achieve intensive dyeing results with good fastness properties, in particular good film stability, high washfastness, and good color retention.The work leading to this invention has now surprisingly shown that colorations produced by applying aminosilicones and pigments to the hair are particularly durable and resistant if a post-treatment agent containing at least one silsesquioxane is applied to the hair after the coloring step.

[0011] A first subject of the present invention is a process for dyeing keratin fibers, in particular human hair, comprising the

[0012] (1) applying a coloring agent (F) to the keratin fibers, which contains (f1) at least one amino-functionalized silicone polymer, and

[0013] (f2) at least one pigment, and the

[0014] (2) Application of a post-treatment agent (N) to the keratin fibers, which contains

[0015] (n1) at least one silsesquioxane, wherein the silsesquioxane (n1) is different from the amino-functionalized silicone polymer (f1).

[0016] The work leading to this invention demonstrated that hair could be intensely colored by using a colorant containing at least one aminosilicone (f1) and one pigment (f2). The film created on the hair by this coloring was particularly stable when post-crosslinked with at least one silsesquioxane (n1) in a post-treatment step. Since the post-crosslinked film was particularly resistant to external influences such as shampooing, the colored hair was characterized by particularly good washfastness.

[0017] Keratin fibers

[0018] Keratin fibers include wool, fur, and feathers, and especially human hair. Human hair is particularly preferred as a keratin fiber.

[0019] Coloring agents

[0020] In the context of this invention, the term "coloring agent" refers to the coloring of keratin material, particularly hair, caused by the use of pigments. In this coloring, the pigments, as color-imparting compounds, are deposited together with the amino-functionalized silicone polymer(s) in a particularly homogeneous, uniform, and smooth film on the surface of the keratin material.

[0021] Application of the colorant (F) on keratin fibers

[0022] In step (1) of the dyeing process according to the invention, a dye (F) containing at least one amino-functionalized silicone polymer (f1) and at least one pigment (f2) is applied to the keratin fibers or human hair. The dye (F) is a ready-to-use dye. Amino-functionalized silicone polymer (f1) in the dye

[0023] The colorant (F) contains at least one amino-functionalized silicone polymer (f1). The amino-functionalized silicone polymer can alternatively be referred to as aminosilicone or amodimethicone.

[0024] Silicone polymers are generally macromolecules having a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, particularly preferably at least 5000 g / mol, which comprise repeating organic units.

[0025] 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 if the maximum molecular weight of the silicone polymer is not more than 10 7 g / mol, preferably not more than 10 e g / mol and particularly preferably not more than 10 5 g / mol.

[0026] Silicone polymers comprise numerous Si-O repeating units, where the Si atoms may carry organic residues such as alkyl or substituted alkyl groups. A silicone polymer is therefore also referred to as polydimethylsiloxane.

[0027] In accordance with the high molecular weight of the silicone polymers, these are based on more than 10 Si-O repeating units, preferably more than 50 Si-O repeating units and particularly preferably more than 100 Si-O repeating units, most preferably more than 500 Si-O repeating units.

[0028] An amino-functionalized silicone polymer is a functionalized silicone that carries at least one structural unit with an amino group. The amino-functionalized silicone polymer preferably carries multiple structural units, each with at least one amino group. An amino group is defined as a primary amino group, a secondary amino group, and a tertiary amino group. All of these amino groups can be protonated in an acidic environment and are then present in their cationic form.

[0029] In principle, good dyeing performance could be achieved with amino-functionalized silicone polymers if they contained at least one primary, at least one secondary, and / or at least one tertiary amino group. However, intense dyeings with the best washfastness were obtained when an amino-functionalized silicone polymer containing at least one secondary amino group was used in the dyeing agent.

[0030] In a particularly preferred embodiment, a method according to the invention is characterized in that a coloring agent (F) is applied to the keratin fibers, which comprises at least one amino-functionalized silicone polymer (f1) having at least one secondary amino group.

[0031] The secondary amino group(s) can be located at various positions on the amino-functionalized silicone polymer. Particularly good color results were obtained when using an amino-functionalized silicone polymer that contains at least one, preferably several, structural units of the formula (Si-amino). -Amino)

[0032] In the structural units of the formula (Si-amino), the abbreviations ALK1 and ALK2 independently represent a linear or branched, divalent Ci-C2o-alkylene group.

[0033] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one amino-functionalized silicone polymer (f1) which comprises at least one structural unit of the formula (Si-Amino), -Amino) where

[0034] ALK1 and ALK2 independently represent a linear or branched, divalent C1-C2o 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 star can be bonded to another oxygen atom, and the oxygen atom adjacent to the star can be bonded to another silicon atom or to a C1-C8 alkyl group.

[0036] A divalent Ci-C2o-alkylene group can alternatively be referred to as a divalent or divalent C1-C2o-alkylene group, which means that each group ALK1 or AK2 can form two bonds.

[0037] In the case of ALK1, one 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, one bond is formed from the secondary amino group to the ALK2 moiety, and the second bond is formed between ALK2 and the primary amino group.

[0039] Examples of a linear divalent C1-C2o-alkylene group include 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-C2o-alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-). In a further particularly preferred embodiment, the structural units of the formula (Si-amino) represent repeating units in the amino-functionalized silicone polymer, so that the silicone polymer comprises several structural units of the formula (Si-amino).

[0040] Particularly suitable amino-functionalized silicone polymers with at least one secondary amino group are listed below.

[0041] Colorations with the very best wash fastness could be obtained when at least one agent was applied to the keratinic material during the coloring process, which contains at least one amino-functionalized silicone polymer comprising structural units of the formula (Si-I) and the formula (Si-II)

[0042] In a further explicitly very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one amino-functionalized silicone polymer (f1) which comprises structural units of the formula (Si-I) and the formula (Si-II) (Si-Il).

[0043] A corresponding amino-functionalized silicone polymer with the structural units (Si-I) and (Si-III) is, for example, the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is marketed 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. Another particularly preferred commercial product is Dowsil AP-8568 Amino Fluid, which is also marketed by the Dow Chemical Company.

[0044] In a further embodiment, the coloring can also be carried out by using a colorant (F) which contains at least one amino-functional silicone polymer of the formula (Si-III), where m and n are numbers chosen so that the sum (n + m) is in the range from 1 to 1000, n is a number in the range from 0 to 999 and m is a number in the range from 1 to

[0045] 1000, R1, R2 and R3, which are the same or different, represent a hydroxy group or a C1-4 alkoxy group, wherein at least one of the groups R1 to R3 represents a hydroxy group;

[0046] Further suitable methods are characterized by a colorant on the keratin fibers, wherein the colorant contains at least amino-functional silicone polymer of the formula (Si-IV), in which p and q are numbers chosen so that the sum (p + q) is in the range 1 to 1000, p is a number in the range 0 to 999 and q is a number in the range 1 to 1000,

[0047] R1 and R2, which are different, represent a hydroxy group or a C1-4 alkoxy group, wherein at least one of the groups R1 to R2 represents a hydroxy group.

[0048] The silicones of formulas (Si-III) and (Si-IV) differ in the grouping at the Si atom that carries the nitrogen-containing group: In formula (Si-III), R2 represents a hydroxyl group or a C1-4 alkoxy group, while the residue in formula (Si-IV) is a methyl group. The individual Si groups, which are designated by the indices m and n or p and q, do not necessarily have to be present as blocks; rather, the individual units can also be randomly distributed, i.e., in formulas (Si-III) and (Si-IV), not every R1-Si(CH3)2 group is necessarily bonded to a -[O-Si(CH3)2]- group.

[0049] Methods according to the invention have also proven particularly effective in producing intensive color results, in which a colorant is applied to the keratin fibers, which contains at least one amino-functional silicone polymer of the formula (Si-V) in the

[0050] A represents a group -OH, -O-Si(CH3)3,-O-Si(CH3)2OH,-O-Si(CH3)2OCH3,

[0051] 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 provisos

[0052] - n > 0 and b + c > 0

[0053] - at least one of the conditions A = -OH or D = -H is fulfilled.

[0054] In the above-mentioned formula (Si-V), the individual siloxane units with the indices b, c and n are statistically distributed, ie they do not necessarily have to be block copolymers.

[0055] The applied colorant may also contain one or more different amino-functionalized silicone polymers represented by the formula (Si-VI)

[0056] M(RaQbSiO(4-ab) / 2)x(RcSiO(4-c) / 2)yM (Si-VI), where in the above formula R is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R 1 HZ is, where R 1is a divalent linking group bonded to hydrogen and the radical 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 radical 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 silicone end group as known in the art, preferably trimethylsiloxy.Non-limiting examples of the radicals represented by R include alkyl radicals such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, and the like; alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl, and the like; phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl, and the like; and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl, and the like; preferably, R is an alkyl radical containing 1 to about 6 carbon atoms, and most preferably, R is methyl. Examples of R 1include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH2CH(CH3)CH2-, phenylene, naphthylene, -CH2CH2SCH2CH2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -CH2CH(CH3)C(O)OCH2-, -(CH2)3CC(O)OCH2CH2-, -C6H4C6H4-, -C6H4CH2C6H4-; and -(CH2)3C(O)SCH2CH2-.

[0057] Z is an organic, amino-functional residue containing at least one functional amino group. A possible formula for Z is NH(CH2) Z NH2, where z is 1 or more. Another possible formula for Z is -NH(CH2) Z (CH2) ZZ NH, where both z and zz are independently 1 or more, this structure including diamino ring structures such as piperazinyl. Z is most preferably a -NHCH2CH2NH2- radical. Another possible formula for Z is -N(CH2) Z (CH2) ZZ NX2 or -NX2, wherein each X of X2 is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

[0058] Q is most preferably a polar, amine-functional radical of the formula -CH2CH2CH2NHCH2CH2NH2. In the formulas, "a" takes on values ​​in the range of about 0 to about 2, "b" takes on 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 R a Qb SiO(4- a -b) / 2 units to the R c SiO (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. When one or more silicones of the above formula are used, the various variable substituents in the above formula can be different for the various silicone components present in the silicone mixture.

[0059] In a further embodiment, a method according to the invention is characterized by the application of a colorant to the keratin fibers, wherein the colorant is an amino-functional silicone polymer of the formula (Si-VII)

[0060] R' a G 3 a -Si(OSiG2)n-(OSiG bR'2- b)mO-SiG 3 a -R' a (Si-Vll), where:

[0061] - G is -H, a phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-

[0062] 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;

[0063] - a stands for a number between 0 and 3, in particular 0; - b stands for a number between 0 and 1, in particular 1,

[0064] - m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably assumes values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values ​​from 1 to 2000, in particular from 1 to 10,

[0065] - R' is a monovalent radical selected from o -QN(R")-CH2-CH2-N(R")2 o -QN(R")2o -QN + (R")3A- o -QN + H(R")2A- o -QN + H2(R")A- o -QN(R")-CH2-CH2-N + R"H2A- , where each Q represents a chemical bond, -CH2-, -CH2-CH2-, -CH2CH2CH2-, -C(CH3)2- , -CH2CH2CH2CH2-, -CH2C(CH3)2-, -CH(CH3)CH2CH2-,

[0066] R" represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH2- CH(CH3)Ph, the Ci-2o-alkyl radicals, preferably -CH3, -CH2CH3, -CH2CH2CH3, - CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, and A represents an anion which is preferably selected from chloride, bromide, iodide or methosulfate.

[0067] In a further embodiment, a method according to the invention is characterized by the application of a colorant to the keratin fibers, wherein the colorant contains at least one amino-functional silicone polymer of the formula (Si-VIIa),

[0068] (CH3)3Si-[O-Si(CH3)2] n [OSi(CH3)]m-OSi(CH3)3(Si-Vlla),

[0069] CH2CH(CH3)CH2NH(CH2)2NH2wherein m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably assumes values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values ​​from 1 to 2000, in particular from 1 to 10.

[0070] According to the INCI declaration, these silicones are called trimethylsilylamodimethicones.

[0071] In a further preferred embodiment, a method according to the invention is characterized by the application of a colorant to the keratin fibers, wherein the colorant contains at least one amino-functional silicone polymer of the formula (Si-VIIb)

[0072] R-[Si(CH3)2-O]ni[Si(R)-O] m -[Si(CH3)2] n2 -R (Si-VIIb), (CH2)3NH(CH2)2NH2, wherein R is -OH, -O-CHs or a -CHs group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2000, preferably between 50 and 150, the sum (n1 + n2) preferably assuming values ​​from 0 to 1999 and in particular from 49 to 149 and m preferably assuming values ​​from 1 to 2000, in particular from 1 to 10.

[0073] These amino-functionalized silicone polymers are referred to as amodimethicones according to the INCI declaration.

[0074] Regardless of which amino-functional silicones are used, colorants according to the invention are preferred that contain an amino-functional silicone polymer whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g, and in particular above 0.4 meq / g. The amine number represents the milliequivalents of amine per gram of amino-functional silicone. It can be determined by titration and can also be expressed in mg KOH / g.

[0075] Furthermore, colorants containing a special 4-morpholinomethyl-substituted silicone polymer are also suitable for use in the process according to the invention. This amino-functionalized silicone polymer comprises structural units of the formulas (S1-VIII) and (Si-

[0076] Corresponding 4-morpholinomethyl-substituted silicone polymers are described below.

[0077] A corresponding amino-functionalized silicone polymer is available under the name

[0078] Amodimethicone / Morpholinomethyl Silsesquioxane Copolymer known and in the form of the raw material

[0079] Belsil ADM 8301 commercially available from Wacker. For example, a 4-morpholinomethyl-substituted silicone can be used that has structural units of the formulas (Si-VIII), (Si-IX), and (Si-X). in which

[0080] R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2;

[0081] R2 stands for -CH3, -OH, or -OCH3.

[0082] Particularly preferred colorants contain at least one 4-morpholinomethyl-substituted

[0083] Silicone of formula (Si-Xl)

[0084] (Si-Xl) in the

[0085] R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3, or -O-CH(CH3)2;

[0086] R2 stands for -CH3, -OH, or -OCH3.

[0087] B represents a group -OH, -O-Si(CH3)3,-O-Si(CH3)2OH,-O-Si(CH3)2OCH3,

[0088] D stands for a group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3, a, b and c independently of one another stand for integers between 0 and 1000, with the proviso that a + b + c > 0 m and n independently of one another stand for integers between 1 and 1000, with the proviso that at least one of the conditions B = -OH or D = -H is met, the units a, b, c, m and n are distributed statistically or in blocks in the molecule.

[0089] Structural formula (Si-XI) is intended to clarify that the siloxane groups n and m do not necessarily have to be directly bonded to an end grouping B or D. Rather, in preferred formulas (Si-VI), a > 0 or b > 0, and in particularly preferred formulas (Si-VI), a > 0 and c > 0, i.e., the terminal grouping B or D is preferably bonded to a dimethylsiloxy grouping. In formula (Si-VI), the siloxane units a, b, c, m, and n are also preferably distributed randomly.

[0090] The silicones used according to the invention represented by formula (Si-VI) can be trimethylsilyl-terminated (D or B = -Si(CH3)3), but they can also be dimethylsilylhydroxy-terminated on two sides or dimethylsilylhydroxy- and dimethylsilylmethoxy-terminated on one side. Silicones particularly preferably used in the context of the present invention are selected from silicones in which

[0091] B = -O-Si(CH3)2OH and D = -Si(CH3)3

[0092] B = -O-Si(CH3)2OH and D = -Si(CH3)2OH

[0093] B = -O-Si(CH3)2OH and D = -Si(CH3)2OCH3

[0094] B = -O-Si(CH3)3and D = -Si(CH3)2OH

[0095] B = -O-Si(CH3)2OCH3 and D = -Si(CH3)2OH. These silicones lead to exorbitant improvements in the properties of hair treated with the agents according to the invention and to significantly improved protection during oxidative treatment.

[0096] The colorants used in the coloring step can contain one or more amino-functionalized silicone polymers, for example, 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.%. The amounts stated here are based on the total amount of all aminosilicones used, which is related to the total weight of the colorant.

[0097] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more amino-functionalized silicone polymers (f1) in a total amount of 0.1 to 20 wt.%, preferably 0.2 to 10 wt.%, more preferably 0.3 to 5 wt.%, even more preferably 0.4 to 3.5 wt.%, and most preferably 0.5 to 2.0 wt.%.

[0098] Pigments (f2) in the dye (F)

[0099] As a second essential component, the colorant (F) used in step (1) of the process according to the invention contains at least one pigment (f2). Pigments within the meaning of the present invention are understood to be color-imparting compounds which have a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. Water solubility can be determined, for example, using the method described below: 0.5 g of the pigment is weighed into a beaker. A 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 finely dispersed pigment, the mixture is filtered. If a portion of undissolved pigment remains on the filter paper, the pigment's solubility is below 0.5 g / L.

[0100] Suitable color pigments can be of inorganic and / or organic origin. In a preferred embodiment, a method according to the invention is characterized in that the aftertreatment agent is applied to keratin material that has been colored by applying at least one inorganic and / or organic pigment.

[0101] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ochre, umber, green earth, burnt sienna, or graphite, for example. Other inorganic color pigments that can be used include black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments.

[0102] Particularly suitable are colored metal oxides, hydroxides, and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates, and / or molybdates. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), and / or carmine (cochineal).

[0103] Colored pearlescent pigments that are also particularly preferred according to the invention are colored pearlescent pigments. These are typically based on mica and / or mica and can be coated with one or more metal oxides. Mica belongs to the class of layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. As an alternative to natural mica, synthetic mica, optionally coated with one or more metal oxides, can also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica and are coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide(s).

[0104] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one inorganic pigment (f2), wherein the inorganic pigment is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or mica, which are coated with at least one metal oxide and / or one metal oxychloride.

[0105] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (f2) which is selected from mica- or mica-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0106] Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[0107] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise:

[0108] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0109] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0110] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0111] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)

[0112] Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0113] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0114] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0115] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE), Cl 77510 (FERRIC FERROCYANIDE)

[0116] Colorona Red Brown, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE)

[0117] Colorona Russet, Merck, Cl 77491 (TITANIUM DIOXIDE), MICA, Cl 77891 (IRON OXIDES)

[0118] Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), D&C RED NO. 30 (Cl 73360)

[0119] Colorona Majestic Green, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 77288 (CHROMIUM OXIDE GREENS)

[0120] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), FERRIC FERROCYANIDE (Cl 77510)

[0121] Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0122] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0123] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0124] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

[0125] Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0126] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0127] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0128] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0129] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0130] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

[0131] Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0132] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0133] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide)

[0134] Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

[0135] Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0136] Other particularly preferred color pigments with the trade name Xirona® include:

[0137] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0138] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0139] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0140] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0141] In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

[0142] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0143] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0144] In a further embodiment, the applied colorant may also contain one or more organic pigments.

[0145] The organic pigments according to the invention are correspondingly insoluble, organic dyes or lakes which can be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0146] Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0147] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic pigment (f2), wherein the organic pigment is preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index Numbers CI 1 1725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0148] The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles comprising a layer of absorbed dyes, the particle-dye unit being insoluble under the aforementioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0149] Alizarin lake, for example, can be used as a colored varnish.

[0150] Pigments with a specific shape can also be used to color the keratin fibers. For example, a pigment based on a lamellar and / or lenticular substrate plate can be used. Furthermore, coloring based on a substrate plate containing a vacuum-metallized pigment is also possible.

[0151] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (f2) which is selected from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0152] The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, more preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, more preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm. Each substrate platelet preferably has a thickness that is as uniform as possible. Due to the low thickness of the substrate platelets, the pigment has particularly high hiding power.

[0153] The substrate platelets are preferably monolithic in structure. Monolithic in this context means consisting of a single, closed unit without fractures, stratification, or inclusions, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous in structure, meaning that no concentration gradient occurs within the platelets. In particular, the substrate platelets are not layered and do not have any particles distributed within them.

[0154] The size of the substrate platelet can be tailored to the specific application, especially the desired effect on the keratin material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 pm, particularly approximately 5 to 100 pm.

[0155] In a preferred embodiment, the aspect ratio, expressed as the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The average size of the uncoated substrate platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Heios device with Quixel wet dispersion. For sample preparation, the sample to be tested was predispersed in isopropanol for 3 minutes.

[0156] The substrate platelets can be made of any material that can be formed into platelets.

[0157] They can be of natural origin or synthetically produced. Materials from which the substrate platelets can be constructed include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. The substrate platelets are preferably made of metal (or metal alloys).

[0158] Any metal suitable for metallic luster pigments can be considered. Such metals include iron and steel, as well as all air- and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum, and silicon, as well as their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum platelets and brass platelets, with aluminum platelets being particularly preferred.

[0159] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance.

[0160] Due to their irregular structure, pigments based on lamellar substrate platelets generate a high degree of scattered light. Furthermore, pigments based on lamellar substrate platelets do not completely cover the existing color of a keratinous material, and effects similar to natural graying can be achieved, for example.

[0161] Lenticular (= lens-shaped) substrate platelets have a generally regular, round edge and are also called "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light predominates in pigments based on lenticular substrate platelets.

[0162] Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated foils. They are characterized by a particularly thin substrate platelet thickness in the range of 5 to 50 nm and a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum-metallized pigment are also referred to as VMP substrate platelets in this application. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized foils.

[0163] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0164] Uncoated lamellar, lenticular, and / or VPM substrate plates, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop. These have proven particularly preferred for use in the colorant.

[0165] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0166] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

[0167] Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0168] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the agent according to the invention is very particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, in particular of 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0169] The pigments (f2) are preferably used in specific quantity ranges in the colorant (F). The colorant used in the coloring process according to the invention may contain one or more pigments, for example, 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. %. The quantities stated here are based on the total amount of all pigments used, which is related to the total weight of the colorant. In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more pigments (f2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably from 0.2 to 2.5% by weight and very particularly preferably from 0.25 to 1.5% by weight.

[0170] Water content in the dye (F)

[0171] The previously described colorant (F) is a ready-to-use agent that is applied to the keratin fibers. This ready-to-use agent preferably has a low to medium water content. It has been found that colorants that contain—based on the total weight of the agent—0.1 to 50.0 wt.%, preferably 0.5 to 35.0 wt.%, more preferably 1.0 to 20.0 wt.%, and particularly preferably 1.5 to 15.0 wt.% water are particularly suitable.

[0172] In a further explicitly very particularly preferred embodiment, a process is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains 0.1 to 50.0 wt.%, preferably 0.5 to 35.0 wt.%, more preferably 1.0 to 20.0 wt.% and particularly preferably 1.5 to 15.0 wt.% water.

[0173] Cosmetic carrier of the colorant (F)

[0174] Due to the previously described water content of the colorant, which is preferably in the medium to low range, the main component of the cosmetic carrier in which the colorant components (f1) and (f2) are present is preferably non-aqueous. The cosmetic carrier is preferably a solvent and / or a polyethylene glycol.

[0175] Suitable solvents include, for example, solvents from the group consisting of 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, phenoxyethanol, and benzyl alcohol. The use of 1,2-propylene glycol is particularly preferred.

[0176] A particularly preferred low-molecular-weight polyethylene glycol is PEG-8. PEG-8 contains an average of 8 ethylene glycol units (x1 = 8), has an average molecular weight of 400 g / mol, and bears the CAS number 25322-68-3. PEG-8 is also known as PEG 400 and is commercially available, for example, from APS.

[0177] Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

[0178] Another suitable polyethylene glycol is PEG-32. PEG-32 contains 32 ethylene glycol units (x1 = 32), has an average molecular weight of 1500 g / mol, and carries the CAS number 25322-68-3. PEG-32 is also known as PEG 1500 and can be purchased commercially, for example, from Clariant.

[0179] A particularly suitable medium-molecular-weight polyethylene glycol is PEG 6000, which is commercially available from National Starch (China). The molecular weight of PEG 6000 is between 6000 and 7500 g / mol, corresponding to a x3 value of 136 to 171.

[0180] Aftertreatment agent (N)

[0181] In step (2) of the method according to the invention, a post-treatment agent (N) is applied to the keratin fibers, in particular human hair. The post-treatment agent (N) is characterized in that it contains at least one silsesquioxane (n1).

[0182] During its application, the silsesquioxane (n1) contained in the post-treatment agent comes into contact with the film previously formed by aminosilicone (f1) and pigment (f2), reacts with it and thus leads to post-crosslinking.

[0183] The first subject of the present invention is therefore a process for dyeing keratin fibers, in particular human hair, comprising the

[0184] (1) Application of a coloring agent (F) on the keratin fibers, which contains

[0185] (f1) at least one amino-functionalized silicone polymer, and

[0186] (f2) at least one pigment, and then the

[0187] (2) Application of a post-treatment agent (N) to the keratin fibers, which contains

[0188] (n1) at least one silsesquioxane, wherein the silsesquioxane (n1) is different from the amino-functionalized silicone polymer (f1).

[0189] For effective post-crosslinking of the film, it has been found to be essential that the silsesquioxane (n1) is structurally different from the amino-functionalized silicone polymer(s) (f1). Therefore, an essential feature of the process according to the invention is that the post-treatment agent (N) contains at least one silsesquioxane (n1) that is different from the amino-functionalized silicone polymer (f1).

[0190] A silsesquioxane (n1) that differs from the amino-functionalized silicone polymer (f1) has a different structure than (f1). Particularly preferably, the silsesquioxane (n1) does not contain an amino group in its structure.

[0191] Very particularly preferred is a method for dyeing keratin fibers, in particular human hair, comprising (1) applying a dyeing agent (F) to the keratin fibers, which contains (f1) at least one amino-functionalized silicone polymer, and

[0192] (f2) at least one pigment, and the

[0193] (2) Application of a post-treatment agent (N) to the keratin fibers, which contains

[0194] (n1) at least one silsesquioxane, wherein the silsesquioxane (n1) does not comprise an amino group.

[0195] Silsesquioxanes, also referred to in the literature as T-resins, are a class of organosilicon compounds with the empirical formula XSiOi s. The name of these compounds is derived from the stoichiometry of the oxygen atoms bonded to the silicon atom. Formally, each silicon atom is bonded to 1.5 oxygen atoms.

[0196] Silsesquioxanes of the empirical formula XSiOi, 5 can adopt several structures, the two most common being a ladder-like structure and a cage-like structure.

[0197] Silsesquioxanes with cage-like structures are known in molecular form, containing 6, 8, 10, and 12 Si atoms. These cages are sometimes designated T6, T8, T10, and T12, respectively (T = tetrahedral vertex). The T8 cages, the most studied representatives, have the formula [XSiO3 / 2]s or RsSi8Oi2. In all cases, each Si center is bonded to three oxygen atoms, which in turn are bonded to other Si centers. The fourth group on the Si atom is usually an X radical, which can be an alkyl group, a halogen atom, hydrogen, an alkoxy group, or another organic moiety. In cubic clusters with Oh symmetry, the Si-O-Si angles are in the range of 145–152° and are bent outward, allowing the Si centers to more easily adopt a tetrahedral geometry. The O-Si-O angles are in a range of: 10YUZ 0 , Si-O bond: 1.55-1.65 Å.

[0198] The work leading to this invention has shown that a particularly pronounced stabilization of the film occurs when the keratin fibers dyed in step (1) are treated with a post-treatment agent containing a reactive silsesquioxane. The epoxy group has proven to be a particularly suitable reactive group in this context.

[0199] In a further particularly preferred embodiment, a method according to the invention is characterized by the

[0200] (2) Application of a post-treatment agent (N) containing at least one silsesquioxane (n1) having at least one epoxy group. An epoxy group, which may alternatively also be referred to as an epoxide group, is understood to be a structural unit of the formula (EPO-I), ie, the epoxy group is a cyclopropane ring in which one of the carbon atoms (ie, a methylene unit) is replaced by an oxygen atom.

[0201] The epoxy group can be linked to the silsesquioxane via a position marked with an asterisk—either directly or via a linker. The remaining positions marked with an asterisk can contain hydrogen atoms, alkyl groups, or other organic moieties.

[0202] The epoxy group is bonded to the silsesquioxane via at least one position marked with an asterisk. The other positions marked with an asterisk can be, for example, a hydrogen atom, a hydroxyl group, or an organic residue. Without being limited to this theory, it is assumed that the epoxy group reacts with the aminosilicone (f1), thus modifying or further crosslinking the film formed during the dyeing process, or even forming another layer around it.

[0203] A structural unit of the formula (Nl) has proven to be a particularly suitable epoxy group or epoxide group in this context where n stands for an integer from 0 to 6, preferably the numbers 2 or 3, and m stands for an integer from 0 to 10, preferably the numbers 0 or 1.

[0204] The index number n represents an integer from 0 to 6. If n is 0 and m is 1, the epoxymethylene unit located outside the square brackets is bonded to the silsesquioxane via the oxygen atom. If n represents 0, then m preferably represents the number 0 or 1.

[0205] When n is 1, the structural unit of formula (Nl) contains a methylene group (-CH2-). When n is 2, the structural unit of formula (Nl) contains an ethylene group (-CH2-CH2-).

[0206] When n is 3, a propylene group (-CH2-CH2-CH2-) is present in the structural unit of formula (NI). Particularly preferably, n represents the number 2 or 3.

[0207] The index number m stands for an integer from 0 to 10. Most preferably, m stands for the numbers 0 or 1 .

[0208] In a further particularly preferred embodiment, a method according to the invention is characterized by the

[0209] (2) Application of a post-treatment agent (N) which contains at least one silsesquioxane (n1) comprising at least one structural unit Si-X, where X represents a group of the formula (N1), where n stands for an integer from 0 to 6, preferably the numbers 2 or 3, and m stands for an integer from 0 to 10, preferably the numbers 0 or 1.

[0210] The structural unit of formula (Nl) is connected to a silicon atom of the silsesquioxane via the position marked with an asterisk. In other words, the structural unit of formula (Nl) and the Si atom together represent a Si-X unit. The silicon atom can, for example, be a Si atom, which in a cage-like silsesquioxane forms a corner of the cage or cube. In the Si-X unit, one bond from the Si atom goes to the X residue, and the three remaining bonds lead preferentially to the oxygen atoms, via which the Si atom is connected to the other Si atoms of the silsesquioxane, preferably the cage.

[0211] Particularly good results were obtained using silsesquioxanes with a cubic structure in the aftertreatment agent (N). In the cubic structure, 8 silicon atoms are arranged at the corners of a cube, with each silicon atom being bonded to three other silicon atoms via oxygen atoms and carrying an organic radical R as the fourth radical. The cubic structure is commonly referred to as a T8 cube and is a Si-O cage framework in spatial representation. Corresponding cage-like silsesquioxanes have an inorganic silicate core and an organic shell formed by the radicals R. In a further very particularly preferred embodiment, an inventive

[0212] Process characterized by the

[0213] (2) Application of a post-treatment agent (N) which contains at least one silsesquioxane

[0214] (n1) of formula (N-II), wherein each radical R is selected independently of the other radicals R in the formula (N-II), and wherein R represents a hydrogen atom, a Ci-Ce alkoxy group, a Ci-Ce alkyl group, a C2-Ce alkenyl group, a halogen-Ci-Ce alkyl group, a hydroxy-Ci-Cs alkyl group, a hydroxy group or a structural unit of the formula (Nl).

[0215] The substituents for the radical R of the compound of formula (N-II) are exemplified below: Examples of a C1-C8 alkoxy group are the methoxy group, the ethoxy group, the propoxy group, and the hexyloxy group. The methoxy group and the ethoxy group are very particularly preferred. Examples of a C1-C8 alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl, and methyl are particularly preferred alkyl radicals. Examples of a C2-C8 alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl, and isobutenyl; preferred C2-C6 alkenyl radicals are vinyl and allyl. Examples of a halogen Ci-Cs alkyl group are the chloromethyl group, the 2-chloroethyl group, the 3-chloropropyl group, the 4-chlorobutyl group, the 5-chloropentyl group, the 6-chlorohexyl group, the bromomethyl group, the 2-bromoethyl group, the 3-bromopropyl group, the 4-bromobutyl group, the 5-bromopentyl group and the 6-bromohexyl group.Preferred examples of a C1-C8-hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl, a 5-hydroxypentyl, and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred. Silsesquioxanes with a cubic structure have proven particularly suitable for solving the problem of the invention when they contain at least one reactive group, in particular at least one epoxy or epoxide group.

[0216] In the case of corresponding T8-silsesquioxanes, the silsesquioxanes according to the invention represent, for example, a silsesquioxane (n1) of the formula (N-II), wherein at least one of the radicals R represents a structural unit of the formula (Nl) described above.

[0217] In a further particularly preferred embodiment, a method according to the invention is characterized by the

[0218] (2) Use of an aftertreatment agent (N) which contains at least one silsesquioxane (n1) of the formula (N-II), wherein at least one of the radicals R represents a structural unit of the formula (Nl).

[0219] Corresponding particularly preferred compounds can be described schematically, for example, by the formula (N-III).

[0220] In the silsesquioxane of the formula (Nl II), exactly one of the R radicals represents a structural unit of the formula (Nl). However, it is further preferred if at least two R radicals, at least 3 R radicals, at least 4 R radicals, at least 5 R radicals, at least 6 R radicals, at least 7 R radicals or even all 8 R radicals represent a structural unit of the formula (Nl). In each of the structural units (Nl), the indices n and m can each be chosen independently of the index numbers of the other structural units of the formula (Nl) contained in the formula (Nl-III). In a further very particularly preferred embodiment, a process according to the invention is characterized by the

[0221] (2) Use of an aftertreatment agent (N) which contains at least one silsesquioxane (n1) of the formula (N-II), where all radicals R represent a structural unit of the formula (Nl).

[0222] An explicitly particularly preferred silsesquioxane, for example, is glycidoxypropylsilsesquioxane, a substance with the CAS number 68611-45-0, which is also alternatively referred to as glycidyl POSS cage mixture; silsesquioxane. The substance can be purchased commercially, for example, under the trade name Glycidyl POSS EP0409 from Hybrid Plastics Inc., 55 WL RUNNELS INDUSTRIAL DR., HATTIESBURG, MS 39401. The INCI name is glycidoxypropylsilsesquioxane.

[0223] The silsesquioxane(s) (n1) are preferably used in specific quantity ranges in the aftertreatment agent (N). The aftertreatment agent used in the coloring process according to the invention may contain one or more silsesquioxanes (n1), for example, in a total amount of 0.01 to 10.0 wt. %, preferably 0.05 to 5.0 wt. %, and particularly preferably 0.1 to 1.5 wt. %. The quantities stated here are based on the total amount of all pigments used, which is related to the total weight of the colorant.

[0224] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the aftertreatment agent (N) - based on the total weight of the aftertreatment agent - contains one or more silsequioxanes (n1) in a total amount of 0.01 to 10.0 wt.%, preferably of 0.05 to 5.0 wt.% and particularly preferably of 0.1 to 1.5 wt.%.

[0225] Dyes (F) and post-treatment agents (N)

[0226] In the process according to the invention, in steps (1) and (2), a colorant (F) and a post-treatment agent (N) are applied to the keratin fibers, wherein the colorant (F) and the post-treatment agent (N) are formulations with different organosilicon compounds (f1) and (n1) respectively and thus also different formulations.

[0227] Dyes (F) and after-treatment agents (N) are used for different purposes and, due to their different intended uses, contain different ingredients. Dyes (F) are intended to color the keratin fibers, so the dye contains the pigments responsible for the coloration (f2). After-treatment agents (N) are used to post-crosslink the colored film on the keratin fibers and, for this purpose, contain the previously described silsesquioxane(s) (n1).

[0228] For this reason, a colorant (F) according to the invention is preferably characterized in that it contains no silsesquioxanes of group (n1). Furthermore, the aftertreatment agent (N) is preferably characterized in that it contains no pigments.

[0229] The water content of the dye (F) and the aftertreatment agent (N) is also preferably different.

[0230] Cosmetic carrier of the aftercare product (N)

[0231] The aftertreatment agent (N) according to the invention preferably contains the silsesquioxane(s) (n1) in a cosmetic carrier. This cosmetic carrier is particularly preferably capable of dissolving the silsesquioxane(s) (n1), causing them to be deposited in as uniform a layer as possible on the film formed in step (1).

[0232] The work carried out within the scope of this invention has shown that a uniform application of the silsesquioxanes (n1) in step (2) is possible especially when the cosmetic carrier is a mixture of water and one or more solvents.

[0233] In a further particularly preferred embodiment, a process according to the invention is characterized in that the aftertreatment agent (N) - based on the total weight of the aftertreatment agent

[0234] - 0.1 to 80 wt.% water and

[0235] - contains one or more solvents in a total amount of 0.1 to 80 wt.%.

[0236] It has been found to be preferred if the water content in the aftertreatment agent (N) - based on the total weight of the aftertreatment agent (N) - is in the range from 1 to 60 wt.%, preferably from 5 to 50 wt.%, more preferably from 10 to 45 wt.%, and particularly preferably from 15 to 40 wt.%.

[0237] Suitable solvents include, for example, solvents from the group consisting of isopropanol, ethanol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol.

[0238] Furthermore, it has been found to be preferred if the aftertreatment agent (N) - based on the total weight of the aftertreatment agent (N) - contains one or more solvents from the group consisting of isopropanol, ethanol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol in a total amount of 1 to 80 wt.%, preferably 10 to 78 wt.%, more preferably 20 to 75 wt.% and particularly preferably 50 to 73 wt.%. Further optional ingredients in the colorant (F) and / or in the aftertreatment agent (N)

[0239] In addition to the components essential to the invention already described, the colorant and / or the after-treatment agent can also contain further optional ingredients, such as solvents; surfactants which are different from the surfactants described above, anionic, non-ionic, zwitterionic and / or cationic polymers; structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethyl isosorbide and cyclodextrins; fiber structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; dyes for coloring the agent; anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides;Protein hydrolysates of animal and / or plant origin, as well as in the form of their fatty acid condensation products or, where appropriate, anionically or cationically modified derivatives; vegetable oils; sunscreens and UV blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones, and flavonols; ceramides or pseudoceramides; vitamins, provitamins, and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax, and paraffins; Swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates; opacifiers such as latex, styrene / PVP, and styrene / acrylamide copolymers;Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2, and air.

[0240] The expert will select these additional substances based on the desired properties of the agent. Regarding further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the expert. The additional active ingredients and excipients are preferably used in the preparations according to the invention in amounts of 0.0001 to 25 wt.%, in particular 0.0005 to 15 wt.%, based on the total weight of the respective agent.

[0241] Steps (1) and (2) of the procedure

[0242] The method according to the invention comprises the application of a coloring agent (F) to the keratin fibers in step (1) and the application of a post-treatment agent (N) to the keratin fibers in step (2). As already described above, it is particularly preferred according to the invention that the keratin fibers are first colored by applying the coloring agent (F) and then the post-treatment agent (N) is applied. The exact time at which the post-treatment agent (N) is applied depends on the needs of the user and can be adapted to their habits.

[0243] It is particularly preferred to apply the after-treatment agent (N) to the freshly colored keratin fibers so that there is a period of only a few minutes to a few hours between rinsing out the colorant (F) and applying the shampoo (S).

[0244] In a further embodiment, a method comprising the

[0245] (1) Application of the colorant (F) on the keratin fibers in a first step, then the

[0246] (2) Application of the after-treatment agent (N) to the keratin fibers in a second step, wherein between steps (1) and (2) there is a period of maximum 72 hours, preferably maximum 48 hours, more preferably maximum 24 hours and most preferably maximum 2 hours.

[0247] A maximum period of 2 hours between performing steps (1) and (2) can, for example, mean that the coloring agent (F) is applied to the keratin fibers, allowed to act on them, and rinsed out. Then, immediately afterward, the after-treatment agent (N) is applied to the keratin fibers and allowed to act on them. Particularly preferably, the after-treatment agent (N) is designed as a leave-on product, so that the hair still treated with the after-treatment agent is dried.

[0248] In a further embodiment, a method comprising the following steps in the given order is particularly preferred:

[0249] (1 a) Application of the colorant (F) to keratin fibers,

[0250] (lb) action of the dye (F) on the keratin fibres,

[0251] (lc) Rinsing out the dye (F), then, immediately after step (1 c),

[0252] (2a) Application of the after-treatment agent (N) to the keratin fibres,

[0253] (2b) action of the after-treatment agent (N) on the keratin fibres, and

[0254] (3) Drying the keratin fibres without prior washing out of the after-treatment agent (N).

[0255] In step (1 a) of the method according to the invention, a colorant which contains at least one amino-functionalized silicone polymer and at least one pigment, in particular the preferred and particularly preferred representatives thereof described above, is applied to the keratin fibers, in particular the hair.

[0256] In the subsequent step (1 b), the previously applied colorant is allowed to act on the hair. A major advantage of the coloring 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 colorant remains on the keratin material for only a comparatively short period of time after application, ranging from 30 seconds to 15 minutes, preferably from 30 seconds to 10 minutes, and particularly preferably from 1 to 5 minutes.

[0257] In step (1 c), the colorant (F) is rinsed or washed out of the hair, preferably with water without the aid of a shampoo and without the use of any other cosmetic or surfactant formulation.

[0258] In step (2a), the after-treatment product (N) is then applied, preferably immediately after rinsing out the colorant and thus on hair that is still wet or towel-damp.

[0259] The action of the post-treatment agent (N) in step (2b) can, for example, take place for a period of 10 seconds to 20 minutes.

[0260] Following step (2b), the keratin fibers are dried in step (3) without prior rinsing of the after-treatment agent (N).

[0261] The after-treatment agent (N) is preferably applied as a leave-on product, with the hair still coated with the after-treatment agent (N) drying either at room temperature or with the aid of an external heat source such as a hair dryer or a straightening iron. During drying, the hair can be heated, for example, to a temperature of 37 to 220°C, preferably 40 to 180°C, more preferably 45 to 150°C, and most preferably 48 to 90°C.

[0262] In a further particularly preferred embodiment, a device according to the invention is characterized by the

[0263] (3) Drying the keratin fibers at a temperature of 37 to 220°C, preferably 40 to 180°C, more preferably 45 to 150°C, and particularly preferably 48 to 90°C without prior rinsing of the after-treatment agent (N). When applied as a leave-on product, the after-treatment agent (N) remains on the hair during drying, so that the exposure time of the after-treatment agent (N) and the drying time of the hair can overlap.

[0264] Examples

[0265] 1 . Formulations

[0266] The following formulations were prepared (all data in wt.% unless otherwise stated)

[0267] 2. Application

[0268] Hair strands (Kerling, type "Euronatur-haar white") were colorimetrically measured. Ready-to-use dye F was applied to the hair strands (liquor ratio: 1 g of dye per 1 g of hair strand) and left on for three minutes. The hair strands were then thoroughly rinsed with water (1 minute). Immediately afterward, after-treatment product (N) was applied to the freshly colored, still-damp strands (liquor ratio: 0.5 g of after-treatment product per 1 g of hair) and left on for five minutes. Using a hairdryer, the strands still coated with after-treatment product (N) were then dried at a temperature of 60°C and then colorimetrically measured again.

[0269] To measure washfastness, the strands were then washed 3 times and 10 times, respectively. For each wash, a commercially available shampoo (0.25 g of Schauma 7 Herbs shampoo per 1 g of hair) was applied to the strand and massaged in with the fingers for 30 seconds. The shampoo was then rinsed out under lukewarm running water for 1 minute, and the strand was dried. The previously described process corresponds to one wash. The process was repeated for each subsequent wash. The hair washed in this way was colorimetrically measured.

[0270] The dyed strands used for comparison were colorimetrically measured without post-treatment and used in the washfastness tests.

[0271] The dE value used to assess color retention is calculated from the L*a*b* color values ​​measured on the respective strand as follows: dE = [ (Li - Lo) 2 + (a> - a0) 2 + (bi - bo)] 1 / 2

[0272] Lo, ao and bo = measurements of the uncolored strand

[0273] Li, ai and bi = measured values ​​of the dyed or dyed and washed strand

[0274] The lower the dE value, the smaller the color difference between the uncolored and colored (or colored and washed) hair. The higher the dE value, the higher the color intensity compared to the uncolored strand.

[0275] The dL value used to assess the brightness is calculated from the L value measured on the respective strand as follows: dL = [(Li - Lo) 2 ] 1 / 2

[0276] Lo = measured value of the uncolored strand

[0277] Li = measured value of the dyed or dyed and washed strand

[0278] The higher the dL value, the greater the difference in brightness compared to the uncolored strand.

[0279] The following color results were obtained

[0280] Immediately after coloring (0 hair washes), the comparison strand and the treated strand had essentially the same color difference to the uncolored hair, i.e. both strands were colored with the same high color intensity.

[0281] However, after 3 washes and after 10 washes, the treated hair strands had a significantly greater color difference to the uncolored hair, which means that the washfastness of the colored strands could be massively improved by the post-treatment with silsesquioxane (n1).

[0282] Immediately after coloring (0 hair washes), the comparison strand and the treated strand had essentially the same brightness difference to the uncolored hair.

[0283] However, after three and ten washes, the treated strand showed a significantly greater difference in brightness compared to the uncolored hair. The improvement in washfastness of the colored strand due to the post-treatment with silsesquioxane (n1) was therefore also reflected in the dL values.

Claims

Patent claims 1. Method for dyeing keratinous fibers, especially human hair, comprising the (1) Application of a dye (F) to the keratinous fibers which contains (f1) at least one amino-functionalized silicone polymer, and (f2) at least one pigment, and the (2) Application of a post-treatment agent (N) to the keratinous fibers, which contains (n1) at least one silsesquioxane, wherein the silsesquioxane (n1) is different from the amino-functionalized silicone polymer (f1).

2. Method according to claim 1, characterized in that the dye (F) contains at least one amino-functionalized silicone polymer (f1) comprising at least one structural unit of the formula (Si-Amino), -Amino) where ALK1 and ALK2 independently represent a linear or branched, divalent C1-C2o alkylene group.

3. Method according to one of claims 1 to 2, characterized in that the dye (F) contains at least one amino-functionalized silicone polymer (f1) comprising structural units of formula (Si-I) and formula (Si-Il) A method according to any one of claims 1 to 3, characterized in that the dye (F) contains, based on the total weight of the dye (F), one or more amino-functionalized silicone polymers (f1) in a total amount of 0.1 to 20 wt.%, preferably 0.2 to 10 wt.%, more preferably 0.3 to 5 wt.%, even more preferably 0.4 to 3.5 wt.%, and most preferably 0.5 to 2.0 wt.%. A method according to any one of claims 1 to 4, characterized in that the dye (F) contains at least one inorganic pigment (f2), wherein the inorganic pigment is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or colored pigments based on mica or micaceous oxide, which are coated with at least one metal oxide and / or one metal oxychloride.A method according to any one of claims 1 to 5, characterized in that the coloring agent (F) contains at least one organic pigment (f2), wherein the organic pigment is preferably selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, and orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470. A method according to any one of claims 1 to 6, characterized in that the dye (F) contains at least one pigment (f2) selected from the group consisting of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet, and vacuum metallized pigments. A method according to any one of claims 1 to 7, characterized in that the dye (F) contains, based on the total weight of the dye (F), one or more pigments (f2) 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.%. A method according to any one of claims 1 to 8, characterized by the (2) Application of a post-treatment agent (N) containing at least one silsesquioxane (n1) with at least one epoxy group. Method according to any one of claims 1 to 9, characterized by the (2) Application of a post-treatment agent (N) containing at least one silsesquioxane (n1) comprising at least one Si-X structural unit, where X represents a grouping of formula (N1), where n represents an integer from 0 to 6, preferably the numbers 2 or 3, and m represents an integer from 0 to 10, preferably the numbers 0 or 1. A method according to any one of claims 1 to 10, characterized by the (2) Application of a post-treatment agent (N) containing at least one silsesquioxane (n1) of formula (N-Il), wherein each residue R is chosen independently of the other residues R in the formula (N-Il), and wherein R represents a hydrogen atom, a Ci-Ce alkoxy group, a Ci-Ce alkyl group, a C2-C6 alkenyl group, a halogen Ci-Ce alkyl group, a hydroxy Ci-Ce alkyl group, a hydroxy group or a structural unit of the formula (Nl). Method according to claim 11, characterized by the (2) Application of a post-treatment agent (N) containing at least one silsesquioxane (n1) of formula (N-Il), wherein at least one of the R groups represents a structural unit of formula (Nl). Method according to one of claims 1 to 12, characterized in that the post-treatment agent (N) - based on the total weight of the post-treatment agent - contains one or more silsequioxanes (n1) in a total amount of 0.01 to 10.0 wt.%, preferably 0.05 to 5.0 wt.% and particularly preferably 0.1 to 1.5 wt.%. Method according to any one of claims 1 to 13, comprising the (1) Application of the dye (F) to the keratinous fibers in a first step, then the (2) Application of the post-treatment agent (N) to the keratinous fibers in a second step, wherein there is a period of at most 72 hours, preferably at most 48 hours, more preferably at most 24 hours and most particularly at most 2 hours between steps (1) and (2). The method of claim 14, comprising the (3) Drying the keratin fibers at a temperature of 37 to 220 °C, preferably from 40 to 180 °C, more preferably from 45 to 150 °C and particularly preferably from 48 to 90 °C without prior washing out of the post-treatment agent (N).

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