Improved performance of pigment-based colorants through application of pretreatment agents

Abstract

The present invention relates to a method for dyeing keratinous materials, particularly human hair, comprising the steps of applying to the keratinous materials a pretreatment agent (V) comprising (V-1) at least one anionic surfactant in an aqueous carrier, and applying to the keratinous materials a dye (F) comprising at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2). The present invention also relates to a multi-component packaging unit containing the two dyes (V) and (F) manufactured in two separate containers.

Description

[Technical Field]

[0001] The subject of the present application is a method for dyeing keratinous materials, in particular human hair, which comprises applying at least two different agents (V) and (F). The agent (V) represents a pre-treatment agent comprising at least one anionic surfactant in a water-containing carrier. The coloring agent (F) comprises at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2).

[0002] A second subject of the present application is a multi-component packaging unit (kit) for dyeing keratinous materials, in particular human hair, comprising two agents (V) and (F) separately contained in two different containers. [Background technology]

[0003] Changing the shape and color of keratin fibers, especially hair, is an important area of ​​modern cosmetics. To change hair color, experts know a variety of coloring systems depending on the coloring requirements. For long-lasting, intense dyeing with good fastness and good gray coverage, oxidation dyes are usually used. Such dyes usually contain an oxidation dye precursor (a so-called developer) and a color-developing component, which, under the influence of an oxidizing agent such as hydrogen peroxide, react with each other to produce the actual dye. Oxidation dyes are characterized by very long-lasting dyeing results.

[0004] When using direct dyes, the already prepared dye diffuses from the colorant into the hair fiber. Compared to oxidative dyes, dyes obtained with direct dyes have a shorter color retention time and are more quickly washable. Direct dye stains usually remain on the hair for 5 to 20 washes.

[0005] The use of color pigments to change the color of hair and / or skin for a short period of time is known. Color pigments are understood to be insoluble coloring substances. They exist in the dye composition as small particles without dissolving and are exclusively attached externally to the surface of hair fibers and / or skin. Therefore, color pigments can usually be removed without residue by washing several times with detergents containing surfactants. Various products of this type are commercially available under the name "hair mascara."

[0006] If a user desires particularly long-lasting coloring, the use of oxidative dyes has been the only option to date. However, despite numerous optimization attempts, the unpleasant ammonia or amine odor has not been completely avoided in oxidative hair dyes. Hair damage associated with the use of oxidative dyes also adversely affects the user's hair. Therefore, a continuing challenge is the search for alternative, high-performance dyeing methods. One viable alternative coloring method that has recently gained increasing attention is based on the use of color pigments.

[0007] Coloring with pigments has several important advantages. Since the pigments are only attached externally to the keratin material, especially to the hair fiber, the damage associated with the coloring process is particularly low. Furthermore, unwanted coloring can be removed quickly and easily without leaving any residue, allowing the user to quickly restore their original hair color without any hassle. This coloring method is therefore particularly attractive, especially for consumers who do not want to change their hair color regularly.

[0008] Recent research has addressed the problem of low durability in this dyeing method. In this regard, it has been found that the washfastness of the coloring results obtained with pigments can be improved by combining them with certain amino-functionalized silicone polymers. Furthermore, by selecting particularly suitable pigments and pigment concentrations on black hair, it has been possible to achieve even lighter color results, which until now have only been possible with oxidative hair treatments (bleaching agents).

[0009] However, in addition to these many advantages, pigment-based coloring methods still have some drawbacks. Because both the pigment and the aminosilicone that immobilizes the pigment are deposited on the surface of the hair fiber, achieving a uniform coloring result depends heavily on the surface structure of the hair being colored. Research conducted in this context has shown that even substances still present on the hair surface during coloring can have a very strong impact on the quality of the subsequent coloring result. For example, those who previously treated their hair with conditioner or styling products obtained colorings with low intensity and very uneven color fading. Without being committed to this theory, it is possible that various ingredients contained in care and / or styling products accumulate in certain areas of the hair and prevent the formation of a uniform colored film during the subsequent coloring process.

[0010] Users desire intense coloration with good uniformity and high reproducibility, and therefore coloring methods where the coloring result depends on the type and amount of other cosmetics that may have been applied first are very unappealing to users. Summary of the Invention [Problem to be solved by the invention]

[0011] The objective of the present application is to find a pigment-based dyeing method that can achieve strong dyeing with good reproducibility. Keratin materials or hair dyed in this way should produce the exact shade and color intensity expected by the user after reading the relevant packaging information or instructions for use, regardless of the hair type or previous use of other cosmetics. The coloring should be characterized by a high degree of uniformity and leveling, even if care or styling products have been used beforehand. [Means for solving the problem]

[0012] Surprisingly, it has been found that this problem can be successfully solved by dyeing keratinous materials, particularly hair, using a two-stage process in which at least two agents (V) and (F) are applied to the keratinous material (keratinous fibers such as hair). Here, agent (V) is a pretreatment agent containing at least one anionic surfactant (V-1) in an aqueous or water-containing carrier. The pretreatment agent (V) is applied to the keratinous material before applying the actual colorant (F), allowed to act, and then rinsed off again, if necessary. After applying the pretreatment agent (V), the actual colorant (F) is applied to the keratinous material to effect dyeing. The colorant (F) is characterized by the inclusion of at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2).

[0013] A first subject of the present invention is a method for coloring keratinous materials, in particular human hair, comprising the following steps: A step of applying a pretreatment agent (V) to keratinous materials; wherein the pretreatment agent is present in a water-containing carrier, (V-1) at least one anionic surfactant; and applying a coloring agent (F) to the keratin material; Here, the colorant is (F-1) at least one amino-functionalized silicone polymer, and (F-2) comprises at least one pigment; The method includes:

[0014] In the research leading to the present invention, it was shown that a particularly intense and uniform coloring result can be obtained on the hair when the hair is colored by successive application of the two agents (V) and (F). Surprisingly, the intensity and uniformity of the coloring result was not affected by the prior application of a conditioner or styling agent. DETAILED DESCRIPTION OF THE INVENTION

[0015] <Keratin substance> Keratinous materials include hair, skin, nails (e.g., fingernails and / or toenails). Wool, fur, and feathers are also included within the definition of keratinous materials.

[0016] Preferably, keratinous materials are understood to be human hair, human skin and human nails (in particular fingernails and toenails). Keratinous materials are understood to be human hair.

[0017] <Coloring agent> The term "colorant" is used in the present invention to refer to the coloring of keratinous materials, in particular hair, brought about by using pigments, which are deposited as colored compounds on the surface of the keratinous materials, in particular in the form of a homogeneous, uniform and smooth film. <Pretreatment agent (V)>

[0018] In the method of the present invention, the pretreatment agent (V) is applied to the keratinous material, the keratinous fibers, before applying the coloring agent (F).

[0019] The pretreatment agent (V) is characterized by containing at least one anionic surfactant (V-1) in an aqueous carrier or a water-containing carrier. <Water content of pretreatment agent>

[0020] The pretreatment agent (V) comprises an anionic surfactant (V-1) in an aqueous or water-containing carrier. Preferably, the pretreatment agent (V) has a high water content. Particularly suitable for use in the method according to the invention are pretreatment agents (V) containing 50.0 to 98.0% by weight, preferably 60.0 to 90.0% by weight, more preferably 70.0 to 90.0% by weight, and very particularly preferably 75.0 to 90.0% by weight, of water, based on the total weight of the pretreatment agent (V).

[0021] In one embodiment, the method according to the present invention is characterized in that the pretreatment agent (V) contains 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 % of water based on the total weight of the pretreatment agent (V).

[0022] <Anionic surfactant in pretreatment agent (V-1)> As an essential component, the pretreatment agent according to the present invention contains at least one anionic surfactant (V-1).

[0023] The term surfactant (T) refers to surface-active substances that can form adsorbed layers at surfaces and interfaces or aggregate in the bulk phase to form micellar colloids or lyotropic mesophases. They are classified into anionic surfactants, which consist of a hydrophobic group and a negatively charged hydrophilic head group; amphoteric or zwitterionic surfactants, which have both a negative and a counter-balancing positive charge; cationic surfactants, which have a hydrophilic group with a positive charge in addition to the hydrophobic group; and nonionic surfactants, which are uncharged but are highly hydrated in aqueous solution and have a strong dipole moment.

[0024] It has been found that certain anionic surfactants (V-1) are particularly suitable for achieving intense, uniform and reproducible coloring results in the subsequent application of the colorant (F) according to the invention.

[0025] Suitable anionic surfactants (V-1) that can be used in the agents of the present invention include: Linear and branched fatty acids (soaps) with 8 to 30 carbon atoms, ·Formula RO-(CH2-CH2O) x -CH2-COOH: ether carboxylic acids of the formula, wherein R is a linear or branched, saturated or unsaturated alkyl group having 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, Acyl isethionates with 8 to 24 carbon atoms in the acyl group, sulfosuccinic acid mono- and / or dialkyl esters having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, α-olefin sulfonates having 8 to 24 carbon atoms, ·Formula R-(OCH2-CH2) x -OSO3 - X + : alkyl sulfates and / or alkyl polyglycol ether sulfates of the formula (wherein R is preferably a linear or branched, saturated or unsaturated alkyl group having 8 to 30 carbon atoms, x=0 or 1 to 12, and X is an alkali metal or ammonium ion); sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds, Esters of tartaric and citric acid with alcohols, which are addition products of approximately 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8-22 C atoms. ·formula: TIFF0007746265000001.tif2465[in the formula, R 1 is preferably an aliphatic hydrocarbon group having 8 to 30 carbon atoms, and R 2 is hydrogen, the group (CH2CH2O) n R 1 or X, n is 0 to 10, and X is hydrogen, an alkali metal, an alkaline earth metal, or NR 3 R 4 R 5 R 6 , (where R 3 ~R 6 are each independently a C1-C4 hydrocarbon group. Alkyl and / or alkenyl ether phosphates of

[0026] Formula (T-1): TIFF0007746265000002.tif26150[In the formula, R1 is a linear or branched, saturated or unsaturated C8-C 30 represents an alkyl group, x represents an integer from 0 to 50, M is a hydrogen atom, ammonium (NH4) + , or the equivalent of a monovalent or polyvalent cation]. Very particularly satisfactory results were obtained when at least one anionic surfactant (V-1) of the formula (I) was used in the pretreatment agent (V).

[0027] In a very particularly preferred embodiment, the method of the present invention comprises the step of: (V-1) Formula (T-1): TIFF0007746265000003.tif26150[In the formula, R1 is a linear or branched, saturated or unsaturated C8-C 30 represents an alkyl group, x represents an integer of 0 to 50; M is a hydrogen atom, ammonium (NH4) + , or the equivalent of a monovalent or polyvalent cation.] The method is characterized by including at least one anionic surfactant.

[0028] The group R1 represents the hydrophobic part of the anionic surfactant and is a linear or branched, saturated or unsaturated C8-C 30 Represents an alkyl group, wherein the group is an unsaturated C8-C 30 When representing an alkyl group, the alkyl group can be mono- or polyunsaturated.

[0029] Preferably, the group R1 is a linear, saturated or unsaturated C8-C 30 Alkyl groups, very preferably the group R1, are linear, saturated or unsaturated C 12 -C 22 Obviously, the radical R1 is a linear, saturated or unsaturated C 12 -C 18 represents R for the alkyl group.

[0030] Saturated linear C8-C 30 Examples of alkyl groups are lauryl, myristyl, cetyl, stearyl, and behenyl groups.

[0031] The index x indicates the number of ethylene oxide groups contained in the anionic surfactant. When x is 0, the anionic surfactant of formula (T-1) has no ethylene oxide units, and in this case, an alkyl sulfate or alkyl sulfate salt is present.

[0032] Examples of alkyl sulfates are sodium lauryl sulfate and sodium myristyl sulfate.

[0033] Preferably, x represents an integer of 0 to 5, and particularly preferably, x represents an integer of 1 to 5.

[0034] The group M is a hydrogen atom, ammonium (NH4) + , or the equivalent of a monovalent or polyvalent cation.

[0035] When M represents a hydrogen atom, the anionic surfactant exists in the form of a protonated (and ethoxylated) sulfate ester. In aqueous solution, the protonated form is in equilibrium with the deprotonated form, which carries an anionic charge. Therefore, the protonated compound of formula (I) is also classified as an anionic surfactant.

[0036] M is ammonium (NH4) + or a monovalent or polyvalent cation equivalent, the anionic surfactant of formula (I) exists in the form of its salt. Wherein the presence of the corresponding monovalent or polyvalent cation equivalent ensures the electroneutrality of the anionic surfactant. Preferably, M represents a monovalent cation, in particular a sodium or potassium cation.

[0037] In a very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) is a linear, saturated or unsaturated C 12 -C 18The method is characterized in that the surfactant (V-1) contains at least one anionic surfactant of formula (T-1), wherein X is an alkyl group, X is an integer of 0 to 5, preferably an integer of 1 to 5, and M is a hydrogen atom or an alkali metal cation, preferably a sodium cation or a potassium cation.

[0038] Particularly preferred anionic surfactants of formula (I) are commercially available, for example, from BASF under the trade name Texapon NSO BZ (BZ = preserved with benzoic acid) and the INCI name sodium laureth sulfate, which has the CAS number 68891-38-3.

[0039] To ensure particularly good coloring results using the method of the present invention, the pretreatment agent preferably contains one or more anionic surfactants (V-1) in a specific amount range. Particularly strong and uniform coloring can be obtained when the pretreatment agent (V) contains one or more anionic surfactants (V-1) in a total amount of 2.0 to 18.0 wt %, preferably 4.0 to 16.0 wt %, more preferably 6.0 to 14.0 wt %, and most preferably 8.0 to 12.0 wt %, based on the total weight of the pretreatment agent.

[0040] In a very particularly preferred embodiment, the method according to the invention is characterized in that the pretreatment agent (V) comprises one or more anionic surfactants (V-1) in a total amount of 2.0 to 18.0 wt. %, preferably 4.0 to 16.0 wt. %, more preferably 6.0 to 14.0 wt. %, and most preferably 8.0 to 12.0 wt. %, based on the total weight of the pretreatment agent.

[0041] <Zwitterionic surfactants and / or amphoteric surfactants in the pretreatment agent> When the pretreatment agent (V) contains not only at least one anionic surfactant (V-1) but also at least one zwitterionic surfactant and / or amphoteric surfactant, the coloring effect achievable by the method of the present invention can be further improved in terms of intensity, uniformity, and reproducibility.

[0042] In a very particularly preferred embodiment, the process according to the invention comprises the steps of: (V-2) At least one zwitterionic surfactant and / or amphoteric surfactant The method is characterized by comprising:

[0043] Very particularly suitable zwitterionic surfactants (V-2) may be selected from the compounds of the following formulae (T-2), (T-3), (T-4) and / or (T-5): TIFF0007746265000004.tif45155 TIFF0007746265000005.tif38150 TIFF0007746265000006.tif38150 TIFF0007746265000007.tif45150[In the formula, R2, R3, R4 and R5 each independently represent a hydrophobic group of the surfactant. R2, R3, R4 and R5 are independently linear or branched, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 12 -C 18 represents an alkyl group]

[0044] The zwitterionic surfactants of formula (T-2), (T-3), (T-4) and / or (T-5) each have, in addition to two methyl groups, a cationic charge in the form of a quaternary nitrogen atom, each containing an R group and further a group with acid functionality. This cationic charge is obtained by deprotonation. Chemical Carboxylic or sulfonic acids It can be It is neutralized by the acid functionality.

[0045] In a very particularly preferred embodiment, the process according to the invention comprises the step of: (V-2) Formula (T-2), (T-3), (T-4) and / or (T-5): TIFF0007746265000008.tif45150 TIFF0007746265000009.tif38150 TIFF0007746265000010.tif38150 TIFF0007746265000011.tif45150 wherein R2, R3, R4, and R5 are independently straight or branched chain, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 12 -C 18 represents an alkyl group.] and wherein the zwitterionic surfactant is selected from the group consisting of:

[0046] The group R2 is a linear or branched, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 11 -C 21 Alkyl groups, very particularly preferably linear, saturated or unsaturated C 11 -C 17 represents an alkyl group.

[0047] The group R3 is a linear or branched, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 11 -C 21 Alkyl groups, very particularly preferably linear, saturated or unsaturated C 11 -C 17 represents an alkyl group.

[0048] The group R4 is a linear or branched, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 12 -C 18 represents an alkyl group.

[0049] The group R5 is a linear or branched, saturated or unsaturated C8-C 30 Alkyl groups, preferably linear, saturated or unsaturated C 12 -C 18 represents an alkyl group.

[0050] Particularly suitable zwitterionic surfactants of formula (T-2) are alkylamidoalkyl betaines. Particularly suitable amphoteric surfactants include those known by the INCI name Cocamidopropyl betaine and the INCI name Cocamidopropyl betaine.

[0051] Particularly suitable zwitterionic surfactants of formula (T-3) are, for example, 12 -C 14 It is an alkyldimethylbetaine, which is available in the form of the commercial product Genagen KB from Global Amines (formerly Clariant) under the INCI name cocobetaine. The CAS number for cocobetaine is 66455-29-6.

[0052] In particular, zwitterionic surfactants of formula (T-2) and (T-4) have been shown to be particularly well suited to solving the problems in the present invention.

[0053] In a further very particularly preferred embodiment, the process according to the invention comprises the steps of: (V-2) at least one zwitterionic surfactant selected from surfactants of formula (T-2) and / or (T-4) The method is characterized by comprising:

[0054] To achieve particularly good dyeing results using the method of the present invention, the pretreatment agent preferably contains one or more amphoteric or zwitterionic surfactants (V-2) in a specific amount range. Particularly strong and uniform coloring can be obtained when the pretreatment agent (V) contains one or more zwitterionic surfactants (V-2) in a total amount of 0.5 to 8.5 wt %, preferably 1.0 to 7.5 wt %, more preferably 1.5 to 6.5 wt %, and most preferably 2.0 to 4.5 wt %, based on the total weight of the pretreatment agent.

[0055] In a very particularly preferred embodiment, the method of the present invention is characterized in that the pretreatment agent (V) comprises one or more zwitterionic and / or amphoteric surfactants (V-2) in a total amount of 0.5 to 8.5 wt. %, preferably 1.0 to 7.5 wt. %, more preferably 1.5 to 6.5 wt. %, and most preferably 2.0 to 4.5 wt. %, based on the total weight of the pretreatment agent.

[0056] <Colorant (F)> According to the method of the present invention, following application of the pretreatment agent (V), a colorant (F) is then applied to the keratinous material. The colorant (F) comprises at least one amino-functionalized silicone polymer (F-1) and at least one pigment (F-2).

[0057] <Amino-functionalized silicone polymer (F-1) in colorant (F)> As the first essential component (F-1) of the present invention, the colorant (F) comprises at least one amino-functionalized silicone polymer, alternatively referred to as aminosilicone or amodimethicone.

[0058] Silicone polymers are macromolecules comprising repeating organic units and having 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.

[0059] The maximum molecular weight of a silicone polymer depends on the degree of polymerization (number of monomers being polymerized) and batch size, and is determined in part by the polymerization method. For purposes of this invention, it is considered that a silicone polymer has a maximum molecular weight of 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferably g / mol or less.

[0060] Silicone polymers contain many Si-O repeating units, and the Si atoms may carry organic groups, such as alkyl or substituted alkyl groups. Silicone polymers are therefore also called polydimethylsiloxanes.

[0061] The silicone polymer, depending on its high molecular weight, is based on more than 10 Si-O repeating units, preferably more than 50 Si-O repeating units, more preferably more than 100 Si-O repeating units, and most preferably more than 500 Si-O repeating units.

[0062] Amino-functionalized silicone polymer is understood to be a functionalized silicone that contains at least one structural unit with amino group.Preferably, amino-functionalized silicone polymer has a plurality of structural units, each of which has at least one amino group.Amino group is understood to mean primary amino group, secondary amino group and tertiary amino group.All of these amino groups can be protonated in acidic environment and exist in cationic form.

[0063] Basically, when the amino-functionalized silicone polymer (F-1) has at least one primary amino group, at least one secondary amino group and / or at least one tertiary amino group, the amino-functionalized silicone polymer (F-1) can produce beneficial effects.However, when the amino-functionalized silicone polymer (F-1) having at least one secondary amino group is used in the colorant (F), the most washing fastness dyeing can be obtained.

[0064] In a very particularly preferred embodiment, the method according to the invention is characterized in that the colorant (F) comprises at least one amino-functionalized silicone polymer (F-1) having at least one secondary amino group.

[0065] The secondary amino group can be present in various positions in the amino-functionalized silicone polymer. Particularly beneficial results were observed when an amino-functionalized silicone polymer (F-1) having at least one, and preferably a plurality of, structural units represented by TIFF0007746265000012.tif7674 was used.

[0066] In the structural unit of formula (Si-amino), the abbreviations ALK1 and ALK2 independently represent linear or branched divalent C1-C 20 Represents an alkylene group.

[0067] In another very particularly preferred embodiment, the process according to the invention comprises the step of: TIFF0007746265000013.tif7674 wherein ALK1 and ALK2 are independently straight or branched chain divalent C1-C 20 represents an alkylene group] The composition is characterized in that it comprises at least one amino-functionalized silicone polymer (F-1) containing at least one structural unit represented by the formula:

[0068] Positions marked with an asterisk (*) indicate a bond to another structural unit of the silicone polymer. For example, the silicon atom adjacent to the asterisk may be bonded to another oxygen atom, which in turn may be bonded to another silicon atom or even to a C1-C6 alkyl group.

[0069] Alternatively, bivalent C1-C 20 The alkylene group is a divalent C-C 20 They are sometimes referred to as alkylene groups, which means that each ALK1 and ALK2 group can form two bonds.

[0070] In the case of ALK1, one bond occurs from the silicon atom to the ALK1 group, and a second bond exists between the ALK1 and the secondary amino group.

[0071] In the case of ALK2, there is one bond from the secondary amino group to the ALK2 group and a second bond between ALK2 and the primary amino group.

[0072] Straight chain divalent C1-C 20 Examples of alkylene groups include methylene (-CH-), ethylene (-CH-CH-), propylene (-CH-CH-CH-), and butylene (-CH-CH-CH-CH-). Propylene (-CH-CH-CH-) is particularly preferred. From a chain length of three carbon atoms, the divalent alkylene group may be branched. Branched-chain divalent C-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0073] In another particularly preferred embodiment, the structural unit represented by the formula (Si-amino) represents a repeating unit in the amino-functionalized silicone polymer (F-1), such that the silicone polymer comprises a plurality of structural units represented by the formula (Si-amino).

[0074] Particularly suitable amino-functionalized silicone polymers (F-1) having at least one secondary amino group are listed below.

[0075] In the method of the present invention, a structural unit represented by formula (Si-I) and a structural unit represented by formula (Si-II): At least one amino-functionalized silicone polymer (F-1) containing TIFF0007746265000014.tif80142 coloring agent Dyeings with the best washfastness were obtained when (F) was applied to keratinous materials.

[0076] In another very particularly preferred embodiment, the process according to the invention is characterized in that the colorant (F) comprises a structural unit of formula (Si-I) and a structural unit of formula (Si-II): TIFF0007746265000015.tif80142.

[0077] A corresponding amino-functionalized silicone polymer having the structural units of formula (Si-I) and formula (Si-II) is, for example, the commercial product DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is sold by Dow Chemical Company under the name "Siloxanes and Silicones, 3-[(2-aminoethyl)amino]-2-methylpropyl Me, Di-Me-Siloxane" and has the CAS number 106842-44-8.

[0078] In another preferred embodiment, the method of the present invention comprises the step of reacting a compound of formula (Si-III): JPEG0007746265000016.jpg51111[In the formula, m and n are numbers selected so 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 are the same or different and are hydroxyl groups or C 1-4 represents an alkoxy group, where at least one of R1 to R3 represents a hydroxy group. The method is characterized by applying to keratinous materials a colorant (F) comprising at least one amino-functional silicone polymer (F-1) represented by the formula:

[0079] Another preferred method of the present invention is a method for producing a compound of formula (Si-IV): JPEG0007746265000017.jpg66150[in formula p and q are numbers chosen so 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 are different and are hydroxyl groups or C 1-4 represents an alkoxy group, and at least one of R1 and R2 represents a hydroxy group. The method is characterized by applying to a keratinous substance a colorant (F) comprising at least one amino-functional silicone polymer (F-1) represented by the formula:

[0080] The silicones represented by formula (Si-III) and formula (Si-IV) differ in the group at the Si atom that has the nitrogen-containing group. In formula (Si-III), R2 is a hydroxy group or C 1-4 The groups in formula (Si-III) and formula (Si-IV) are alkoxy groups, while the groups in formula (Si-IV) are methyl groups. The individual Si groups designated by the subscripts m and n or p and q do not necessarily exist as blocks; rather, the individual units may be present in a statistically distributed manner. That is, in formula (Si-III) and formula (Si-IV), not all R-Si(CH) groups are necessarily bonded to -[O-Si(CH)] groups.

[0081] Also, the formula (Si-V): TIFF0007746265000018.tif54114 [In the formula, A represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3; b, n, and c represent integers of 0 to 1000; For more information n>0 and b+c>0 At least one of the conditions A = -OH or D = -H is met. It has also been found that the method of the invention, in which a colorant (F) comprising at least one amino-functional silicone polymer (F-1) of the formula: is applied to keratin fibers, is particularly effective in terms of the desired effect.

[0082] In the above formula (Si-V), the individual siloxane units with the subscripts b, c and n are statistically distributed, ie, they are not necessarily block copolymers.

[0083] The colorant (F) is represented by the formula (Si-VI): TIFF0007746265000019.tif1092 [wherein R is a hydrocarbon or hydrocarbon group having 1 to about 6 carbon atoms, and Q is a group of the general formula -R 1 HZ (where R 1 is a divalent linking group to which a group Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogen atoms and hydrogen are bonded, and Z is an organic amino functional group containing at least one amino functional group; a is a number ranging from about 0 to about 2, b is a number ranging from about 1 to about 3, a+b is 3 or less, c is a number ranging from about 1 to about 3, x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, y is a number ranging from 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 known in the art, preferably trimethylsiloxy. The composition may further comprise one or more of various amino-functionalized silicone polymers of the formula:

[0084] Non-limiting examples of groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, and isohexyl; alkenyl groups such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, and alkylallyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl; phenyl and benzyl groups; halohydrocarbon groups such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, and chlorophenyl; and sulfur-containing groups such as mercaptoethyl, mercaptopropyl, mercaptohexyl, and mercaptophenyl. Preferably, R is an alkyl group having from 1 to about 6 carbon atoms, and most preferably, R is methyl. R 1 Examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CHCH(CH)CH-, phenylene, naphthylene, -CHCHSCHCH-, -CHCHOCH-, -OCHCH-, -OCHCHCH-, -CHCH(CH)C(O)OCH-, -(CH)CC(O)OCHCH-, -CHCH-, -CHCHCH-; and -(CH)C(O)SCHCH-.

[0085] Z is an organic amino functional group containing at least one amino functional group. One formula for Z is NH(CH) z NH, where z is 1 or greater. Another formula for Z is -NH(CH). z (CH2) zz NH, where z and zz are both independently 1 or greater, and this structure includes a diamino ring structure such as piperazinyl. Z is most preferably a -NHCHCHNH group. Another formula for Z is -N(CH) z (CH2) zz NX2 or -NX2, wherein each X in X2 is independently hydrogen and C 1-12 alkyl groups, and zz is 0.

[0086] Q is most preferably a polar amino functional group of the formula -CH2CH2CH2NHCH2CH2NH2, where a ranges from about 0 to about 2, b ranges from about 2 to about 3, a+b is less than or equal to 3, and c ranges from about 1 to about 3. R a Q b SiO (4-a-b) / 2 Units and R c SiO (4-c) / 2 The molar ratio of the units ranges from 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 more than one silicone of the above formula is used, the various variable substituents in the above formula may be different for the various silicone components present in the silicone mixture.

[0087] In a particularly preferred embodiment, the method of the present invention comprises the step of reacting a compound of formula (Si-VII): TIFF0007746265000020.tif11142[In the formula, ·G is -H, phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-CH2CH2CH3, -CH2CH2CH3, -O-CH(CH3)2, -CH(CH3)2, -O-CH2CH2 CH2CH3, -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, especially 0, ·b represents a number between 0 and 1, especially 1, m and n are numbers such that the sum (m+n) is between 1 and 2000, preferably between 50 and 150, n preferably takes a value between 0 and 1999 and between 49 and 149, and m preferably takes a value between 1 and 2000 and between 1 and 10, R' is QN(R'')-CH2-CH2-N(R'')2 QN(R'')2 QN + (R'')3A- QN + H(R'')2A - QN + H2(R'')A - QN(R'')-CH2-CH2-N + R''H2A - [Here, each Q is a chemical bond, -CH2-, -CH2-CH2-, -CH2CH2CH2-, C(CH3)2-, -CH2CH2CH2CH2-, -CH2C(CH3)2-, or -CH(CH3)CH2CH2-; R'' is -H, -phenyl, -benzyl, CH2-CH(CH3)Ph, C 1-20 represent the same or different alkyl groups, preferably selected from the group consisting of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, A represents an anion preferably selected from chloride, bromide, iodide or methosulfate. is a monovalent group selected from The method is characterized by applying an amino-functional silicone polymer (F) represented by the formula:

[0088] In a particularly preferred embodiment, the method of the present invention comprises the step of reacting a compound of formula (Si-VIIa): TIFF0007746265000021.tif21123 [wherein m and n are numbers such that the sum (m+n) is between 1 and 2000, preferably between 50 and 150, n preferably takes a value between 0 and 1999 and between 49 and 149, and m preferably takes a value between 1 and 2000 and between 1 and 10] The method is characterized by applying to a keratinous substance a colorant (F) comprising at least one amino-functional silicone polymer (F-1) represented by the formula:

[0089] In their INCI name, these silicones are called trimethylsilylamodimethicones.

[0090] In another preferred embodiment, the method of the present invention provides a compound of formula (Si-VIIb): TIFF0007746265000022.tif21111 [wherein R represents an -OH, -O-CH3 or -CH3 group; m, n1, and n2 are numbers such that the sum (m+n1+n2) is between 1 and 2000, preferably between 50 and 150, the sum (n1+n2) preferably having a value between 0 and 1999 and between 49 and 149, and m preferably having a value between 1 and 2000 and between 1 and 10. The method is characterized by applying to keratinous materials a colorant (F) comprising at least one amino-functional silicone polymer represented by the formula:

[0091] In INCI name, these amino-functionalized silicone polymers are called amodimethicones.

[0092] Regardless of which amino-functional silicone is used, the colorant (F) according to the present invention preferably comprises an amino-functional silicone polymer having an amine value of more than 0.25 meq / g, preferably more than 0.3 meq / g, more preferably more than 0.4 meq / g. The amine value represents the milliequivalent of amine per gram of amino-functional silicone. The amine value can be measured by titration and is expressed in mg KOH / g.

[0093] Additionally, colorants (F) containing specific 4-morpholinomethyl-substituted silicone polymers (F-1) are also suitable for use in the method of the present invention. These amino-functionalized silicone polymers contain structural units represented by formula (Si-VIII) and structural units represented by formula (Si-IX). TIFF0007746265000023.tif49139

[0094] The corresponding 4-morpholinomethyl substituted silicone polymer is shown below. The corresponding amino-functionalized silicone polymer is known under the name amodimethicone / morpholinomethylsilsesquioxane copolymer and is commercially available in the form of the raw material Belsil ADM 8301 E from Wacker.

[0095] 4-morpholinomethyl-substituted silicones include, for example, those represented by the formulae (Si-VIII), (Si-IX) and (Si-X): TIFF0007746265000024.tif63145 [In the formula, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 is -CH3, -OH, or -OCH3. Silicones having structural units represented by the following formula can be used.

[0096] A particularly preferred colorant (F) in the present invention is a colorant represented by the formula (Si-XI): TIFF0007746265000025.tif66155[In the formula, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 is -CH3, -OH or -OCH3; B represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3; a, b, and c independently represent integers from 0 to 1000, provided that a+b+c>0; m and n each independently represent an integer of 1 to 1000; however, At least one of the conditions B = -OH or D = -H is met, The units a, b, c, m and n are statistically distributed or block-like in the molecule. The silicone compound contains at least one 4-morpholinomethyl-substituted silicone represented by the formula:

[0097] In structural formula (Si-XI), it is intended to indicate that the siloxane groups n and m are not necessarily directly bonded to the terminal groups B or D, respectively. Rather, in preferred formula (Si-VI), a > 0 or b > 0, and in particularly preferred formula (Si-VI), a > 0 and c > 0, i.e., the terminal groups B or D are preferably bonded to dimethylsiloxy groups. Also, in formula (Si-VI), the siloxane units a, b, c, m, and n are preferably statistically distributed.

[0098] The silicones of formula (Si-VI) used in accordance with the present invention may be trimethylsilyl terminated (D or B = -Si(CH3)3), but may also be dimethylsilylhydroxy terminated at both ends, or dimethylsilylhydroxy terminated and dimethylsilylmethoxy terminated at one end. Particularly preferred silicones in the present invention are those in which, in each relation, B=-O-Si(CH3)2OH and D=-Si(CH3)3 B=-O-Si(CH3)2OH and D=-Si(CH3)2OH B=-O-Si(CH3)2OH and D=-Si(CH3)2OCH3 B=-O-Si(CH3)3 and D=-Si(CH3)2OH B=-O-Si(CH3)2OCH3 and D=-Si(CH3)2OH These silicones provide a significant improvement in the hair properties of hair treated with the agent of the present invention and significantly improved protection in oxidative treatments.

[0099] It has been found to be particularly advantageous when the colorant of the present invention contains an amino-functionalized silicone polymer (F-1) in a specific range of amount: Particularly satisfactory results have been obtained when the colorant contains one or more amino-functionalized silicone polymers (F-1) 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 colorant.

[0100] Within the scope of another particularly preferred embodiment, the method of the invention is characterized in that the colorant (F) comprises one or more amino-functionalized silicone polymers (F-1) in a total amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.3 to 3.0% by weight, and very particularly preferably 0.4 to 2.5% by weight, based on the total weight of the colorant.

[0101] <Pigment (F-2) in Colorant (F)> As a second essential component of the present invention, the colorant (F) used in the method of the present invention comprises at least one pigment.

[0102] A pigment within the meaning of the present invention is a coloring compound having a solubility in water of less than 0.5 g / L, preferably less than 0.1 g / L, and more preferably less than 0.05 g / L at 25°C. Water solubility can be measured, for example, by the following method: 0.5 g of pigment is weighed into a beaker. A magnetic stirring bar is added. 1 L of distilled water is then added. The mixture is heated at 25°C for 1 hour while stirring with a magnetic stirrer. If undissolved pigment components are visible in the mixture after this time, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated due to the high strength of the finely dispersed pigment, the mixture is filtered. If undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0103] Suitable color pigments may be of inorganic and / or organic origin.

[0104] In a preferred embodiment, the agent (F) according to the invention is characterized in that it contains at least one coloring compound (F-2) selected from the group consisting of inorganic pigments and / or organic pigments.

[0105] In a preferred embodiment, the colorant (F) in the present invention is characterized by containing at least one inorganic pigment and / or organic pigment (F-2).

[0106] Preferred color pigments are selected from synthetic or natural inorganic pigments. Naturally occurring inorganic color pigments can be prepared, for example, from chalk, ochre, umber, green earth, calcined sienna, or graphite. Also usable as inorganic color pigments are black pigments such as black iron oxide, colored pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments.

[0107] Particularly suitable are colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfates, complex metal cyanides, metal sulfates, chromates and / or molybdates. Preferred colored 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 sulfosilicate, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), Prussian blue (iron ferrocyanide, CI 77510) and / or carmine (cochineal).

[0108] In the present invention, colored pearlescent pigments are also particularly preferred color pigments. They are usually mica and / or mica-based, and may be coated with one or more metal oxides. Mica belongs to the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, sodalite, biotite, lepidolite, and margarite. To prepare pearlescent pigments combined with metal oxides, mica, such as muscovite or phlogopite, is coated with metal oxide.

[0109] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can be used as pearlescent pigments. Particularly preferred pearlescent pigments are based on natural or synthetic mica and coated with one or more of the above-mentioned metal oxides. By varying the thickness of the metal oxide layer, the color of the respective pigment can be changed.

[0110] In another preferred embodiment, the method of the invention is characterized in that the colorant (F) comprises at least one coloring compound (F-2) from the group of inorganic pigments, preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfates, complex metal cyanides, metal sulfates, bronze pigments, and / or from colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0111] In another preferred embodiment, the composition according to the invention is characterized in that it comprises at least one coloring compound (F-2) from the group of pigments selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxides (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or Prussian blue (iron ferrocyanide, CI 77510).

[0112] Examples of particularly suitable color pigments are commercially available from Merck under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron®, from Sensient under the trade names Ariabel® and Unipure®, from Eckart Cosmetic Colors under the trade name Prestige® and from Sunstar under the trade name Sunshine®.

[0113] Particularly preferred color pigments under the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxide) Colorona Passion Orange, Merck, Mica, CI77491 (Iron Oxide), 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 oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxide), 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 Oxide) 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 Green) 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 Oxide (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 Oxide) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxide) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxide) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxide) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxide), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxide, 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 Oxide) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides)

[0114] Other particularly preferred color pigments under the trade name Xirona® are, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0115] Other particularly preferred color pigments under the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI77499 (iron oxide), silica Unipure Yellow LC 182 EM, Sensient, CI77492 (iron oxide), silica

[0116] In another embodiment, the composition according to the invention may also contain one or more coloring compounds (F-2) from the group consisting of (a) organic pigments.

[0117] Organic pigments in the context of the present invention are correspondingly insoluble organic dyes or color lacquers which may be selected, for example, from the group consisting of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, perinone, perylene, diketo-pyrrolopyrrole, indigo, thioindigo, dioxazine and / or triarylmethane compounds.

[0118] Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI42090, CI69800, CI69825, CI73000, CI74100, CI74160, yellow pigments with a color index of CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005, green pigments with a color index of CI61565, CI61570, CI74260, and orange pigments with color indexes CI11725, CI15510, CI45370, CI71105, and red pigments with color indexes CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915 and / or CI75470.

[0119] In another particularly preferred embodiment, the method of the present invention is characterized in that the colorant (F) is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a Color Index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a Color Index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a Color Index of CI 61565, CI 61570, CI 74260, green pigments with a Color Index of CI 11725, CI 15510, CI45370, CI71105, orange pigments with a color index of CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915 and / or CI75470.

[0120] The organic pigment may be a color paint. In the sense of the present invention, the term "color lacquer" refers to particles comprising a layer of absorbed dye, and the particles and dye units are insoluble under the above conditions. The particles may be, for example, inorganic materials, such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or aluminum.

[0121] For example, alizarin color varnish can be used.

[0122] For excellent lightfastness and temperature resistance, it is particularly preferred to use the above pigments in the colorant (F) of the method of the present invention. It is also preferred that the pigments used have a specific particle size. Thus, in the present invention, at least one pigment has an average particle size D of 1.0 to 50 μm, preferably 5.0 to 45 μm, more preferably 10 to 40 μm, and even 14 to 30 μm.50 It is advantageous to have an average particle size D 50 can be measured, for example, using dynamic light scattering (DLS).

[0123] The pigment (F-2) constitutes the second essential component of the colorant of the present invention and is preferably used in the agent in an amount within a specific range. Particularly satisfactory results have been obtained when the colorant contains one or more pigments (F-2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight, and most preferably 0.25 to 1.5% by weight, based on the total weight of the colorant.

[0124] In another very particularly preferred embodiment, the method according to the invention is characterized in that the colorant (F) comprises one or more pigments (F-2) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.2 to 2.5% by weight, particularly preferably 0.25 to 1.5% by weight, based on the total weight of the colorant.

[0125] As an optional component, the coloring agent (F) used in the method of the present invention may contain one or more direct dyes. Direct-acting dyes are dyes that act directly on hair and do not require an oxidation step to form color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0126] Direct dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 0.5 g / L and are therefore not considered pigments. Preferably, direct dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 1.0 g / L.

[0127] Direct dyes can be classified into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0128] In another preferred embodiment, the method of the present invention is characterized in that the colorant (F) further comprises an anionic direct dye, a nonionic direct dye and a cationic direct dye.

[0129] Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, HC Blue 16, Basic Violet 2, 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.

[0130] As non-ionic direct dyes, non-ionic nitro and quinone dyes and natural azo dyes can be used. Suitable non-ionic direct dyes are those described under the following international names or trade names: 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 known compounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)-aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2 -nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0131] In the course of the research leading to the present invention, it was found that dyeings with good color strength and fastness properties can also be produced when using an agent (F) comprising at least one anionic direct dye (F-2).

[0132] Therefore, in a further embodiment, the process according to the invention is characterized in that the colorant (F) comprises at least one anionic direct dye.

[0133] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms of the carboxylic acid or sulfonic acid groups (-COOH, -SO3H) can be converted to their deprotonated forms (-COO - , -SO3 - The proportion of the protonated form increases with decreasing pH. When direct dyes are used as their salts, the carboxylic acid or sulfonic acid groups are present in deprotonated form and are neutralized with the corresponding stoichiometrically equivalent cation to maintain electrical neutrality. The acid dyes of the present invention can also be used in the form of their sodium salts and / or potassium salts.

[0134] Acid dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 0.5 g / L and are therefore not considered pigments. Preferably, acid dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 1.0 g / L.

[0135] Alkaline earth salts (e.g., calcium and magnesium salts) or aluminum salts of acid dyes often have lower solubilities than the corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25°C, 760 mmHg), they are not included in the definition of direct dyes.

[0136] An essential feature of acid dyes is their ability to form an anionic charge, the resulting carboxylic or sulfonic acid group usually being attached to a variety of chromophore systems, such as those found in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0137] In another embodiment, the method for coloring keratin materials is characterized in that the dyeing component (F) comprises 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, each dye from the above group having at least one carboxylic acid group (-COOH), sodium carboxylate group (-COONa), potassium carboxylate group (-COOK), sulfonic acid group (-SO3H), sodium sulfonate group (-SO3Na) and / or potassium sulfonate group (-SO3K).

[0138] For example, suitable acid dyes include 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 no. B001), Acid Yellow 3 (COLIPA no. 54, D&C Yellow No. 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA no. 29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85 E102 (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 no. 015), 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; KATSU 201; sodium salt-free; Brown No. 201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D&C Brown No. 1), Acid Red 14 (CI 14720), Acid Red 18 (E124, Red18; CI16255), Acid Red 27 (E123, CI16185, C-Rot46, Real red D, FD&C Red Nr.2, Food Red 9, Naphthol red S), Acid Red 33 (Red33, Fuchsia Red, D&C Red33, CI17200), Acid Red 35 (CI C.I.18065)、Acid Red 51(CI45430、Pyrosin B、Tetraiodofluorescein、Eosin J、Iodeosin)、Acid Red 52(CI45100、Food Red106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red 73(CI27290)、Acid Red 87(Eosin、CI45380)、Acid Red 92(COLIPA n°53、CI 45410)、Acid Red 95(CI45425、Erythtosine,Simacid Erythrosine Y)、Acid Red 184(CI15685)、Acid Red 195、Acid Violet 43(Jarocol Violet 43、Ext.D&C Violet n°2、C.I.60730、COLIPA n°063)、Acid Violet 49(CI42640)、Acid Violet 50(CI50325)、Acid Blue 1(Patent Blue、CI42045)、Acid Blue 3(Patent Blue V、CI42051)、Acid Blue 7(CI42080)、Acid Blue 104(CI42735)、Acid Blue 9(E133、Patent blue AE、Amido blue AE、Erioglaucin A、CI42090、C.I.Food Blue 2)、Acid Blue 62(CI62045)、Acid Blue 74(E132、CI73015)、Acid Blue 80(CI61585)、Acid Green 3(CI42085、Foodgreen1)、Acid Green 5(CI42095)、Acid Green 9(C.I.42100)、Acid Green 22(C.I.42170)、Acid Green 25(CI61570、Japan Green 201、D&C Green No.5)、Acid Green 50(Brilliant Acid Green BS、C.I.44090, Acid Brilliant Green BS, E142), Acid Black 1(Black n°401, Naphthalene Black 10B, Amido Black 10B, CI20470, COLIPA n°B15), Acid Black 52(CI15711), Food Yellow 8(CI14270), 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. .

[0139] For example, the water solubility of an anionic direct dye can be measured as follows: 0.1 g of anionic direct dye is introduced into a beaker. A magnetic stir bar is added. 100 mL of water is then added. The mixture is heated to 25°C while stirring magnetically. Stir for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residues are still present, increase the amount of water, for example, in 10 mL increments. Add water until the amount of dye used is completely dissolved. If the dye strength is too high to visually evaluate the dye-water mixture, filter the mixture. If undissolved dye remains on the filter paper, repeat the solubility test with more water. If 0.1 g of anionic direct dye dissolves in 100 mL of water at 25°C, the solubility of the dye is 1.0 g / L.

[0140] Acid Yellow 1 is referred to as 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water (25° C.) of at least 40 g / L. Acid Yellow 3 is a mixture of the mono- and disulfonic acid sodium salts of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a solubility in water (25° C.) of 20 g / L. Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, and its solubility in water is greater than 40 g / L (25°C). 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 highly soluble in water at 25°C. Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its solubility in water is greater than 7 g / L at 25 °C. Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has very high water solubility of greater than 20% by weight. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate, and its solubility in water is 2.5 g / L (25° C.). Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, and its solubility in water is greater than 10 g / L (25° C.). 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 solubility in water of greater than 20% by weight (25°C).

[0141] Thus, in another embodiment, the method according to the present invention is characterized in that the colorant (F) is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 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.

[0142] The direct dyes can be used in various amounts in the colorant (F) depending on the desired color intensity. Particularly satisfactory results have been obtained when the colorant (F) contains one or more direct dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight, and very particularly preferably 0.5 to 4.5% by weight, based on the total weight of said colorant (F).

[0143] The colorant (F) may also contain at least one photochromic dye or thermochromic dye as the coloring compound (F-2).

[0144] Photochromic dyes are dyes that undergo a reversible change in hue in response to irradiation with UV light (sunlight or black light). In this process, UV light modifies the chemical structure of the dye, resulting in a change in the dye's absorption behavior (photochromy).

[0145] Thermochromic dyes are dyes that undergo a reversible change in hue in response to temperature changes. During this process, the chemical structure of the dye changes with temperature, resulting in a change in the dye's absorption behavior (thermochromism).

[0146] The colorant (F) may contain one or more photochromic dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight, and most preferably 0.5 to 4.5% by weight, based on the total weight of the colorant (F).

[0147] The colorant (F) may contain one or more thermochromic dyes (b) in a total amount of 0.01 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.2 to 6.0% by weight, and most preferably 0.5 to 4.5% by weight, based on the total weight of the colorant (F).

[0148] <Further optional components in agent (V) and / or agent (F)> In addition to the components essential to the present invention already described, the pretreatment agent (V) and / or the colorant (F) may also contain other optional components.

[0149] The agent may also contain other active ingredients, auxiliaries and additives, such as solvents, C8-C 30 Fatty alcohols, C8-C 30 Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30 fatty components such as fatty acid diglycerides and / or hydrocarbons; polymers, structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example lecithin and cephalin; perfume oils, dimethyl isosorbide and cyclodextrin; fibre structure improving active ingredients, in particular mono-, di- and oligosaccharides, for example glucose, galactose, fructose, fructose and lactose; dyes for colouring the formulation; anti-dandruff active ingredients, for example piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and / or plant origin and fatty acid condensates or optionally in the form of anionic or cationically modified derivatives; vegetable oils; light stabilizers and UV blockers; active ingredients, for example panthenol, Pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and its salts, bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarin, 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 paraffin; swelling agents and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea, primary, secondary and tertiary phosphates; opacifying agents, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlizing agents, such as ethylene glycol mono- and and distearate and PEG-3-distearate; and blowing agents such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0150] The selection of these other substances will be made by those skilled in the art depending on the desired properties of the agent. Other optional ingredients and the amounts of such ingredients to be used are specified in the relevant manuals known to those skilled in the art. The additional active ingredients and auxiliary agents are preferably used in the preparations of the present invention in amounts of 0.0001 to 25% by weight and 0.0005 to 15% by weight, respectively, based on the total weight of each agent.

[0151] However, the purpose of the pretreatment agent (V) is to remove any material deposited on the surface of the keratinous materials by the previous application of a conditioner or styling agent. It is believed that polymers and / or cationic surfactants, due to their high affinity for keratinous materials, may adversely affect subsequently applied pigment colorants.

[0152] For this reason, it is particularly preferred that the pretreatment agent (V) according to the present invention does not contain polymers and cationic surfactants, or that the amounts thereof be minimized.

[0153] In a further preferred embodiment, the process according to the invention is characterized in that the total content of all polymers contained in pretreatment agent (V) is less than 0.5 wt.-%, preferably less than 0.1 wt.-%, very preferably less than 0.01 wt.-%, based on the total weight of said pretreatment agent.

[0154] In a further preferred embodiment, the method according to the invention is characterized in that the total content of all cationic surfactants contained in the pretreatment agent (V) is less than 0.5 wt. %, preferably less than 0.1 wt. %, and very preferably less than 0.01 wt. %, based on the total weight of the pretreatment agent.

[0155] <pH value of pretreatment agent (V) and / or colorant (F)> The pH values ​​of the agents (V) and (F) according to the invention can be adjusted to a slightly acidic to alkaline pH.

[0156] In one embodiment, the pretreatment agent (V) has a pH of 2.0 to 6.5, preferably 2.5 to 6.0, more preferably 3.0 to 5.5, and most preferably 3.5 to 5.0. When the pretreatment agent (V) having these pH values ​​was used by the method of the present invention, coloring of particularly high color intensity could be obtained.

[0157] In another embodiment, the pretreatment agent (V) has a pH of 7.0 to 11.5, preferably 7.5 to 11.0, and most preferably 8.0 to 10.5. When the pretreatment agent (V) having these pH values ​​was used according to the method of the present invention, particularly good uniform coloring could be obtained.

[0158] The pH value of the colorant (F) according to the present invention can be adjusted to a slightly acidic to alkaline pH. Highly preferably, the colorant (F) has a pH in the range of 5.0 to 10.0, preferably 6.0 to 9.5, more preferably 6.0 to 8.7, and most preferably 6.0 to 7.5.

[0159] Alkalizing and acidifying agents known to those skilled in the art can be used to set the desired pH value, respectively. For purposes of the present invention, the pH value is measured at a temperature of 22°C.

[0160] As an alkalizing agent, the agent may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0161] The alkanolamine that can be used in the agent of the present invention is preferably selected from the primary amine that has the C2-C6 alkyl base with at least one hydroxyl group.Preferred alkanolamine is selected from the group formed by 2-aminoethan-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, 2-amino-2-methylpropan-1,3-diol.

[0162] Particularly preferred alkanolamines according to the invention are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.Accordingly, a particularly preferred embodiment is characterized in that the agent according to the invention comprises an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol as alkalizing agent.

[0163] For the purposes of the present invention, an amino acid is an organic compound containing at least one protonatable amino group and at least one -COOH or -SOH group in its structure. Preferred amino acids are aminocarboxylic acids, particularly α-(alpha)aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0164] According to the present invention, a basic amino acid is an amino acid with an isoelectric point pI greater than 7.0.

[0165] Basic α-aminocarboxylic acid comprises at least one asymmetric carbon atom.In the context of the present invention, any enantiomer can be equally used as specific compound or their mixture, especially as racemate.However, it is particularly advantageous to use the naturally preferred isomer form, usually L-configuration.

[0166] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. Thus, in another particularly preferred embodiment, the agent of the present invention is characterized in that the alkalizing agent is a basic amino acid from the group of arginine, lysine, ornithine and / or histidine.

[0167] Furthermore, the product may contain other alkalizing agents, in particular inorganic alkalizing agents, which may be used in the present invention, preferably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0168] In the present invention, the desired pH value can be adjusted by a buffer system. A buffer solution or buffer system is generally understood to be a mixture of a weak or medium-strength acid (e.g., acetic acid) and a completely dissociated neutral salt of the acid (e.g., sodium acetate). When some base or acid is added, the pH value hardly changes (buffering). The effect of the buffer substance contained in the buffer solution is caused by the dissociation equilibrium of the weak acid or weak base. due to hydrogen ions or weak acids or bases by forming water Based on the oxidation reaction of oxide ions.

[0169] The buffer system may be formed from a mixture of an inorganic or organic acid and the corresponding salt of the acid.

[0170] Acids can be buffered with all salts of weak acids and strong bases, and bases can be buffered with salts of strong acids and weak bases. Strong hydrochloric acid (completely dissociated into ions) can be buffered by adding, for example, sodium acetate. According to the equilibrium, TIFF0007746265000026.tif8150 Hydrochloric acid is converted by sodium acetate to weak acetic acid, forming sodium chloride, which dissociates only slightly in the presence of excess sodium acetate. An effective buffer for both acids and bases is a mixture of a weak acid and its salt.

[0171] Examples of buffer systems known from the literature are acetic acid / sodium acetate, boric acid / sodium borate, phosphoric acid / sodium phosphate, and bicarbonate / sodium carbonate.

[0172] The pH of the agent of the present 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.

[0173] For the purposes of this invention, an organic buffer system is understood to be a mixture of an organic acid and its conjugate base, where the organic acid radical means that the conjugate base of the organic acid is also organic, and the cations present to neutralize the acidic anionic charge can be inorganic or organic.

[0174] Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid (H3PO4), etc. Phosphoric acid is a medium-strength acid and is particularly preferred.

[0175] A particularly suitable inorganic acid is potassium dihydrogen phosphate. Potassium dihydrogen phosphate has the molecular formula KH2PO4 and CAS number 7778-77-0. It has a molar mass of 136.09 g / mol. It is very soluble in water (222 g / L at 20°C) and reacts acidically in water. A 5% aqueous solution of potassium dihydrogen phosphate has a pH of 4.4.

[0176] Another particularly preferred inorganic acid is sodium dihydrogen phosphate. Sodium dihydrogen phosphate has the molecular formula NaH2PO4 and CAS numbers 7558-80-7 (anhydrous), 10049-21-5 (monohydrate), and 13472-35-0 (dihydrate). Anhydrous sodium dihydrogen phosphate has a molar mass of 119.98 g / mol. Sodium dihydrogen phosphate reacts acidically in aqueous solution.

[0177] A particularly preferred salt of the two acids is dipotassium hydrogen phosphate. Dipotassium hydrogen phosphate has the molecular formula KHPO and 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.

[0178] Also, a particularly preferred salt of the two acids is disodium hydrogen phosphate. Disodium hydrogen phosphate has the molecular formula NaHPO and 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.

[0179] Examples of organic acids include citric acid, succinic acid, tartaric acid, lactic acid, acetic acid, malic acid, malonic acid, and maleic acid.

[0180] Examples of the corresponding salts of these organic acids include sodium and potassium salts of citric acid, sodium and potassium salts of succinic acid, sodium and potassium salts of tartaric acid, sodium and potassium salts of lactic acid, sodium and potassium salts of acetic acid, sodium and potassium salts of malic acid, sodium and potassium salts of malonic acid, and sodium and potassium salts of maleic acid.

[0181] <Order of Method Steps> As mentioned above, the pretreatment agent (V) is applied before the application of the coloring agent (F). In this context, it has proven particularly advantageous to apply the pretreatment agent (V) to the keratinous materials, leave it to act for a specific time, and then rinse it off again with water.

[0182] Another subject matter is therefore a method for coloring keratin fibers, in particular human hair, comprising the following steps: (1) applying a pretreatment agent (V) to keratin fibers (the pretreatment agent (V) is disclosed in detail in the description of the first subject of the present invention); (2) exposing the keratin fibers to the pretreatment agent applied in step (1); (3) Rinse off the pre-treatment agent with water (4) applying a coloring agent (F) to the keratin fibers (said coloring agent is disclosed in detail in the description of the first subject of the present invention); (5) exposing the keratin fibers to the colorant applied in step (4); and (6) With water coloring agent Rinse off the The method includes:

[0183] Expressly quite particularly preferred is a method for coloring keratin fibers, in particular human hair, which comprises the following steps in the indicated order: (1) applying a pretreatment agent (V) to keratin fibers (the pretreatment agent (V) is disclosed in detail in the description of the first subject of the present invention); (2) exposing the keratin fibers to the pretreatment agent applied in step (1); (3) A step of rinsing the pretreatment agent with water; (4) applying a coloring agent (F) to the keratin fibers (the coloring agent is disclosed in detail in the description of the first subject of the present invention); (5) exposing the keratin fibers to the colorant applied in step (4); and (6) With water coloring agent Rinse off the The method includes:

[0184] In step (1) of the method according to the present invention, a pretreatment agent (V) comprising at least one anionic surfactant in a water-containing carrier is applied to the hair.

[0185] In the next step, the previously applied pretreatment agent (V) is allowed to act on the keratin fibers. In this context, different exposure times are possible, for example, from 30 seconds to 60 minutes. Exposure times of 30 seconds to 5 minutes are preferred.

[0186] Following the action of the pre-treatment agent (V) on the keratin fibers, in step (3), the pre-treatment agent is finally rinsed off with water. In a preferred embodiment, the pre-treatment agent (V) is rinsed off with water alone, i.e., without using a post-treatment agent or shampoo other than those according to the present invention.

[0187] In principle, the user can freely choose the application period of the two agents (V) and (F).

[0188] However, the coloring agent (F) must be applied to the keratinous material or hair after rinsing off the pretreatment agent (V). For this reason, in the present invention, it is essential that no other agents, such as conditioners or styling agents, be applied between the application of the two agents (V) and (F). Thus, the maximum time interval between the application of the two agents (V) and (F) is usually limited to a maximum of 24 hours.

[0189] It has been found to be advantageous to have a period of at most 24 hours, preferably at most 12 hours, more preferably at most 6 hours, and very particularly preferably at most 3 hours between rinsing off the pretreatment agent (V) with water and applying the colorant (F) to the keratin fibers.

[0190] In a further preferred embodiment, the process according to the invention is characterized in that between step (3) and step (4) there is a period of at most 24 hours, preferably at most 12 hours, even more preferably at most 6 hours, very particularly preferably at most 3 hours.

[0191] In a further preferred embodiment, the method according to the invention is characterized in that step (4) is carried out directly after step (3). Step (4) is used to apply a colorant.

[0192] The exposure of the keratin fibers to the colorant (F) in step (5) can be, for example, for a period ranging from 15 seconds to 30 minutes, preferably for a period ranging from 30 seconds to 15 minutes, and more preferably for a period ranging from 1 to 15 minutes.

[0193] Thereafter, in step (6), the colorant (F) is finally rinsed off with water. In a preferred embodiment, the colorant (F) is rinsed off with water alone, i.e., without using any post-treatment agent or shampoo other than those according to the present invention.

[0194] <Multi-component packaging unit> For user convenience, the user is preferably provided with all necessary agents in a multi-component packaged unit (kit).

[0195] Another subject of the present invention is therefore a multi-component packaging unit (kit) for dyeing keratinous materials, comprising separately prepared: a first container containing a pretreatment agent (V), said pretreatment agent (V) being disclosed in detail in the description of the first subject of the invention, and a second container containing a colorant (F), said colorant (F) being disclosed in detail in the description of the first subject of the invention, A multi-component packaging unit comprising:

[0196] With respect to further preferred embodiments of the multi-component packaging unit according to the invention, the same applies mutatis mutandis to the method of the invention. [Example]

[0197] 1. Preparation The following formulations were prepared (all data in % by weight unless otherwise stated):

[0198] [Table 1]

[0199] [Table 2]

[0200] [Table 3]

[0201] 2. Apply to hair strands First, the hair tresses (Kerling) were treated with conditioner: for this purpose, the conditioner was applied to damp hair (0.2 g per gram of hair) and left to act for 5 minutes, after which it was rinsed with water.

[0202] Each pretreatment (V) was applied to a still damp hair tress. For this purpose, 0.2 g of pretreatment (V) per gram of hair was applied to each tress, massaged for 30 seconds, and then rinsed with water.

[0203] A control tress was treated directly with colorant (F) without the application of pre-treatment (V).

[0204] The colorant (F) was then applied directly to the still damp hair: for this purpose, 0.2 g of colorant (F) per gram of hair was massaged in and left to act for 5 minutes, after which the hair was rinsed again with water.

[0205] After treatment, the hair tresses were calorimetrically measured using a Data color Spectraflash 450 colorimeter.

[0206] The dE value used to assess apparent color intensity is derived from the L*a*b* colorimetric values ​​measured on each hair tress section as follows: TIFF0007746265000030.tif10155L0, a0 and b0 = Measurements of the reference hair strand L i , a i and b i = measured value of coloration obtained with the method according to the invention

[0207] [Table 4]

[0208] 3. Application at the hair studio In three subjects, the conditioner was applied first: for this purpose, the conditioner was applied to damp hair, left to act for 5 minutes, and then rinsed off with water.

[0209] Next, two types of pretreatment agents (V1) and (V2) were applied to the still-wet hair of two subjects, respectively, and then massaged in for 30 seconds, followed by rinsing with water.

[0210] Pretreatment agent (V) was not applied to any of the subjects.

[0211] Next, each subject coloring agent (F) was applied. coloring agent (F) was massaged into the hair for 5 minutes and then rinsed again with water.

[0212] The color intensity and uniformity were evaluated visually by an experienced person.

[0213] [Table 5] Preferred embodiments of the present specification include at least the following. [1] A method for dyeing keratinous materials, in particular human hair, comprising the steps of: a step of applying a pretreatment agent (V) to keratinous materials, wherein the pretreatment agent is present in a water-containing carrier and comprises (V-1) at least one anionic surfactant; and, A method comprising the step of applying a coloring agent (F) to a keratinous material, wherein said coloring agent comprises (F-1) at least one amino-functionalized silicone polymer and (F-2) at least one pigment. [2] The pretreatment agent (V) is (V-1) of formula (T-1): TIFF0007746265000033.tif26156 [In the formula, R 1 is a linear or branched, saturated or unsaturated C 8 -C 30 represents an alkyl group, x represents an integer of 0 to 50, M represents a hydrogen atom, ammonium (NH 4 ) + or its monovalent or polyvalent cation equivalent]. The method according to [1], characterized in that it comprises at least one anionic surfactant. [3] The pretreatment agent (V) is a linear, saturated or unsaturated C 12 -C 18 The method according to [2], characterized in that it comprises at least one anionic surfactant (V-1) of formula (T-1), wherein X is an alkyl group, X is an integer of 0 to 5, preferably an integer of 1 to 5, and M is a hydrogen atom or an alkali metal cation, preferably a sodium cation or a potassium cation. [4] The method according to any one of [1] to [3], wherein the pretreatment agent (V) contains one or more anionic surfactants (V-1) in a total amount of 2.0 to 18.0 wt %, preferably 4.0 to 16.0 wt %, more preferably 6.0 to 14.0 wt %, and most preferably 8.0 to 12.0 wt %, based on the total weight of the pretreatment agent. [5] The method according to any one of [1] to [4], wherein the pretreatment agent (V) contains (V-2) at least one zwitterionic surfactant and / or amphoteric surfactant. [6] The pretreatment agent (V) is (V-2) of the formula (T-2), (T-3), (T-4) and / or (T-5): TIFF0007746265000034.tif144133 [In the formula, R 2 、R 3 、R 4 、R 5 are independently linear or branched, saturated or unsaturated C 8 -C 30 Alkyl groups, preferably linear, saturated or unsaturated C 12 -C 18 represents an alkyl group] The method according to [5], characterized in that it contains at least one zwitterionic surfactant selected from the surfactants listed below. [7] The method according to any one of [1] to [6], wherein the pretreatment agent (V) contains one or more zwitterionic surfactants and / or amphoteric surfactants (V-2) in a total amount of 0.5 to 8.5 wt %, preferably 1.0 to 7.5 wt %, more preferably 1.5 to 6.5 wt %, and most preferably 2.0 to 4.5 wt %, based on the total weight of the pretreatment agent. [8] The method according to any one of [1] to [7], wherein the colorant (F) comprises at least one amino-functionalized silicone polymer (F-1) having at least one secondary amino group. [9] The colorant (F) has the formula (Si amino): TIFF0007746265000035.tif7674 wherein ALK1 and ALK2 are independently a linear or branched divalent C 1 -C 20 represents an alkylene group] The method according to any one of [1] to [8], characterized in that the method comprises at least one amino-functionalized silicone polymer (F-1) comprising at least one structural unit of the formula:

[10] The colorant (F) is represented by the formula (Si-I) and the formula (Si-II): TIFF0007746265000036.tif83156 The method according to any one of [1] to [9], characterized in that the method comprises at least one amino-functionalized silicone polymer (F-1) containing a structural unit of the formula:

[11] The method according to any one of [1] to

[10] , characterized in that the colorant (F) comprises one or more amino-functionalized silicone polymers (F-1) 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 very preferably 0.4 to 2.5 wt. %, based on the total weight of the colorant.

[12] The method according to any one of [1] to

[11] , characterized in that the colorant (F) comprises at least one inorganic pigment (F-2) preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfates, complex metal cyanides, metal sulfates, bronze pigments, and / or mica or mica-based colored pigments coated with at least one metal oxide and / or metal acid chloride.

[13] Colorant (F) is carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color indexes CI42090, CI69800, CI69825, CI73000, CI74100, CI74160, yellow pigments with color indexes CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005, green pigments with color indexes CI61565, CI61570, CI74260, orange pigments with color indexes CI11725, CI15510, CI45370, CI71105 The method according to any one of [1] to

[12] , characterized in that the method comprises at least one organic pigment (F-2), preferably selected from the group consisting of color pigments and red pigments having a color index of CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915 and / or CI75470.

[14] The method according to any one of [1] to

[13] , characterized in that the colorant (F) contains one or more pigments (F-2) in a total amount of 0.01 to 10.0 wt %, preferably 0.1 to 5.0 wt %, more preferably 0.2 to 2.5 wt %, and very preferably 0.25 to 1.5 wt %, based on the total weight of the colorant.

[15] A method for coloring keratin fibers, in particular human hair, comprising the following steps: (1) A step of applying the pretreatment agent (V) according to any one of [1] to [7] to keratin fibers. (2) exposing the keratin fibers to the pretreatment agent applied in step (1); (3) Rinse off the pre-treatment agent with water (4) A step of applying the colorant (F) described in [1] to

[14] to keratin fibers. (5) Exposing the keratin fibers to the colorant applied in step (4). (6) Rinse off the colorant with water A method comprising:

[16] The method according to

[15] , characterized in that the time between steps (3) and (4) is at most 24 hours, preferably at most 12 hours, more preferably at most 6 hours, and most preferably at most 3 hours.

[17] A kit for dyeing keratinous materials, comprising: a first container containing the pretreatment agent (V) according to any one of [1] to [7]; A second container containing the colorant (F) according to any one of [1] to

[14] . Includes a kit.

Claims

1. 1. A method for dyeing keratinous materials comprising the following steps in the order given: (1) a step of applying a pretreatment agent (V) to a keratin material, wherein the pretreatment agent (V) is present in a water-containing carrier and comprises (V-1) at least one anionic surfactant; (2) exposing the keratinous material to the pretreatment agent (V) applied in step (1); (3) a step of rinsing the pretreatment agent (V) with water; (4) applying a colorant (F) (excluding those containing tannins) to the keratin material, wherein the colorant (F) comprises (F-1) at least one amino-functionalized silicone polymer and (F-2) at least one pigment; (5) exposing the keratinous material to the colorant (F) applied in step (4); and (6) A step of rinsing off the colorant (F) with water Including, Here, (V-1) is represented by the formula (T-1): [In the formula, R １ is a linear or branched, saturated or unsaturated C ８ -C ３０ represents an alkyl group, x represents an integer of 0 to 50, M represents a hydrogen atom, ammonium (NH ４ ) ＋ or the equivalent of a monovalent or polyvalent cation] is an anionic surfactant represented by (F-1) is an amino-functionalized silicone polymer having at least one secondary amino group, No other steps are performed between steps (3) and (4), and the time between steps (3) and (4) is a maximum of 24 hours. method.

2. The pretreatment agent (V) is R １ is a linear, saturated or unsaturated C １２ -C １８ 2. The method according to claim 1, characterized in that it comprises at least one anionic surfactant (V-1) of formula (T-1), wherein x is an alkyl group, x is an integer from 0 to 5, and M represents a hydrogen atom or an alkali metal cation.

3. The method according to claim 1 or 2, wherein the pretreatment agent (V) comprises one or more anionic surfactants (V-1) in a total amount of 2.0 to 18.0 wt %, based on the total weight of the pretreatment agent.

4. The method according to any one of claims 1 to 3, wherein the pretreatment agent (V) comprises (V-2) at least one zwitterionic surfactant and / or amphoteric surfactant.

5. The pretreatment agent (V) is (V-2) a compound represented by the formula (T-2), (T-3), (T-4) and / or (T-5): [In the formula, R ２ , R ３ , R ４ , R ５ are independently straight or branched chain, saturated or unsaturated C ８ -C ３０ represents an alkyl group] 5. The method of claim 4, further comprising the step of:

6. The method according to any one of claims 1 to 5, wherein the pretreatment agent (V) comprises one or more zwitterionic surfactants and / or amphoteric surfactants (V-2) in a total amount of 0.5 to 8.5 wt%, based on the total weight of the pretreatment agent.

7. The colorant (F) has the formula (Si amino): wherein ALK1 and ALK2 are independently a linear or branched divalent C １ -C ２０ represents an alkylene group] 7. The method according to claim 1, further comprising the step of:

8. The colorant (F) is represented by the formula (Si-I) and the formula (Si-II):

8. The method according to claim 1, further comprising the step of:

9. 9. The method according to claim 1, wherein the colorant (F) comprises one or more amino-functionalized silicone polymers (F-1) in a total amount of 0.1 to 8.0 wt. %, based on the total weight of the colorant.

10. 10. The method according to claim 1, wherein the colorant (F) comprises at least one inorganic pigment (F-2) selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfates, complex metal cyanides, metal sulfates, bronze pigments, and / or mica or mica-based colored pigments coated with at least one metal oxide and / or metal oxychloride.

11. The colorant (F) is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color indexes of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, and CI 74160, yellow pigments with color indexes of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, and CI 47005, green pigments with color indexes of CI 61565, CI 61570, and CI 74260, and green pigments with color indexes of CI 11725, CI 15510, CI 45370, and CI 7110.

11. The method according to claim 1, characterized in that the pigment (F-1) contains at least one organic pigment selected from the group consisting of an orange pigment having a color index of 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.

12. 12. The method according to claim 1, wherein the colorant (F) comprises one or more pigments (F-2) in a total amount of 0.01 to 10.0 wt %, based on the total weight of the colorant.

13. A kit for dyeing keratinous materials, comprising separately packaged a first container containing the pretreatment agent (V) according to any one of claims 1 to 6; A second container containing the colorant (F) according to any one of claims 1 and 7 to 12. Including, A kit for use in the method according to any one of claims 1 to 12.

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